Coordination Chemistry Reviews 296 (2015) 91–124

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Coordination Chemistry Reviews

journal homepage: www.elsevier.com/locate/ccr

Review

Recent advances in synthetic methods and applications of colloidal

silver chalcogenide quantum dots
Rijun Gui a,∗ , Hui Jin a , Zonghua Wang a,∗ , Lianjiang Tan b
a
College of Chemical Science and Engineering, Collaborative Innovation Center for Marine Biomass Fiber, Materials and Textiles of Shandong Province,
Shandong Sino-Japanese Center for Collaborative Research of Carbon Nanomaterials, Laboratory of Fiber Materials and Modern Textiles, The Growing Base
for State Key Laboratory, Qingdao University, Qingdao, Shandong 266071, PR China
b
Shanghai Center for Systems Biomedicine, Key Laboratory of Systems Biomedicine, Ministry of Education, and Bio-ID Center, School of Biomedical
Engineering, Shanghai Jiao Tong University, Shanghai 200240, China

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 92
2. Development of silver chalcogenide QDs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 93
3. Methods for synthesizing silver chalcogenide QDs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 93
3.1. Synthesis of Ag2 S QDs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 94
3.1.1. Organic phase synthesis methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 94
3.1.2. Aqueous phase synthesis methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 96
3.1.3. Polar phase synthesis methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 99
3.1.4. Biomimetic synthesis methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 99
3.1.5. Cation-exchange synthesis methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 99
3.2. Synthesis of Ag2 Se QDs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 100
3.2.1. Organic phase synthesis methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 101
3.2.2. Aqueous phase synthesis methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 102
3.3. Synthesis of Ag2 Te QDs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 104
4. Applications of silver chalcogenide QDs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 104
4.1. Silver chalcogenide QDs for bioimaging . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 104
4.1.1. In vitro and in vivo imaging of silver chalcogenide QDs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 105
4.1.2. Toxicity assessment of silver chalcogenide QDs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 108
4.1.3. Bioimaging of Ag2 S QDs in drug delivery . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 112
4.2. Silver chalcogenide QDs for chemo-/bio-detection . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 112
4.3. Silver chalcogenide QDs in QDSSCs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 114
4.4. Silver chalcogenide QDs for photocatalysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 118
4.5. Silver chalcogenide QDs with antimicrobial and surface-enhanced Raman scattering (SERS) activities . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 119
4.6. Silver chalcogenide QDs as thermoelectric materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 121
5. Conclusions and outlooks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 121
Acknowledgments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 122
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 122

a r t i c l e i n f o a b s t r a c t

Article history: Narrow bandgap colloidal semiconductor nanocrystals have attracted increasing attention in recent years
Received 22 October 2014 and studies have demonstrated their significant applications in optics, electronics, biomedicine, mate-
Accepted 30 March 2015 rials science, and other areas. During the past decade, many studies have investigated colloidal silver
Available online 10 April 2015
chalcogenide (Ag2 X, X = S, Se, Te) quantum dots (QDs) due to their numerous advantages, such as near-
infrared (NIR) emission, ultralow toxicity, high photo-/colloidal stability, low cost, and facile synthesis.

∗ Corresponding authors. Tel.: +86 532 85950873; fax: +86 532 85950873.
E-mail addresses: guirijun@qdu.edu.cn (R. Gui), wangzonghua@qdu.edu.cn (Z. Wang).

http://dx.doi.org/10.1016/j.ccr.2015.03.023
0010-8545/© 2015 Elsevier B.V. All rights reserved.
92 R. Gui et al. / Coordination Chemistry Reviews 296 (2015) 91–124

Keywords: Compared with conventional NIR QDs (which contain heavy metal elements such as Cd, Hg, or Pb), NIR
Application emissive Ag2 X QDs avoid the intrinsic hazard of heavy metal ions and they have ultralow toxicity in
Photoluminescence biomedical applications. However, no previous review has summarized the synthetic methods and appli-
Quantum dot cations of Ag2 X QDs in a systematic manner. In this review, we discuss previously reported synthetic
Silver chalcogenide
methods and the advantages of directly synthesized and surface functionalized Ag2 X QDs, as well as
Synthesis
reporting their potential applications in bioimaging, chemo-/bio-detection, QD-sensitized solar cells, and
photocatalysis, as well as antimicrobials and thermoelectric materials. Recent methods for synthesizing
Ag2 X QDs are discussed in detail. The unique optoelectronic properties of Ag2 X QDs and their assemblies
make these QDs excellent materials for a broad range of applications, and thus their assemblies and prop-
erties are highlighted. Finally, we suggest the future exploration of highly efficient synthetic methods and
the potential application fields of Ag2 X QDs.
© 2015 Elsevier B.V. All rights reserved.

1. Introduction
In the past two decades, colloidal semiconductor nanocrystals
(NCs), also known as quantum dots (QDs), have represented one
of the major advances in materials science. Before 1998, QDs were
only considered as materials for photonics and electronics appli-
cations due to their unique optical and electronic properties. For
instance, QDs with multiple emissions and minimal spectral over-
lap can be excited by a single light source [1]. By changing their
size, shape, and composition, QDs can be manipulated to emit over
a broad range of wavelengths. These features favor their uses in
displays and in the optoelectronics fields. In 1998, QDs were first
employed as luminescent probes in the biomedical field by two
research groups [2,3]. Subsequently, considerable efforts have been
made to obtain high-quality QDs by optimizing synthesis methods,
functionalizing the surfaces of QDs to promote their biocompati-
bility, or coupling the QDs to targeting molecules (or therapeutic
agents) with complementary functions [4,5]. In the past decade,
most of these research areas have been pursued with the ultimate
goal of employing QDs in clinical settings [6], although there have
been increasing concerns about the potential hazards of QDs due
to their heavy-metal contents (e.g., Cd, Pb, and Hg) [7].
In recent years, attention has focused increasingly on narrow
bandgap QD materials that are active in the near-infrared (NIR)
region. QDs with NIR photoluminescence (PL) have attracted great
interest because of their high potential in biomedicine and energy
conversion [8]. The NIR region is widely considered to be a key diag-
nostic window for biomedical applications, such as in vitro (vivo)
imaging or tracking (to facilitate deep tissue imaging), diagnostics,
and photodynamic therapy [9–12]. In previous studies, the typical
NIR-emitting QDs mainly comprised CdTe, PbS, InAs, CdSe/ZnTe,
and CdHgTe QDs [13–17]. These QDs have narrow bandgaps, but
the intrinsic hazard of heavy metal ions limits their further appli-
cations in biosystems. Thus, CuInS2 and CuInGaSe NIR QDs with
lower toxicity have been synthesized in the organic phase, but
they require tedious synthetic procedures, harsh reaction condi-
tions, and post-treatments that entail ligand exchange and phase
transfer [18,19].
Compared with the optical imaging of cultured cells and live
animals in the traditional NIR (NIR-I, 700–950 nm) and visible
(450–700 nm) regions, PL in the second NIR (NIR-II, 1.0–1.4 ␮m)
region is optimal due to its much lower albedo and endogenous
autofluorescence, as well as its remarkably enhanced signal-to-
noise ratio [20,21]. During the past decade, NIR-II-emitting QDs
have been prepared and developed to facilitate in vivo imaging
applications. However, most of these QDs (such as PbS, PbSe, and
CdHgTe) are still affected by the potential problem of toxicity
[5,22–24]. By contrast, silver chalcogenide semiconductor NCs are
ideal materials for the preparation of low-toxicity NIR QDs. The
typical NCs have a narrow bandgap (0.9–1.1, 0.15, and 0.67 eV
for bulk Ag2 S, Ag2 Se, and Ag2 Te, respectively) [25–27] and they
have the potential for NIR-II PL emission. Compared with conven-
tional QDs that exhibit NIR emission, Ag-based binary NIR-emitting
QDs are more promising, especially in bioimaging applications
due to the absence of toxic components. In addition, the silver
chalcogenide NCs have ultralow solubility product constants (e.g.,
Ksp (Ag2 S) = 6.3 × 10−50 ; Ksp (Ag2 Se) = 2.0 × 10−64 ; correspondingly
Ksp (CdS) = 8.0 × 10−27 ; Ksp (CdSe) = 6.31 × 10−36 ), which enable the
minimal release of Ag ions into biosystems compared with the Cd-
based QDs utilized extensively in biomedical research [28].
For biomedical applications, the silver chalcogenide QDs (espe-
cially Ag2 S and Ag2 Se QDs with appropriate bandgaps) exhibit
excellent PL emissions, ranging from the NIR-I to NIR-II regions.
Ag2 Te QDs that usually emit in the infrared (IR) region (based on
their narrow bandgap) are applied in optoelectronics (e.g., IR lasers,
modulators, amplifiers), as solar cells with extended IR adsorption,
and as field effect transistor materials because of their excellent
thermoelectric properties [29]. However, although Ag2 Te QDs can
be used as fluorophores in biological tissue research, their biomed-
ical applications have been reported only rarely, which is probably
due to the relatively poor performance of Ag2 Te QDs in bioimag-
ing and chemo-/bio-sensing applications compared with similar
applications of Ag2 S and Ag2 Se QDs.
In recent years, colloidal silver chalcogenide (Ag2 X, X = S, Se,
and Te) QDs have been a hot topic in several excellent studies
[20,26,38,39,42–53], particularly in bioimaging applications. How-
ever, only one review has addressed Ag2 X QDs [54]. This review,
which was published in 2013, summarized the synthetic methods
and IR optical properties of metal chalcogenide QDs. In a broad
summary of metal chalcogenide QDs, this review only listed some
previous studies to give a brief introduction Ag2 X QDs, but with-
out providing a systematic classification of the different synthetic
methods and applications of Ag2 X QDs. According to our research,
the literature summarized in this previous review of the synthetic
methods and applications of Ag2 X QDs was not adequate, and thus
an imbalanced account of Ag2 X QDs was provided. In addition, this
review did not consider recent advances in the synthetic methods
and applications of photoluminescent silver chalcogenide QDs. In
the past decade, many studies have investigated NIR-emitting Ag2 X
QDs and related research has confirmed their significant poten-
tial, especially in biomedical applications. Thus, there is a need
for an overall review of recent developments in Ag2 X QDs (with
ultralow-toxicity and NIR emission) to facilitate further research.
Before we proceed with our review, we must mention sev-
eral previous reviews related to other NIR QDs. First, Rogach et al.
reviewed NIR-emitting semiconductor QDs for tumor imaging and
targeting, especially CdTe, CdTe/ZnS, and CdTe/CdSe QDs [55].
Gao et al. reviewed NIR QDs as optical probes for tumor imag-
ing by analyzing CdTe/ZnS, CdTe/CdSe, InAsx P1−x /InP/ZnSe, CuInSe,
and Cu:InP/ZnSe QDs [56]. Aswathy et al. reviewed NIR QDs for
 R. Gui et al. / Coordination Chemistry Reviews 296 (2015) 91–124
Scheme 1. The total architecture of this review involving synthetic methods (in
green fonts) and applications (in black fonts) of silver chalcogenide (Ag2 X, X = S, Se,
Te) quantum dots.
deep tissue imaging, including CdTeSe/CdS, InAs/ZnSe, CdTe/CdSe,
InAs/InP/ZnSe, PbS, CdHgTe, CdTe/CdS, and CdTe/CdSe/ZnS QDs
[10]. Ma et al. reviewed NIR QDs in terms of their synthe-
sis, functionalization, and analytical applications, where they
focused on InAs, InAs/CdSe(ZnS, ZnCdS, InP/ZnSe), PbS, PbSe, CdTe,
CdTe/CdSe(CdS), CdSe/CdTe/ZnSe, CdTeSe, CdSeTe/CdS(CdZnS),
CdHgTe, Mn:CdTe, and Cu:InP QDs [57]. Recently, Pichaandi et al.
reviewed NIR-emitting QDs, including recent progress in their
synthesis and characterization, where they focused on PbSe, PbS,
PbSe/CdSe, and PbS/CdS QDs [58]. However, these reviews only
summarized conventional NIR QDs and they did not consider NIR-
emitting Ag2 X QDs.
In our review, we highlight the various synthetic methods and
optical properties (related to different characteristics) of Ag2 X QDs,
where the aim is to make safe and efficient NIR-emitting QDs for
a variety of applications, particularly in bioimaging, chemo-/bio-
detection, QD-sensitized solar cells (QDSSCs), and photocatalysis,
as well as in antimicrobial and thermoelectric materials. More-
over, we summarize various synthetic methods, where we focus
on recent advances in the utilization of Ag2 X QDs in significant
applications. Finally, we consider the future exploration of highly
efficient synthetic methods and the potential applications of high-
quality Ag2 X QDs in different fields (Scheme 1). In our review,
we do not cover other types of metal chalcogenide QDs because
these have been reviewed previously [54], and we do not address
the heterostructures (e.g., doped, core/shelled, alloyed, or hybrid
nanostructures) of Ag2 X QDs, partly to limit the length of this
review, but also because these heteronanostructural QDs maintain
their NIR-emitting properties only poorly, and thus they deviate
from the main focus of this review. Therefore, we limit our scope to
Ag2 X QDs and we focus on the methods used for synthesizing pho-
toluminescent binary Ag2 S, Ag2 Se, and Ag2 Te QDs, which emit from
the NIR-I to NIR-II regions. We summarize various applications
(e.g., QDs-sensitized solar cells, photocatalysts, antimicrobials, and
thermoelectric materials) of binary Ag2 X QDs and the QD-based
assemblies employed. However, these assemblies are based only
on simple conjugation or mixtures with organic molecules, or inor-
ganic compositions, and thus heterostructures of Ag2 X QDs are not
fabricated.
93
2. Development of silver chalcogenide QDs
In 1999, Brelle et al. first reported the synthesis of Ag2 S semi-
conductor colloidal nanoparticles (NPs) capped by cysteine and
glutathione (GSH). The as-synthesized Ag2 S NPs had an average
diameter of ca 9 nm and they exhibited a continuous increase in the
absorption cross-section (600–800 nm), but their emission proper-
ties were not stated [30]. In 2003, Zhao et al. reported controllable
assemblies of order semiconductor Ag2 S nanostructures, including
several superstructures assembled from Ag2 S NPs [31]. In 2004,
monodisperse Ag2 S NCs were prepared by reacting metal-thiolate
and thioacetamide in a pure dodecanethiol solvent [32]. Liu et al.
described the synthesis of Ag2 S QDs in water-in-CO2 microemul-
sions, which was the first example related to Ag2 S QDs [33]. Next,
the first example of a photoluminescent Ag2 S QD was reported
by Wang et al. in 2010 [26]. They developed NIR photolumines-
cent Ag2 S QDs from a single source precursor. Subsequently, many
studies have investigated the preparation of highly efficient Ag2 S
QDs to facilitate their further applications, especially in biomedi-
cal (e.g., bioimaging and chemo-/bio-detection) and optoelectronic
fields (e.g., QDSSCs and photocatalysts).
Next, we discuss the development of Ag2 Se QDs. In 2009, Li
et al. first prepared Ag2 Se NCs via a facile wet route using AgNO3
and selenium powders as precursors and octadecylamine as the
solvent [34]. In 2011, Yarema et al. reported the hot injection syn-
thesis of Ag-chalcogenide NCs (Ag2 Se, Ag2 Te, and Ag2 S; 2–4 nm),
and demonstrated the bandgap energies of the NCs within the NIR
spectral region [25]. The as-prepared Ag2 Se NCs produced size-
tunable PL with PL quantum yields (PLQYs) > 1.7%. This was the first
example of photoluminescent Ag2 Se NCs or QDs. Further studies
of the synthesis and applications of photoluminescent Ag2 Se QDs
were reported subsequently.
Ag2 Te nanostructures were reported in earlier studies, including
nano-wires/tubes/rods/particles [35–40], but luminescent Ag2 Te
NCs or QDs were described rarely. Liu et al. used a rapid injec-
tion method to prepare Ag2 Te NCs, which exhibited NIR absorption
and photoconductive responses [39]. Zhou et al. synthesized sulfur-
doped Ag2 Te NPs using a solvothermal approach to generate the
desired electrical resistivity, but no luminescence was observed
[40]. In 2011, Yarema et al. prepared 3.2 nm Ag2 Te NCs, where the
PL was found to peak at 1300 nm and it reached up to 1500 nm [25].
PL from Ag2 Te NCs or QDs had not been reported previously, so this
was the first example of photoluminescent Ag2 Te NCs. Later, Chen
et al. developed cation exchange between Ag ions and prepared
CdTe QDs in aqueous solution, as well as obtaining NIR-II-emitting
Ag2 Te QDs [41]. Most of the studies of Ag2 Te NCs (or QDs and
NPs) with different nanostructures have focused on analyzing their
thermoelectric properties, whereas there have been few studies of
synthetic methods and biomedical applications of photolumines-
cent Ag2 Te QDs.
3. Methods for synthesizing silver chalcogenide QDs
Next, we summarize the methods used for synthesizing
photoluminescent Ag2 X QDs, but we do not consider non-
photoluminescent Ag2 X NCs (or NPs) and their heteronanos-
tructural nanomaterials. Before the study of photoluminescent
Ag2 X QDs, many investigations focused on the synthesis of non-
photoluminescent binary and heterostructural Ag2 X NCs or NPs
[30–32,34,39]. Although these earlier studies are helpful for the
synthesis of photoluminescent Ag2 X QDs, there are also remarkable
differences between the methods used to synthesize photolumi-
nescent QDs and non-photoluminescent NCs. We provide brief
outlines of synthetic methods for photoluminescent Ag2 X QDs
in the following sections, which allow the reader to determine
94 R. Gui et al. / Coordination Chemistry Reviews 296 (2015) 91–124
the appropriate synthetic methods (e.g., organic-/aqueous-/polar-
phase, biomimetic synthesis, and cation exchange), reaction
conditions (e.g., reaction temperatures and times), materials used
(e.g., amounts and ratios of precursors, solvents, and ligands), and
the characteristics of the Ag2 X QDs produced (e.g., maximum emis-
sion wavelengths and PLQYs). More specific details are given in
each section, which can help to differentiate each type of synthetic
method. We describe previously reported methods for synthesiz-
ing Ag2 X QDs, as well as comparing and summarizing the specific
details of each method.
3.1. Synthesis of Ag2 S QDs
To facilitate our review of the synthesis methods for photolu-
minescent Ag2 S QDs, Table 1 provides a brief summary of the key
synthesis parameters and product characteristics. These methods
are classified mainly based on the solvents used, including inor-
ganic solvents, water-soluble solvents, water, and biosystems. We
illustrate each method class and we compare the differences among
these methods. In the final part of this section, we consider the
future exploration of the methods for synthesizing high-quality
photoluminescent Ag2 S QDs.
3.1.1. Organic phase synthesis methods
Prior to the method reported by Wang et al. [26], NIR QDs
with low or no toxicity in living bodies were considered desir-
able because most of the previously reported NIR QDs contained
heavy metal elemental forms with known acute or chronic toxicity
[70,71]. Thus, Wang et al. reported a new method for synthesiz-
ing single-crystalline and monodisperse Ag2 S QDs by employing a
single source precursor, (C2 H5 )2 NCS2 Ag (Fig. 1A). The oleic acid-
capped Ag2 S QDs exhibited NIR emission with a sharp peak at
1058 nm and they could be dispersed easily in apolar organic
solvents (e.g., cyclohexane). To obtain the desired NIR emission
property, the requisite characteristic of the Ag2 S product is a
monoclinic phase. All of the peaks in the powder X-ray diffrac-
tion (XRD) patterns matched those of monoclinic Ag2 S (acanthite
type, space group P21 /n) and the calculated lattice constants
were a = 4.226 Å, b = 6.928 Å, and c = 7.858 Å. Transmission elec-
tron microscope (TEM) images showed that the as-prepared Ag2 S
QDs were monodisperse with a size of 10.2 ± 0.4 nm, and HRTEM
images confirmed that the Ag2 S QDs were single-crystalline with
an interplane distance in the lattice fringes of ca 0.28 nm, which
corresponds to that of the (1 1 2) facets in Ag2 S. A discernible
absorption peak was detected in the NIR window at 920 nm, which
is the lowest energy excitonic absorption peak of Ag2 S QDs. Rel-
ative to the band-gap energy of bulk ˛-Ag2 S (Eg = 1.1 eV), the
lowest-energy exciton transition peak of Ag2 S QDs exhibited a
blue shift, thereby implying that the Ag2 S NCs behave within
the quantum-confinement regime. The PL spectrum of Ag2 S QDs
excited with a 785 nm laser diode exhibited a symmetric emission
peak centered at 1058 nm, as well as an impressive full-width at
half-maximum as low as 21 nm, which could be attributed to the
narrow size distribution of Ag2 S QDs. Moreover, Wang et al. also
reacted (C2 H5 )2 NCS2 Na3 ·H2 O (i.e., Na(DDTC)) with AgNO3 to pre-
pare Ag(DDTC) [108]. Using the same method (see [26]), Wang et al.
also synthesized 1-dodecanethiol-capped Ag2 S QDs that measured
2.4–7 nm, with typical NIR emission properties (with PL peaks at
975–1175 nm).
High temperatures are possible in organic-phase synthesis
methods, which promote the rapid formation of Ag2 S nuclei. Sur-
face ligands regulate the slow growth of Ag2 S nuclei to produce
Ag2 S QDs, which can effectively anneal out surface defects. In
addition, the low toxicity and appropriate narrow bandgap of
Ag2 S QDs make them excellent NIR-emitting QDs. In subsequent
studies [42,59], hydrophobic Ag2 S QDs prepared according to the
methods described above were coated with a surfactant (dihy-
drolipoic acid, DHLA) to yield water-dispersible DHLA-capped
Ag2 S QDs, or reacted with amine-functionalized six-armed
poly(ethylene glycol) (6-PEG) to obtain highly water-soluble (in
water, buffers, and sera) 6-PEG-Ag2 S QDs. Therefore, hydrophobic
Ag2 S QDs are likely to undergo a phase transfer from the organic
phase to the water phase via ligand exchange on the surfaces of
QDs to gain hydrophilic Ag2 S QDs. This treatment facilitates fur-
ther applications of Ag2 S QDs in water-soluble systems, especially
as new and nontoxic NIR-emitting QDs for efficient in vivo imaging.
Given its bulk bandgap of 0.9–1.1 eV and negligible toxic-
ity, nanoscale ˛-Ag2 S is a potential candidate for NIR QDs. Pang
et al. designed a two-step method for preparing emission-tunable
NIR Ag2 S QDs that ranged from the NIR-I to NIR-II regions
(690–1227 nm) [43]. This method was based on previous reports
of NIR-emitting Ag2 S QDs with specific PL emissions [25,26]. First,
small Ag2 S QDs were synthesized by injecting hexamethyldisi-
lathiane ((TMS)2 S) into a mixture of silver acetate/CH3 COOAg and
organic solvents at a given temperature under Ar flow. Second,
large Ag2 S QDs were prepared via seed-mediated growth, with
the dropwise addition of AgNO3 , 1-octylamine, and sulfur pow-
der (dissolved in toluene) into a toluene solution that contained
small Ag2 S QDs (Fig. 1B). TEM images of the products synthesized
in step one suggested that the products were spherical particles
measuring 1.5 ± 0.4 nm in diameter, which had a narrow size distri-
bution. An HRTEM image showed that the particles had clear crystal
structures with obvious atomic planes. The atomic planes with a d-
spacing of 0.238 nm in the NCs could be indexed as the (1 0 3) facet
of monoclinic ˛-Ag2 S. The XRD results detected weak and indis-
tinguishable diffraction peaks, which may have been attributable
to their small size and amorphous surface ligands. After thermal
treatment at 180 ◦ C under Ar flow for 1 h, the XRD spectrum was
greatly improved and it agreed well with monoclinic Ag2 S. Energy
diffraction X-ray (EDX) data confirmed that the products comprised
elemental Ag and S with an Ag:S atomic ratio of 1.7:1, which was
close to the stoichiometry of the bulk Ag2 S. As a consequence of
quantum confinement, the first exciton peak appeared at 655 nm
(1.9 eV) in the UV–Vis spectrum, which was clearly blue-shifted
compared with the band gap of bulk Ag2 S (0.9–1.1 eV). The PL exci-
tation spectrum also exhibited a well-defined exciton peak, which
agreed well with the UV–Vis spectrum. The room temperature PL
emission peak of 1.5 nm Ag2 S NCs in n-hexane solution was located
at 813 nm, with a full-width at half-maximum of 65 nm. The PL
quantum yield was 0.18% using indocyanine green (ICG) as a refer-
ence standard (quantum yield, QY = 13% in dimethyl sulphoxide).
The PL decay kinetics were found to be multiexponential with
an average lifetime of 57 ns, which may be ascribed to inhomo-
geneities on the surfaces of the NCs. Pang et al. demonstrated that
with a lower initial injection temperature, fewer monomers were
consumed to form the initial nuclei and more monomers were
retained for the growth process. These emission-tunable NIR Ag2 S
QDs have potential applications in nano-diagnostics and multicolor
bioimaging.
Robinson et al. developed a rational synthesis method for
producing monodisperse metal sulfide NCs in organic nonpolar
solutions [62]. Using (NH4 )2 S and AgCl as precursors, large-scale
monodisperse Ag2 S NCs (emitted at ca 940 nm) were synthesized in
a single reaction at room temperature. This low-temperature tech-
nique can be used to produce small NCs (such as ca 5 nm Ag2 S QDs).
Although Ag2 S QDs were prepared using this method without heat-
ing, the PLQYs (not described in the article) of the as-prepared Ag2 S
QDs could be low due to the presence of numerous surface defects
compared with hot-injection methods [42,43,59,63]. In addition,
when utilizing AgNO3 and sulfur powder as precursors, Ag2 S QDs
could be obtained in organic solvents at 150 ◦ C or 180 ◦ C [63,64]. The
coating ligand (dodecylamine) on the surface of the resulting Ag2 S
 R. Gui et al. / Coordination Chemistry Reviews 296 (2015) 91–124 95

Table 1
Comparison of synthetic conditions for preparing Ag2 S QDs with different reaction temperature (temp.), precursors, solvents, capping ligands, emission wavelengths,
diameters and PLQYs.

Precursors Solvents Capping ligands Temp. (◦ C) Emission (nm) PLQY (%) Ref.

(C2 H5 )2 NCS2 Ag, AgNO3 , Na(DDTC) 1-Octadecene, Oleic acid, 200 1058 No report [26]
1-dodecanethiol octadecylamine 130–160 975–1175 [108]
(C2 H5 )2 NCS2 Ag 1-Dodecanethiol, DHLA 230 1150–1200 5.8 [59]
cyclohexane,
ethanol
(C2 H5 )2 NCS2 Ag 1-Dodecanethiol, DHLA, 6PEG (phase 210 1200 15.5 [42]
cyclohexane, transfer)
ethanol
CH3 COOAg, (TMS)2 S, sulfur powder, AgNO3 1-Octadecene, 1-Octylamine 110 690–1227 0.18 [43]
myristic acid,
toluene
AgCl, (NH4 )2 S Oleylamine, Oleylamine Room temp. 940 No report [62]
trioctylphosphine
AgNO3 , sulfur powder Toluene, Dodecylamine, 150 1045 2.5 [63]
dodecylamine GSH (phase
ethanol, GSH, transfer)
water
AgNO3 , sulfur powder Ethanol, water, Alkanethiol 180 1225 No report [64]
hexane, oleic acid
AgNO3 , Na2 S Water 2MPA 90 780–950 7–39 [47]
AgNO3 , GSH Water GSH 95 960–1015 1.97 [61]
AgNO3 , S-N2 H4 ·H2 O Water GSH Room temp. 624–727 1.2 [45]
AgNO3 , DMSA Water DMSA 70 or 90 780–920 6.5 [68]
AgNO3 , Na2 S Water BSA, antiVEGF 25 or 37 660–840 No report [46]
AgNO3 , Na2 S Water BSA Room temp. 1050–1294 1.8 [21]
AgNO3 , S-N2 H4 ·H2 O Water Multidentate 95 687–1096 14.2–16.4 [67]
polymers
AgNO3 , Na2 S Water Ribonuclease-A Room temp. 980 No report [66]
AgNO3 , 3-MPA Ethylene glycol MPA 145 510–1221 2.1 [44]
CH3 COOAg, GSH Ethylene glycol GSH 150 1106 3.3 [60]
CdS QDs, AgNO3 Water GSH (cation Room temp. 905–1090 2.3 [65]
exchange)
AgNO3 , Na2 S Cultured HepG2 Intracellular GSH Room temp. 945 1.56 [69]
cells

Fig. 1. (A) (a) Synthesis of Ag2 S NIR QDs from a single source precursor of Ag(DDTC), (b) XRD patterns of the as-prepared Ag2 S QDs, (c) TEM image of Ag2 S QDs, (d) HRTEM
image of a single Ag2 S QDs, (e) NIR absorption spectrum of as-obtained Ag2 S QDs, (f) NIR PL emission spectrum of Ag2 S QDs at room temperature under ex = 785 nm
(Reproduced with permission from Ref. [26], Copyright 2010, American Chemical Society). (B) (a) Synthesis of PL-tunable NIR Ag2 S QDs, (b) TEM and inserted HRTEM images
of Ag2 S NCs synthesized in step one, (c) XRD patterns of 1.5 nm Ag2 S NCs before (a) and after (b) thermal treatment at 180 ◦ C under Ar flow for 1 h, (d) EDX, (e) absorption
(a), excitation (b), and PL spectra of Ag2 S NCs synthesized in step one (Reproduced with permission from Ref. [43], Copyright 2012, American Chemical Society).
96 R. Gui et al. / Coordination Chemistry Reviews 296 (2015) 91–124
QDs was replaced by GSH to form hydrophilic GSH-capped Ag2 S
QDs [63]. Ligand exchange occurred on the surface of the QDs and
it was accompanied by a phase transfer process, which enhanced
the water-soluble performance of Ag2 S QDs, thereby facilitating
their further applications in biosystems.
In these organic phase synthesis methods for Ag2 S
QDs (as shown in Table 1), low cost inorganic silver salts
(CH3 COOAg/AgNO3 /AgCl) can be used as the Ag precursors,
thereby avoiding the use of expensive, toxic, pyrophoric, and
unstable organometallic reagents (e.g., (C2 H5 )2 NCS2 Ag). As
reported by Peng et al. [72], the previously used Cd(CH3 )2 -related
Cd precursors could be replaced by CdO to significantly accelerate
developments in the synthesis of high-quality Cd chalcogenide NCs
[73,74]. In addition, sulfur powders (used extensively as a sulfur
source) are involved in the synthesis of Ag2 S QDs, thereby ensuring
the use of low cost precursors. However, the use of various organic
solvents (e.g., 1-octadecene, 1-dodecanethiol, trioctylphosphine,
and toluene) during synthesis may lead to side effects or hazards in
applications. From the perspectives of green chemistry and indus-
trial applications, the usage of toxic and expensive pyrophoric
solvents and organometallic reagents should be eliminated [75,76].
The PLQYs of the prepared Ag2 S QDs in the organic phases could
reach as high as 15.5% (at a reaction temperature of 230 ◦ C) after
ligand exchange post-treatment [42] compared with 0.18 or 2.5%
for the Ag2 S QDs prepared at <150 ◦ C [43,63]. These experimental
results indicate that a higher temperature favors the production
of Ag2 S QDs with high PLQYs. Furthermore, these high PLQYs can
be maintained almost unchanged around the surfaces of Ag2 S QDs
after the ligand exchange process.
3.1.2. Aqueous phase synthesis methods
Hydrophobic Ag2 S QDs prepared in organic phases can be con-
verted into hydrophilic QDs via ligand exchange on the surfaces of
QDs, while still maintaining the PLQYs almost unchanged, although
the synthesis procedures are relatively tedious, where they require
harsh reaction conditions, as well as expensive and hazardous
solvents. However, hydrophilic Ag2 S QDs are required, especially
for biomedical applications (due to their negligible toxicity and
excellent NIR PL). Thus, aqueous synthesis or direct synthesis in
water-soluble media is highly desirable because the QDs obtained
can be applied directly to biosystems without additional post-
treatments using ligand exchange or phase transfer. In addition,
the Ag2 S QDs can undergo conversion from the organic phase to
the aqueous phase using synthetic methods. In recent years, many
studies have addressed the development of aqueous synthesis
methods for Ag2 S QDs [21,45,47,61,65–68]. To review these studies,
we provide a classification based on the capping ligands employed.
In particular, the aqueous phase synthesis methods employed for
Ag2 S QDs can be divided into two main classes: small molecule
ligand-capped Ag2 S QDs and macromolecule ligand-capped Ag2 S
QDs.
3.1.2.1. Small molecule ligand-capped Ag2 S QDs. Using a simple
aqueous method (2-mercaptopropionic acid (2MPA) as a capping
reagent), Hocaoglu et al. prepared highly stable and NIR-emitting
Ag2 S QDs, where the PL emission wavelengths of the QDs could
be tuned between 780 and 950 nm [47]. It was shown that the
slow decomposition rate (e.g., 1 month) of 2MPA facilitated the
deposition of more sulfur onto the surfaces of the QDs, thereby
resulting in slight particle growth and improved luminescence
(QY = 7–39%) by pacifying the surface traps. In addition to the high
PLQYs, the improved cytocompatibility (e.g., in NIH/3T3 cell lines)
and excellent colloidal stability (e.g., >1 year because the surface
COOH groups yield a strong negative zeta potential) of these QDs
make them promising candidates for bio-applications, especially
for in vivo imaging. This was the first example of an aqueous phase
synthesis method for Ag2 S QDs (Fig. 2A).
Using reduced GSH as both the sulfur source and stabilizer,
Tan et al. synthesized water-dispersible Ag2 S QDs via a one-pot
solution procedure and reported that the PLQY of the QDs was
1.97% (Fig. 2B) [61]. Lin et al. employed a novel sulfur-hydrazine
hydrate complex (S-N2 H4 ·H2 O) as the S2− source and GSH as the
capping reagent to synthesize photoluminescent Ag2 S NCs (Fig. 2C)
[45], which exhibited luminescence at emission peak wavelengths
from 624 nm to 724 nm (Fig. 2D). Under normal light, a yellow-
transparent solution gradually changed into a brown one as the size
of the NCs increased (Fig. 2E). Under UV irradiation (365 nm), these
samples exhibited red and size-dependent PL emission (Fig. 2F).
GSH (a small biomolecule) functions as a key scaffold to prevent
the overgrowth of NCs and it provides several functional groups
(e.g., COOH and NH2 ) that facilitate the dispersion of Ag2 S NCs
in aqueous solution, as well as their high biocompatibility. Com-
pared with that when using a hydrothermal reaction (at 90 ◦ C or
95 ◦ C) [47,61], the PLQY of the Ag2 S NCs was relatively low (1.2%),
which may be attributable to the specific reaction performed at
room temperature [45]. By contrast, a higher reaction temperature
(rather than room temperature) and a longer reaction time (only
30 min in [45]) were more effective for enhancing the growth of
particles (as well as shifting the PL emission peak toward a longer
wavelength, e.g., in the NIR-II region), while also annealing out the
surface defects of QDs to yield higher PLQYs.
Recently, Hocaoglu et al. synthesized size-tunable Ag2 S QDs
that emitted in the NIR region by decomposing meso-2,3-
dimercaptosuccinic acid (DMSA) in water [68]. DMSA could slowly
release the sulfur at reaction temperatures of 50–90 ◦ C (at pH
7–10) [81]. In experiments, DMSA acted simultaneously as the
sulfur source, coating agent, and metal-chelating reagent, thereby
improving the cytocompatability of the QDs significantly [82,83].
In addition to the hydrothermal reaction (at 70 ◦ C or 90 ◦ C), the
Ag2 S QDs prepared with NIR emission (780–920 nm) had a PLQY as
high as 6.5%. According to the experimental results reported in [47]
(QY = 7–39%) and [68] (QY = 6.5%), a slower sulfur release rate (dur-
ing the incubation stage after synthesis, or in the synthesis stage)
is a key factor that markedly improves the PLQYs of the Ag2 S QDs
obtained.
3.1.2.2. Macromolecule ligand-capped Ag2 S QDs. A low temperature
reaction consumes less energy, but the room temperature synthesis
of high quality Ag2 S QDs with high PLQYs and NIR emission is still
challenging. In addition to extending the reaction time, the choice
of capping ligand is also significant. It has been demonstrated
that biomacromolecules or artificial polymers with sufficient active
groups (e.g., COOH, NH2 , OH, or SH) can conjugate with Ag+ to
form coordinating complexes (e.g., Ag+ -thiolate) [77], which func-
tion as good stabilizers on the surfaces of the Ag2 S QDs. Yan et al.
reported the one-pot fabrication of bovine serum albumin (BSA)-
stabilized Ag2 S QDs and bio-conjugation of the QDs with vascular
endothelial growth antibody (anti-VEGF) for targeted in vivo can-
cer imaging (Fig. 3A) [46]. Without high temperature and inert gas
protection, BSA-stabilized Ag2 S QDs were synthesized in aqueous
solution (25 ◦ C or 37 ◦ C), which exhibited intense NIR PL, ultrasmall
size, and low in vivo toxicity. After incubating BSA with AgNO3
to allow the formation of a BSA-Ag+ mixture, Na2 S (as the sulfur
source) was added to the mixture under intense agitation to pro-
mote the growth of NCs. After incubating for 12 h at 37 ◦ C, Ag2 S
QDs were obtained with PL emitted at 660–840 nm. The range of
the emission wavelengths was broader than that obtained when
using small molecular GSH as the capping ligand (624–724 nm) and
a shorter reaction time (30 min) [45].
Similarly, Yu et al. reported the facile one-pot biomimetic syn-
thesis of water-dispersible NIR-II-emitting ultrasmall Ag2 S QDs,
 R. Gui et al. / Coordination Chemistry Reviews 296 (2015) 91–124 97

Fig. 2. (A) Aqueous synthesis of 2-MPA coated Ag2 S NIR QDs (Reproduced with permission from Ref. [47], Copyright 2012, The Royal Society of Chemistry). (B) Synthetic
strategy of Ag2 S NPs (Reprinted with permission from Ref. [57], Copyright 2012, Wiley-VCH). (C) The facile formation process of the aqueous-phase synthesis of photolu-
minescent Ag2 S NCs. (D) PL normalized emission spectra of resultant photoluminescent Ag2 S NCs in aqueous solution. The photographs of Ag2 S NCs in aqueous solution for
samples S1, S2, S3, and S4: (E) under normal light illumination and (F) under UV light illumination (C–F, Reprinted with permission from Ref. [45], Copyright 2013 American
Chemical Society).

where the PL emission peaks could be tuned from 1050 to 1294 nm
(Fig. 3C) [21]. It was confirmed that a lower precursor molar ratio
of Ag:S (from 3:1 to 1:10) yielded QDs with an increased diam-
eter. As the Ag:S ratio was reduced, the absorption spectra of
the as-prepared Ag2 S QDs extended from the UV–Vis region into
the NIR region (Fig. 3D), and the corresponding emission spectra
shifted toward the NIR-II region (Fig. 3F). The results were similar
to those obtained for Ag2 S QDs with similar diameters (1.6–6.8 nm),
which were prepared in organic solvents [26,42,59]. The bandgap
(Eg ) values of these QDs ranged from 1.23 to 0.94 eV (Fig. 3E),
thereby suggesting that the Eg of Ag2 S QDs is size-dependent and
larger than that of the related bulk materials (0.85 eV). Dynamic
light scattering (DLS) measurements showed that the hydrody-
namic diameter of the QDs in water was approximately 10 nm.
The difference in the diameters measured by TEM (average par-
ticle size of ca 3.3 nm) and DLS may be attributable to different
surface species on the QDs prepared in the aqueous phase. The
small size of these fluorescent probes has many advantages in bio-
applications. Zeta potential measurements of the Ag2 S QD solution
(in water) detected a slightly negative surface charge (–31.1 eV),
which indicates that the surface charge was dominated by the
bound BSA. Ag2 S QDs dispersed in water (inset) exhibited no obvi-
ous flocculation in water after standing for several months at room
temperature. It is likely that the surface-bound BSA prevented the
aggregation and growth of the QDs.
During the aqueous synthesis of Ag2 S QDs, the two examples
mentioned above [21,46] used the same capping ligand (BSA) and
precursors (AgNO3 and Na2 S), as well as low temperature reaction
conditions. For comparison, Yan et al. varied the Ag:S ratio among
6:1, 4:1, and 1:1, where the corresponding PL was emitted at 660,
750, and 840 nm [46], while Yu et al. tuned the ratio among 3:1, 1:2,
1:3, 1:5, and 1:10 (1050–1294 nm) [21]. This indicates that the high
excess of sulfur precursors compared with silver precursors pro-
moted a dramatic red-shift in the PL emission wavelengths, which
favors the rapid production of Ag2 S QDs with PL emissions in the
NIR-II biological window.
Undoubtedly, BSA-stabilized Ag2 S QDs have good biocompat-
ibility and they can be applied as a promising NIR PL probe for
bioimaging [21], but the lower PLQYs (only 1.8%) of the QDs proba-
bly constrain their practical use during in vitro and in vivo imaging.
Gui et al. used thiol-based multidentate polymers (poly(acrylic
acid)-graft-cysteamine-graft-ethylenediamine) as capping ligands
to synthesize Ag2 S QDs in aqueous solution (Fig. 3B) [67], where
it was found that the multidentate polymers could minimize the
hydrodynamic size of QDs, as well as overcoming the issues of
colloidal stability, photobleaching, and PL brightness of tissues
reported in previous studies [78–80]. Experimental results suggest
that a thin coating (1.6–1.9 nm) of polymer ligands is responsible for
the high PLQYs (14.2–16.4%) of the Ag2 S QDs. The coating thickness
of BSA around the QDs is ca 6.7 nm [21,46], which indicates that the
BSA does not coat the QDs compactly, thereby yielding Ag2 S QDs
with a low PLQY (1.8%) [21]. In summary, thiol-based polymer lig-
ands have a strong intrinsic metal-chelating action, which allows
them to be used in the fabrication of high affinity metal-ligand
98 R. Gui et al. / Coordination Chemistry Reviews 296 (2015) 91–124

Fig. 3. (A) Synthesis of NIR PL BSA-stabilized Ag2 S QDs and antiVEGF bioconjugated Ag2 S QDs (Reprinted with permission from Ref. [46], Copyright 2013, The Royal Society
of Chemistry). (B) Schematic illustration of the formation process of PL Ag2 S QDs (Reprinted with permission from Ref. [63], Copyright 2014, The Royal Society of Chemistry).
(C) Proposed formation mechanism of Ag2 S QDs. (D) UV–vis–NIR absorbance spectra of the QDs in water synthesized by different Ag/S molar ratios and pure BSA in water.
(E) (˛hv)1/2 as a function of photon energy (hv) for Ag2 S QDs and (F) their NIR PL spectra, (G) DLS spectra and photograph and (H) zeta-potential measurement of BSA capped
Ag2 S QDs in aqueous solution (C–H, Reprinted with permission from Ref. [21], Copyright 2013, IOP Publishing Ltd.).
 R. Gui et al. / Coordination Chemistry Reviews 296 (2015) 91–124
clusters [76]. The abundant thiols in each multidentate polymer
unit mean that the polymers play important roles as excellent
nucleating agents and then as capping agents during the QD growth
process [45,77]. A previous study [67] showed that the appropri-
ate selection of capping ligands is vital and a compact coating of
thiol-based polymer ligands on the surfaces of QDs yields a higher
PLQY. Although the Ag:S ratio was not tested at different values, the
Ag:ligand ratio was varied from 1:5 to 1:1 and the corresponding PL
was emitted from 687 to 1096 nm (into the NIR-II region). Further-
more, the reaction time was relatively short (10–150 nm) because
a hydrothermal reaction was performed (95 ◦ C), rather than a reac-
tion at room temperature or 37 ◦ C.
Chen et al. reported the synthesis of Ribonuclease-A conju-
gated Ag2 S QDs clusters in the aqueous phase using a biomimetic
route [66]. Ribonuclease-A (similar to BSA) served as both a sta-
bilizer reagent and a biomolecule to modify the surfaces of Ag2 S
QDs, thereby avoiding aggregation and decreasing the cytotoxicity.
This synthesis was conducted only for 5 min at room temperature,
where it yielded the corresponding PL emission at 980 nm (the
PLQYs were not reported). According to other studies (summarized
in Section 3.1.2.1), we made some reasonable deductions, as fol-
lows. The PLQY of the prepared QDs would have been relatively
low due to the lower reaction temperature and shorter reaction
time. Moreover, the use of thiol-free or thiol-less capping ligands
hindered the production of Ag2 S QDs with high PLQYs.
Based on all of these aqueous-phase synthesis methods for
high quality NIR-emitting Ag2 S QDs, some important parameters
can be determined, i.e., the molar ratio of the Ag:S precursors
(lower), Ag:ligand ratio (higher), release rate of sulfur sources
(slower), reaction temperature (higher), reaction time (longer),
and the choice of surface-capping ligands (thiol-rich biocompat-
ible polymers obtained by short-chain molecular polymerization
are preferable to other types of water-soluble ligands).
3.1.3. Polar phase synthesis methods
Using CH3 COOAg as the silver precursor, GSH as both the sul-
fur source and a capping reagent, and ethylene glycol (EG) as the
solvent, water-soluble Ag2 S QDs were prepared at 150 ◦ C, which
exhibited PL emission peaks at 1106 nm and with a PLQY of 3.3%
(Fig. 4A) [60]. Tian et al. developed a one-step synthesis method for
preparing Ag2 S QDs with tunable PL emissions (510–1221 nm) [44]
by utilizing AgNO3 as the silver precursor, 3-mercaptopropionic
(MPA) as both the sulfur source and a capping reagent, and EG as
the solvent. The synthesis reaction was performed at 145 ◦ C and
the Ag2 S QDs obtained were terminated with COOH groups, and
thus they exhibited good water solubility (Fig. 4B). By changing
the amount of AgNO3 added and the growth time of NCs, the first
exciton peaks of the as-synthesized Ag2 S QDs ranged from 353 to
1010 nm (3.53–1.23 eV) (Fig. 4C), unlike the bandgap of the bulk
Ag2 S (0.9–1.1 eV). This dramatic red-shift change was attributed
to the quantum confinement effect of QDs. The red-shift changes
also extended to the corresponding room-temperature PL emission
spectra of the Ag2 S QDs (Fig. 4D).
To highlight the quantum confinement effect of Ag2 X QDs, we
provide the following summary. Sahu et al. investigated quantum
confinement in Ag2 Se semiconductor NCs (QDs) [106], where they
prepared Ag2 Se NCs with average diameters of 2.7–10.4 nm, which
exhibited narrow optical absorption features in the near- to mid-
IR. They demonstrated that these features were broadly tunable
due to quantum confinement and they provided the longest wave-
length absorption peaks (6.5 ␮m) yet reported for colloidal NCs.
Langevin et al. reported the size-dependent extinction coefficients
and transition energies of NIR ˇ-Ag2 Se colloidal QDs [107], where
the results showed that the energy of the first observed transi-
tion decreased asymptotically with the colloidal QD size toward
a value of 1.1 eV, which was significantly greater than that of the
99
ˇ-Ag2 Se bulk bandgap. The molar extinction coefficient of this
absorption was proportional to r0 2.7±0.2 , where r0 is the QD radius.
At higher energies, the extinction coefficient eventually followed
the classically predicted cubic power law with r0 . Zhang et al.
reported the controlled synthesis of Ag2 S QDs and the experimen-
tal determination of the exciton Bohr radius [108]. For the first
time, they systematically investigated the size-dependent excited
state optical properties of Ag2 S QDs based on PL using PL excitation
and time-resolved PL spectroscopy. The experimental exciton Bohr
radius of the Ag2 S QDs was determined as 2.2 nm, which agreed
well with the theoretical results.
Compared with the organic phase methods for the synthesis of
Ag2 S QDs [42,59], the polar-phase (water-soluble small molecule
polar solvents, such as EG) synthesis consumes less energy and it
can yield NIR-I (even NIR-II)-emissive PL, but also relatively low
PLQYs [44,60]. Compared with aqueous-phase synthesis methods
for Ag2 S QDs [45–47,66,68], the polar-phase synthesis (usually
conducted above 100 ◦ C, which is higher than hydrothermal reac-
tion temperatures) is much easier for producing NIR emissions,
but it also consumes more energy. Although this specific method
has some limitations, its performance is intermediate between the
organic-phase and aqueous-phase synthesis methods. Tian et al.
reported the first example of the direct synthesis of water-soluble
NIR PL Ag2 S QDs stabilized by MPA in EG solvent [44]. Subsequently,
Hocaoglu et al. reported the first direct aqueous synthesis of 2MPA-
capped Ag2 S QDs with NIR emissions (also in 2012) [47]. The direct
aqueous synthesis of NIR-emitting Ag2 S QDs has attracted increas-
ing attention mainly due to the requirement for green synthesis and
the excellent biomedical applications of Ag2 S QDs, as demonstrated
in the past five years.
3.1.4. Biomimetic synthesis methods
Biochemical reactors or biosystems are powerful tools for the
controllable synthesis of nanomaterials [84–87]. For example,
small Au clusters (1.3 nm) have been synthesized in a quasi-
biosystem [87]. Biosynthesis (i.e., direct synthesis in biosystems)
of semiconductor NCs was first demonstrated in unicellular yeast,
which was shown to yield CdS QDs by adding inorganic Cd salts
[88]. Subsequently, Cd-containing QDs have been synthesized uti-
lizing fungi, bacteria, or yeasts in biosystem reactors [89–93].
Recently, the biochemical synthesis of CdTe QDs has been con-
ducted favorably using earthworms [94] and NIR-emitting PbS QDs
were prepared in microorganisms [95]. In particular, methods for
the biomimetic synthesis of NCs have been applied to obtain NIR-
emitting Ag2 S QDs, where GSH is used often as a reductive or
sulfur source during the intracellular biosynthesis of QDs. The opti-
cal properties of biosynthesized QDs are similar to those of their
counterparts synthesized in common chemical synthesis reactions
[94,95]. Tan et al. described the intracellular synthesis of NIR Ag2 S
QDs in cultured HepG2 cancer cells (Fig. 5) [69]. By employing the
endogenous GSH (2–8 mM) in cancer cells (which have much higher
GSH contents than normal cells) [96–98], the delivery of precursors
(AgNO3 and Na2 S) into the cancer cells yielded Ag2 S QDs (PL emit-
ted at 945 nm and a PLQY of 1.56%). This is an interesting strategy
for the biomimetic synthesis of NIR-emitting Ag2 S QDs, which may
inspire researches to explore other biosynthesis routes for produc-
ing photoluminescent NCs. In addition, the high GSH (as a capping
ligand) content in cancer cells favors the intracellular synthesis
of QDs. This strategy may be extended to other PL QDs, thereby
offering new insights into the direct synthesis of bioimaging agents
in situ.
3.1.5. Cation-exchange synthesis methods
Efficient and fast cation-exchange was achieved previously
for Cd-based NCs (e.g., CdS, CdSe, and CdTe NCs) by using
Ag+ ions to form cognate Ag-based NCs in organic phases
100 R. Gui et al. / Coordination Chemistry Reviews 296 (2015) 91–124

Fig. 4. (A) Synthetic strategy of Ag2 S NPs (Reprinted with permission from Ref. [56], Copyright 2013, American Chemical Society). (B) Synthesis of water-soluble carboxylic
acid-terminated Ag2 S QDs with tunable emissions. (C) Absorption and (D) corresponding PL spectra of Ag2 S NCs synthesized under different conditions: 60 mM of AgNO3 ,
growth time 90 s (curve “a”); 5 mM of AgNO3 , growth time: 5 min (curve “b”), 15 min (curve “c”), 60 min (curve “d”). The bright-field (left) and PL (right, pseudocoloured
image) photographs (D, inset) of Ag2 S NCs corresponded to curve “c” (B–D, Reprinted with permission from Ref. [44], Copyright 2012, Elsevier).

[41,61,99–101], but the materials obtained did not exhibit PL
emission. Alivisatos et al. [99] employed a typical NC semicon-
ductor system where CdSe was reacted with Ag+ ions to generate
Ag2 Se NCs by facile cation-exchange. Next, they developed a
colloidal route for synthesizing CdS-Ag2 S nanorod superlat-
tices by partial cation-exchange [100]. In addition, Yu et al.
developed a syringe pump-assisted method for synthesizing
water-soluble cubic structural Ag2 Se NCs via a cation-exchange
reaction between ZnSe NCs and Ag+ ions [101]. The driving force of
cation-exchange is the large difference in solubility between Cd-
chalcogenide and Ag-chalcogenide NCs (e.g., Ksp (CdS) = 8.0 × 10−27 ;
Ksp (Ag2 S) = 6.3 × 10−50 ; and Ksp (CdSe) = 6.31 × 10−36 ;
Ksp (ZnSe) = 3.2 × 10−35 ; Ksp (Ag2 Se) = 2.0 × 10−64 ). A nano-size
effect makes this transition highly convenient and rapid in
ambient conditions (far less than 1 s) [99]. Recently, Gui et al.
synthesized biocompatible NIR-emitting Ag2 S QDs by facile
cation exchange using newly prepared visible-light emit-
ting GSH-capped CdS QDs with Ag+ ions in aqueous solution
(Fig. 6) [65]. The QDs obtained exhibited typical NIR-II emis-
sions (905–1090 nm) with a PLQY of 2.3%. This method for
synthesizing Ag2 S QDs was conducted at room temperature and
in ambient aqueous solution, which makes it relatively facile.
Compared with other aqueous phase synthesis methods at room
temperature [21,45,66,69], the PLQY of the Ag2 S QDs prepared
using this method is relatively high. The relatively high PLQY of
CdS QDs and the high efficiency of cation exchange can maximize
the avoidance of surface traps. However, in reactions performed at
room temperature, the growth of NCs is generally slow and surface
defects will present on the NCs. Apart from these limitations, the
inherent properties of Ag-chalcogenide QDs yield lower PLQYs
compared with Cd-chalcogenide QDs [43,45]. Another method
[65] suggests the possibility of the practical utilization of highly
luminescent Cd-chalcogenide QDs (as well as Zn-chalcogenide
QDs) for the facile synthesis of Ag2 S QDs with NIR emission based
on a highly efficient cation exchange reaction.
3.2. Synthesis of Ag2 Se QDs
In this section, we will employ similar approaches (as described
for Ag2 S QDs) to review the methods for synthesizing photolumi-
nescent Ag2 Se QDs. In particular, Table 2 summarizes the important
synthesis parameters and product characteristics. Before the first
 R. Gui et al. / Coordination Chemistry Reviews 296 (2015) 91–124 101

Fig. 5. Synthetic strategy of Ag2 S QDs in cultured HepG2 cancer cells.

Reprinted with permission from Ref. [65], Copyright 2014, American Chemical Society.

report of photoluminescent Ag2 Se NCs or QDs [25], many studies
of Ag2 Se NCs were reported [34,103,104] but they did not exhibit
PL emission, and thus we do not review these studies.
3.2.1. Organic phase synthesis methods
In 2011, Yarema et al. adapted an earlier method for producing
PbSe NCs by replacing the Pb precursor with an appropri-
ate Ag precursor (i.e. silver(I)-trifluoroacetate) [25], where they
used oleylamine as a coordinating solvent and trioctylphosphine
selenide (TOPSe) as the Se source. Previously, this group pro-
posed the concept of quasi-seeded growth by cation-exchange
mediated nucleation. This concept was utilized in the synthesis
of PbSe (Ag2 Se) NCs by employing SnSe (PbSe) intermedi-
ate nuclei [25,105]. In a typical experiment using lithium
bis(trimethylsilyl)amide (Li[N(SiMe3 )2 ]), Ag2 Se NCs were obtained
at <100 ◦ C (ca 70 ◦ C). The synthesis reaction excluded any cation
exchange process from the SnSe nuclei and the Ag2 Se NCs obtained
emitted at ca 1030–1250 nm (NIR-II region), while the PLQY was
1.7%. This was the first example of photoluminescent Ag2 Se NCs.
Langevin et al. employed almost the same method as [25] to pre-
pare ˇ-Ag2 Se QDs, which exhibited a spherical orthorhombic phase
at low temperature with an average diameter of <5.0 nm [107].
Tian et al. described a hot injection method for preparing Ag2 Se
QDs. In experiments, they used 1-octanethiol as a capping lig-
and to efficiently balance the nucleation and growth process in
QDs (Fig. 7A) [50]. Using CH3 COOAg and TOPSe as precursors and
1-octadecene as the solvent, Ag2 Se QDs with tunable PL were
synthesized in the NIR-II biological window range from 1080 to
1330 nm. The PLQY of the QDs reached up to 9.58%. UV–Vis–NIR and
PL spectra were utilized to characterize the optical properties of the
as-prepared Ag2 Se QDs. As the reaction time increased, the Ag2 Se
QDs exhibited red-shift absorption in the range of 770–1070 nm
and red-shift PL emission in the range of 1080–1330 nm. After
replotting in the “Tauc plot” format, the absorption spectra could
be used to calculate the optic band gaps of QDs. The particle sizes
calculated from the “Tauc plot” ((ahv)1/2 vs hv) and the band gap
(Eg (bulk)) of orthorhombic Ag2 Se QDs agreed well with the TEM
results, thereby indicating that the red shifts of absorption by the
Ag2 Se QDs were related to a quantum size effect. In addition, Tian
et al. substituted 11-mercaptoundecanoic acid for 1-octanethiol
on the surfaces of QDs, thereby transferring Ag2 Se QDs from the
organic phase to the aqueous phase by ligand exchange. After the
phase transfer process, the Ag2 Se QDs dispersed well in water
and they retained a PLQY of up to 3.33%. Wang et al. designed
a Ag precursor by dissolving AgNO3 in a mixture of oleylamine
and toluene under heating, where NaHSe was used as the Se pre-
cursor [51]. The two precursors were mixed under stirring and
then heated to 180 ◦ C and aged for 1 h to obtain oil-soluble 1-
dodecanethiol-capped Ag2 Se QDs. After surface ligand exchange
with poly(maleic anhydride-alt-1-octadecene)-poly(ethylene glu-
col) (C18-PMH-PEG), the QDs were transferred to water with a yield
of ca 100% [109]. The Ag2 Se QDs capped by C18-PMH-PEG had a
PLQY of 29.4%.
In organic-phase synthesis methods for Ag2 Se QDs
[25,50,51,107], inorganic silver salts (e.g., CH3 COOAg) can be
used as the Ag precursor to replace harmful organometallic
reagents (e.g., Ag[N(SiMe3 )2 ]). In addition, inorganic NaHSe can be
used to substitute for TOPSe (Se powder dissolved in pyrophoric

Table 2
Comparison of synthetic conditions for the preparation of Ag2 Se QDs with different reaction temperatures (temp.), precursors, solvents, capping ligands, PL emission
wavelengths, diameters and PLQYs.

Precursors Solvents Capping reagents Temp. (◦ C) Emission (nm) PLQY (%) Ref.

Ag(I)-trifluoroacetate, Li[N(SiMe3 )2 ], TOPSe Oleylamine TOP, oleylamine, 70 1030–1250 1.7 [25][107]

CH3 COOAg, TOPSe 1-Octadecene 1-Dodecanethiol 180 1080–1330 9.58, 3.33 [50]
AgNO3 , NaHSe Oleylamine, 1-Dodecanethiol, 180 1300 29.4 [51]
toluene, C18-PMH-PEG
1-dodecanethiol
AgNO3 , l-alanine, Na2 SeO3 , GSH Water GSH 90 700–820 ∼3 [49]
AgNO3 , Na2 SeO3 Water Multidentate Room temp. 966–1228 11.1–12.2 [102]
polymers
102 R. Gui et al. / Coordination Chemistry Reviews 296 (2015) 91–124

Fig. 6. (A) Schematic illustration of aqueous synthesis of NIR-emitting biocompatible Ag2 S QDs through cation exchange of CdS QDs with Ag+ ions. (B) UV–vis absorption
spectra and (C) PL emission spectra of CdS QDs prepared at different reaction times (from A1 to D1 : 30, 60, 120 and 180 min). (D) UV–vis absorption spectra and (E) PL emission
spectra of Ag2 S QDs (from A2 to D2 ) prepared from corresponding CdS QDs (as depicted from A1 to D1 ) via cation exchange.
Reprinted with permission from Ref. [61], Copyright 2014, The Royal Society of Chemistry.

solvent, i.e., TOP) as the Se precursor during synthesis. These unique
properties are advantageous for the organic-phase synthesis of
Ag2 Se QDs, e.g., low cost and non-toxicity. Furthermore, the use of
inorganic precursors promotes the synthesis reaction at a lower
temperature (ca 180 ◦ C) compared with using organometallic
precursors and pyrophoric solvents. After undergoing a phase
transfer, hydrophobic the Ag2 Se QDs prepared in organic phases
(e.g., PLQY of 9.58%) can be converted into hydrophilic QDs (QY
of 3.33%). This indicates that the PLQY of hydrophilic Ag2 Se QDs
decreases markedly after phase transfer. However, after efficient
ligand exchange (surface modification by water-soluble polymers,
e.g., C18-PMH-PEG) rather than substituting hydrophobic surface
ligands with a small molecule (e.g., 11-mercaptoundecanoic acid),
the resulting polymer-capped hydrophilic Ag2 Se QDs can have
high PLQYs (e.g., 29.4%). In summary, the selection of appropriate
precursors, solvents, and reaction temperatures is critical for
obtaining PL Ag2 Se QDs during organic phase synthesis. In partic-
ular, the choice of water-soluble capping ligands has a significant
effect on the production of hydrophilic Ag2 Se QDs with high PLQYs
during phase transfer treatment.
3.2.2. Aqueous phase synthesis methods
The organic phase synthesis of NIR-II-emitting Ag2 Se QDs has
been reported in many studies [25,50,51,107], but the QDs synthe-
sized in organic phases need to be transferred to aqueous phases for
further applications. To avoid additional post-treatments to achieve
water solubilization, direct aqueous synthesis is a better strategy
for obtaining water-dispersible NCs, particularly for biomedical
 R. Gui et al. / Coordination Chemistry Reviews 296 (2015) 91–124 103

Fig. 7. (A): (a) Strategy for preparing Ag2 Se QDs with tunable emission in the second near-infrared window, (b) absorption, (c) PL emission spectra of the as-prepared Ag2 Se
QDs with different reaction times: (a) 5 s, (b) 1 min, (c) 5 min, (d) 10 min, (e) 20 min, (f) 30 min, (g) 45 min and (h) 1 h, (d) PL emission spectra and (e) pictures of Ag2 Se
QDs emitting at 1090 nm before/after ligand exchange (Reprinted with permission from Ref. [50], Copyright 2013, American Chemical Society). (B): (a) Photographic and
schematic illustration of the synthetic procedure of multidentate polymer (MDP)-capping Ag2 Se QDs, (b) TEM, (c) HRTEM micrographs of MDP-capping Ag2 Se QDs with
inserted SAED pattern, (d) EDX spectrum and (e) XRD pattern of Ag2 Se QDs, (f) visible–NIR absorption and (g) emission spectra of MDP-capping Ag2 Se QDs synthesized
with different reaction times corresponding to 0.5, 1, 1.5, 2 and 3 h, excited by a 4880 nm laser, (h) PL lifetime measurements for Ag2 Se QDs, exhibiting a decay time of
135.3 ± 11.5 ns according to monoexponential fitting, (i) PL intensity changes of Ag2 Se QDs and ICG under continuous irradiation of a mercury lamp at a power output of
50 W for 3 h (Reprinted with permission from Ref. [98], Copyright 2014, American Chemical Society).

applications. Pang et al. first developed a strategy for synthesiz-
ing NIR PL-tunable, small (<3 nm), water-dispersible Ag2 Se QDs in a
mimetic biochemical reaction at 90 ◦ C [49]. Based on selenite reduc-
tion from SeO3 2− to GSSeH (with the aid of GSH, NADPH (reduced
nicotinamide adenine dinucleotide phosphate) and GR (glutathione
reductase)), the synthesis of Ag2 Se QDs was achieved using GSSeH
(which can react with heavy metal ions, e.g., Ag+ ions [110]) as the
Se precursor. The Ag2 Se QDs obtained exhibited PL emission over
a wavelength range of 700–820 nm, with a PLQY of ca 3%. Recently,
Tan et al. reported the aqueous synthesis of Ag2 Se QDs at room
temperature using multidentate polymers (poly(acrylic acid)-graft-
mercaptoethylamine) as capping ligands, Na2 SeO3 and AgNO3 as
precursors, and NaBH4 and N2 H4 ·H2 O as promoters (Fig. 7B) [102].
The Ag2 Se QDs exhibited PL emission from 966 to 1228 nm, with
PLQYs of 11.1–12.2%. The average size of the Ag2 Se QDs synthe-
sized with a reaction time of 3 h was 5.9 ± 0.8 nm, according to
TEM images. A HRTEM micrograph showed the lattice fringes of
Ag2 Se QDs with an interplanar spacing of 0.232 nm, which could be
assigned to the (0 1 3) facets of an orthorhombic Ag2 Se (ˇ-Ag2 Se)
crystal. The selected area of an electron diffraction image indicated
the presence of diffraction rings typical of ˇ-Ag2 Se NCs. EDX anal-
ysis indicated the presence of silver, selenium, and sulfur elements
in the MDP-capping Ag2 Se QDs, where the atomic ratio of silver
relative to selenium was similar to the stoichometry of the bulk
Ag2 Se. XPS was employed to analyze the element valence state of
the Ag2 Se QDs. The peaks at 373.82 and 367.59 eV were ascribed to
the core levels of Ag 3d3/2 and Ag 3d5/2 , respectively, thereby sug-
gesting that the oxidation state of silver was univalent in the QDs.
The peak at 54.06 eV was identified as Se 3d, which indicated the
presence of elemental selenium. The XRD pattern verified the QDs
as ˇ-Ag2 Se structures. Both the absorption and emission spectra
exhibited red shifts as the reaction time increased. Thus, by chang-
ing the reaction time to modify the QD size, the NIR-II emissions of
the QDs could be tuned from 966 to 1228 nm. The PL data for the
QDs were fitted to a monoexponential decay model, which indi-
cated a characteristic lifetime of 135.3 ns and this was similar to the
values reported previously for Ag2 Se NC QDs. The photostability of
the Ag2 Se QDs was examined by exposing the QDs to continuous
irradiation by a mercury lamp at ambient temperature. The QDs
retained over 80% of the original PL intensity after irradiation for
104 R. Gui et al. / Coordination Chemistry Reviews 296 (2015) 91–124
3 h, where ICG was almost photobleached within the same period.
These results demonstrate the good chemical stability and photo-
stability of MDP capped-Ag2 Se QDs, which are promising as NIR-II
probes for bioimaging.
Another study [67] also used multidentate polymers as capping
ligands to prepare NIR-emitting Ag2 S QDs, where the utilization of
thiol-based multidentate-polymer ligands yielded high PLQYs for
the Ag2 Se QDs prepared in aqueous solution compared with those
when employing other small molecules or macromolecules, or
thiol-free/-less polymers, as capping ligands. In addition to the high
PLQYs of the Ag2 Se QDs, this study was conducted at room tem-
perature, so the synthesis method (i.e., ambient one-pot aqueous
synthesis) is simpler compared with other aqueous phase synthesis
methods.
3.3. Synthesis of Ag2 Te QDs
Many studies have explored different structural Ag2 Te NCs,
including nano-wires, tubes, rods, and particles [35–41], but only
two have reported photoluminescent Ag2 Te QDs [25,41]. Much
effort has been directed at the development of thermoelectric
properties in Ag2 Te NCs [29,40,111–115], which are probably
attributable to ˇ-Ag2 Te, a known narrow bandgap semiconductor
with high electron conductivity and low lattice thermal conduc-
tivity. These advantages favor the use of Ag2 Te NCs as suitable
room-temperature thermoelectric materials [116,117]. Photolu-
minescent Ag2 Te QDs also yield the low temperature monoclinic
ˇ-phase of Ag2 Te [41]. In 2011, Yarema et al. prepared Ag2 Te NCs
with an average diameter of 3.2 nm, where the PL emissions from
Ag2 Te NCs were found to peak at 1300 nm and they reached up
to 1500 nm [25]. The PL emission properties of Ag2 Te NCs had not
been reported previously. Thus, ca 3.2 nm Ag2 Te QDs were pre-
pared in organic phases with an emission peak at 1300 nm (without
a report of PLQY), which comprised the first example of photo-
luminescent Ag2 Te NCs. Subsequently, Chen et al. demonstrated
facile cation exchange between Ag+ ions and prepared CdTe QDs in
aqueous solution to yield NIR-II-emitting Ag2 Te QDs (Fig. 8) [41].
The Ag2 Te QDs obtained exhibited PL emissions with peak wave-
lengths from 900 to 1300 nm, with a PLQY of 2.1%. This was the
first report of the PLQYs of Ag2 Te QDs. The bulk Ag2 Te semiconduc-
tor with a low temperature ˇ-phase had an optical energy gap of
0.67 eV and the emission wavelengths of the corresponding Ag2 Te
QDs are expected to lie within the second biological window. Fol-
lowing cation exchange and purification, silver and tellurium were
identified as the QD components. Numerous near-monodisperse
spherical particles were observed in low magnification images and
the crystal lattice fringes were identified in HRTEM images. The
hydrodynamic size of the Ag2 Te QDs was determined by DLS. The
XRD patterns of the QDs agreed mostly with the low tempera-
ture monoclinic ˇ-phase of Ag2 Te. The colloidal stability of the
Ag2 Te/ZnS core/shell QDs was evaluated by incubating the QDs
in water, 1× phosphate-buffered saline, and fetal bovine serum
at 37 ◦ C. The PL intensity was recorded at different times and up
to 90% of the PL was preserved after incubation for 72 h, thereby
suggesting that these QDs would be highly stable in bioimag-
ing applications. The photostabilities of Ag2 Te QDs and Ag2 Te/ZnS
core/shell QDs were evaluated by continuously exciting the QDs
with a 405 nm laser (50 mW). Little photobleaching was observed
after continuous excitation of the QDs for up to 120 min, thereby
demonstrating the high capacity of these QDs for long-term imag-
ing and tracking. By contrast, significant photobleaching of ICG
was observed under continuous excitation with a 722 nm laser
(50 mW).
Ag-chalcogenide QDs with relatively low PLQYs have been
reported [25,49], which may be due to the inherent properties of
Ag-based semiconductor NCs. The previously reported PLQYs of
Ag2 Te QDs (only 2.1%) should be improved markedly before they
are suitable for biomedical applications. Unfortunately, current
studies of Ag2 Te NPs (or NCs and QDs) with different nanos-
tructures are focused mainly on their thermoelectric properties.
There have been studies of the synthetic methods and biomedical
applications of Ag2 Te QDs. According to the methods used for syn-
thesizing Ag2 S and Ag2 Se QDs, high PLQYs may be achieved using
thiol-based multidentate polymers as capping ligands during the
aqueous phase synthesis of Ag2 Te QDs.
In contrast to Ag2 X QDs, the PLQYs of other NIR QDs have been
investigated. Composited QDs made of CdTe and HgTe (alloyed
Cdx Hg1−x Te) QDs, which emitted in the visible and NIR spectra,
had a QY of 40–60% [24]. When an outer inorganic shell (ZnS or
CdS) passivated the core-surface states (CdSe QDs), a high PLQY
of up to 80% was obtained [118]. Mao et al. prepared high qual-
ity water-dispersed NIR-emitting CdTeS-alloyed QDs with a PLQY
of 68% [119]. Typically, lead-based NIR QDs (e.g., PbS and PbSe)
yielded high QYs (>70%) for small QDs (1.5–4 nm), but about 20–30%
for larger QDs (5–10 nm) [58]. In particular, the monodisperse PbSe
QDs had a high PLQY of about 85%, which was measured using IR-25
dye as the standard [120,121]. Hines et al. measured a PLQY of 20%
for PbS QDs [14]. InAs QDs had high QYs (35–50%) when a passivat-
ing shell of CdSe, ZnS, ZnSe, or ZnCdS was grown [18,122–124].
Further PLQY data for other NIR QDs were summarized by Ma
et al. (InAs, 2.5%; InAs/CdSe(ZnS, ZnCdS, InP/ZnSe), 19–90%; PbS,
10–26%; CdTe, <20%; CdTe/CdSe(CdS), 8–70%; CdSe/CdTe/ZnSe,
60%; CdTeSe, 37%; CdSeTe/CdS(CdZnS), 10–15%; CdHgTe, <20%;
Mn:CdTe 10–15%; Cu:InP QDs, 20%) [57]. These results show that
the PLQYs of other NIR QDs are generally higher than those of Ag2 X
QDs.
4. Applications of silver chalcogenide QDs
The last few years have seen great improvements in the applica-
tions of narrow bandgap colloidal silver chalcogenide QDs. Various
promising applications of binary Ag2 S, Ag2 Se, and Ag2 Te QDs
have been reported, and their feasibility has been confirmed. The
applications of silver chalcogenide QDs have focused mainly on
bioimaging, chemo-/bio-detection, QDSSCs, and photocatalysis, as
well as in antimicrobial and thermoelectric materials. To review
the previous significant applications of QDs, we divide all of the
applications into six classes and we summarize each class in the
following. Each class includes different silver chalcogenide QDs
and applications. To compare and analyze the different applica-
tions of QDs, we highlight some critical synthesis parameters or
product characteristics of the QDs, including their surface modifi-
cation or assemblies, optical or electronic properties, application
areas, matrices, analytes, and detection limits.
4.1. Silver chalcogenide QDs for bioimaging
Photoluminescent colloidal semiconductor QDs have attracted
increasing attention, especially in high-resolution cellular imag-
ing and long-term in vivo observation of cell trafficking and tumor
targeting [125]. Due to their excellent luminescence performance
and negligible toxicity, silver chalcogenide QDs have potential uses
in bioimaging applications, which have been confirmed widely in
the past decade. To better understand the uses of different silver
chalcogenide QDs in bioimaging applications, we summarize many
of their applications in Table 3, which is based on different surface
modifications, assemblies, and the bioimaging areas or objectives of
the as-synthesized Ag2 S and Ag2 Se QDs. There have been no reports
of bioimaging applications using photoluminescent Ag2 Te QDs, so
they are excluded from the table.
 R. Gui et al. / Coordination Chemistry Reviews 296 (2015) 91–124 105

Fig. 8. (A) Schematic illustration of aqueous synthesis of Ag2 Te QDs and Ag2 Te/ZnS core/shell QDs based on cation exchange of CdTe QDs with Ag+ ions, and photographs of
CdTe QDs (left) and Ag2 Te QDs (right) prepared via cation exchange. Optical characterization of CdTe QDs and Ag2 Te QDs. (B) Absorption spectra of CdTe QDs synthesized
with various reaction times (from bottom to top: 15, 30, 45, 60, 90, and 150 min). (C) Corresponding PL spectra of CdTe QDs. (D) Absorption spectra of Ag2 Te QDs prepared
from CdTe QDs via cation exchange (corresponding CdTe QDs and Ag2 Te QDs are depicted in the same color). (E) PL spectra of Ag2 Te QDs prepared from CdTe QDs via cation
exchange, (F) EDX characterization, (G) low magnification and HRTEM images, (H) hydrodynamic size distributions of Ag2 Te QDs, (I) colloidal stability of Ag2 Te/ZnS QDs in
water, 1× PBS, and fetal bovine serum, (J) photostability of Ag2 Te/ZnS QDs, Ag2 Te QDs and ICG molecules in water.
Reprinted with permission from Ref. [41], Copyright 2013 American Chemical Society.

4.1.1. In vitro and in vivo imaging of silver chalcogenide QDs
Since the first report of photoluminescent Ag2 S QDs synthesis
by Wang et al. in 2010 [26], there have been many applications
of silver chalacogenide QDs in bioimaging. We divide the appli-
cations of Ag2 S QDs into three groups. The first group appeared
in 2012 [20,42,44,45], while the second and third groups were
reported in 2013 [46,60,61,127] and 2014 [48,69,126,128–130],
respectively. For Ag2 Se QDs, only three studies have reported imag-
ing applications, i.e., in 2012 [49], 2013 [51], and 2014 [102]. In this
section, we highlight the in vitro and in vivo imaging applications of

Table 3
Comparisons of different surface modifications, assemblies and bioimaging areas of synthesized Ag2 S and Ag2 Se QDs.

Synthesized QDs Surface modifications or assembles Bioimaging areas Ref.

Ag2 S QDs Capped with DHLA, conjugated with Erbitux/RGD Imaging in MDA-MB-468/U87 MG cells [20]
Ag2 S QDs Capped with DHLA, conjugated with 6PEG Imaging in a xenograft 4T1 tumor of mice [42]
Ag2 S QDs Capped with 3-MPA Imaging in nude mice [44]
Ag2 S QDs Capped with GSH Imaging in MC3T3-EI cells [45]
Ag2 S QDs Capped with BSA, conjugated with antiVEGF Imaging in U-87 MG tumor-bearing mice [46]
Ag2 S QDs Capped with GSH, conjugated with CS-SNO Imaging in L929 cells [60]
Ag2 S QDs Capped with GSH, conjugated with SNO Imaging in L929 cells and nude mice [61]
Ag2 S QDs Capped with DHLA, PEGylated QDs Imaging in tumor-bearing Balb/c mice [127]
Ag2 S QDs Conjugated with PEG, labeled with hMSCs Imaging tracking in living mice [48]
Ag2 S QDs Capped with GSH Imaging in HepG2 cells [69]
Ag2 S QDs Capped with 3-MPA Imaging in MCF-7 cells [126]
Ag2 S QDs Capped with DHLA, PEGylated QDs Imaging in lymphatic drainage of nude mice [128]
Ag2 S QDs Capped with GSH, conjugated with CS and RBS Imaging in L9292 cells and nude mice [130]
Ag2 S QDs Capped with 3-MPA, conjugated with cRGD, DOX and DOX-cRGD Imaging in U87 cells and MDA-MB-231 tumor-bearing mice models [129]
Ag2 Se QDs Capped with 1-dodecanethiol and C18-PMH-PEG Imaging in L929 cells and hMSCs [51]
Ag2 Se QDs Capped with GSH Imaging in nude mice [49]
Ag2 Se QDs Capped with multidentate polymers Imaging in nude mice [102]
106 R. Gui et al. / Coordination Chemistry Reviews 296 (2015) 91–124
photoluminescent Ag2 S and Ag2 Se QDs, as well as describing some
significant studies to facilitate their understanding.
4.1.1.1. In vitro imaging of Ag2 S QDs. Wang et al. first reported a
new type of NIR Ag2 S QDs in 2010 [26] and they also reported the
molecular imaging of living cells using Ag2 S QDs as a novel NIR-II
PL probe in 2012 [20]. Wang et al. synthesized DHLA-capped Ag2 S
QDs, which were then conjugated with cetuximab (Erbitux) pro-
tein or with cyclic arginine-glycine-aspartic acid (RGD) to yield
DHLA-Ag2 S QDs/Erbitux or DHLA-Ag2 S QDs/RGD conjugates for
targeted NIR-II PL imaging applications in human breast cancer cell
lines (MDA-MB-468), or human glioblastoma cell lines (U87 MG)
(Fig. 9A). These two cell lines have very different expression levels
of two types of membrane receptor, i.e., epidermal growth factor
receptor (EGFR) and ˛v ˇ3 integrin, which correspond to MDA-MB-
468 and U87 MG, respectively [131,132]. Both the EGFR-positive
MDA-MB-468 cell lines treated with DHLA-Ag2 S QDs/Erbitux con-
jugates and the ˛v ˇ3 -positive U87 MG cell lines treated with
DHLA-Ag2 S QDs/RGD conjugates exhibited high NIR PL signals
(red-white), whereas the corresponding negative groups produced
virtually no signal. In addition, very little NIR-II PL was observed
in both cell lines using the negative controls with uncoated DHLA-
Ag2 S QDs. These results demonstrate that Ag2 S QDs can be utilized
for selective cell targeting in imaging applications by acting as effi-
cient NIR-II nanoprobes with a high PL intensity. Furthermore, Ag2 S
QDs can be functionalized further to obtain biologically active or
inert surface coatings for specific targets.
Many studies have investigated the in vitro imaging appli-
cations of Ag2 S QDs with functionalized surface modifications.
The as-synthesized Ag2 S QDs were capped by thiol-based small
molecules (e.g., DHLA, 3MPA, or GSH) and then conjugated further
with biomacromolecules (e.g., Erbitux, RGD, BSA, or antiVEGF) or
biocompatible polymers (e.g., PEG, C18-PMH-PEG, or multidentate
polymers), or they were assembled with functional compositions
(e.g., chitosan (CS), S-nitrosothiol (SNO), doxorubicin (DOX), or
Fe4 S3 (NO)7 − (RBS)) to fabricate advanced carrier systems for use in
the in vitro PL imaging tracking of drug release. Surface-modified
or functionalized Ag2 S QDs have been applied successfully to the
in vitro imaging of some cancer cell lines, including MC3T3-EI, MCF-
7, L929, and HepG2 cells. In a typical study from 2013 [60], Tan et al.
designed interesting nanospheres, which comprised CS-based SNO
and encapsulated Ag2 S QDs. The nanospheres incubated in L929
cells exhibited bright NIR PL and satisfactory photostability under
NIR irradiation (Fig. 9B). This system allows NIR-excitation to NIR-
emission, and thus it is appealing for in vitro imaging. The utilization
of NIR-excitation to NIR-emission can effectively avoid potential
interference from internal autofluorescence (or background PL),
thereby allowing penetration to high depths in tissues (or organs),
as well as minimizing the harm to cells [133].
4.1.1.2. In vivo imaging of Ag2 S QDs. Yan et al. fabricated BSA-
stabilized Ag2 S QDs in aqueous solution via a one-pot synthetic
method. The QDs obtained were then bioconjugated with anti-
VEGF for targeted in vivo cancer imaging (Fig. 10A) [46]. The PL
signals derived from antiVEGF-Ag2 S QDs appeared in tumors after
30 min post-administration and the NIR PL signal in tumors was still
detected at 24 h post-administration. The highly specific targeting
ability of anti-VEGF-Ag2 S QDs for VEGF-positive U-87 MG tumors
allowed the long-term retention of the QDs in tumor sites [134]. The
clearance rate of anti-VEGF-Ag2 S QDs in tumor-bearing mice was
much slower than that in normal mice because the high affinity
of anti-VEGF for tumors prevented the QDs from being metabo-
lized. In addition to intense NIR PL emission, the ultra-small size
and ultra-low in vivo toxicity facilitated the successful application
of anti-VEGF-Ag2 S QDs to the targeted imaging of VEGF-positive U-
87 MG human glioblastoma tumor-bearing mice. Moreover, NIR PL
Ag2 S QDs (660–840 nm) may have great potential after conjugation
with other functional biomolecules, thereby serving as a versatile
molecular probe platform for in vivo cancer imaging.
PL imaging in the NIR-II (1000–1400 nm) region is more
desirable than that in the visible (450–750 nm) and traditional
NIR-I (750–900 nm) regions because of reduced photon scattering,
deeper tissue penetration, and lower autofluorescence [135–137].
Before the first report of Ag2 S QDs as a new generation of NIR-II
fluorophores [42], single-walled carbon nanotubes (SWNTs) were
the only class of NIR-II fluorophores [138]. However, the relatively
low PLQYs and poor biocompatibility of SWNTs limited their appli-
cations to in vivo imaging with sufficient temporal resolution [131].
Dai et al. reported DHLA-capped Ag2 S QDs conjugated with 6PEG
for NIR-II PL imaging of a xenograft 4T1 tumor [42]. Fig. 10B shows
the time-course of NIR-II PL images of the same mouse injected with
6PEG-Ag2 S QDs over a long period of time (up to 24 h) after inject-
ing via the tail vein. Given the enhanced permeability and retention
effect in the tumor vasculature [139], there was a steady increase in
NIR-II PL from 6PEG-Ag2 S QDs in tumor regions, and a decrease in
NIR-II PL from other organs and skin between 30 min post-injection
and 24 h post-injection, thereby resulting in an increased tumor-to-
background ratio (TBR) over time. The TBR was well above the Rose
criterion for 4–24 h post-injection, thereby facilitating the posi-
tive imaging and detection of tumors [140]. Visual inspection of
the same mouse indicated the high uptake of Ag2 S QDs in tumor
areas, which darkened after the accumulation of QDs at 24 post-
injection. These experimental results suggest that biocompatible,
heavy metal-free 6PEG-Ag2 S QDs can be used as an imaging con-
trast agent with bright PL in the NIR-II biological window, thereby
yielding deep inner organ registration, dynamic tumor contrast,
and fast tumor detection.
In addition to the two studies mentioned above, many applica-
tions of Ag2 S QDs have been reported in in vivo imaging. In general,
the Ag2 S QDs employed were capped by 3-MPA (or GSH, DHLA, etc.)
or conjugated with PEG (or CS, RGD, etc.) for imaging applications in
tumor-bearing mice. These studies also confirmed the feasibility of
using functionalized Ag2 S QDs for in vivo imaging due to their high
brightness, the photochemical stability of NIR PL, and ultralow tox-
icity in small living animals. After conjugation with specific units
(e.g., Erbitux, RGD, or VEGF), NIR-emitting Ag2 S QDs can be used
for targeted in vivo imaging in tumor-bearing mice, thereby indi-
cating their biomedical potential, especially as promising imaging
contrast agents.
4.1.1.3. In vivo imaging and real-time tracking. In vivo imaging
tracking and the real-time visualization of tissues, organs, or
labeled cells in living mice can improve our understanding of cir-
culation system-related physiological and pathological processes,
as well as yielding clinical diagnostics and therapy. NIR-II emit-
ting agents (e.g., SWNTs and Ag2 S QDs) have been used successfully
for imaging mouse hind limb vasculatures and tumor detection at
an ultrahigh spatial resolution of 30 ␮m and a temporal resolu-
tion of <50 ms, which is not possible using traditional PL imaging
or tomographic imaging, such as magnetic resonance imaging and
position emission tomography. Recently, Wang et al. reported the
in vivo real-time visualization of tissue blood flow and angiogen-
esis by using Ag2 S QDs that emitted in the NIR-II window [128].
After subcutaneous injection with PEGylated Ag2 S QDs into a foot-
pad, time-course NIR-II PL imaging was performed in the lymphatic
drainage of nude mice, where the lymph nodes and vessel anatomy
observed with QDs were much sharper due to the reduced scat-
tering and absorbance of photons in the NIR-II window. The ideal
penetration depth with high feature fidelity indicates the potential
use of Ag2 S QDs in providing direct visual guidance to surgeons
throughout the entire sentinel lymph node mapping procedure,
thereby minimizing inaccuracies during incision and dissection. In
 R. Gui et al. / Coordination Chemistry Reviews 296 (2015) 91–124 107

Fig. 9. (A) In vitro targeted cellular imaging. NIR-II PL images (1100–1700 nm) of MDA-MB-468 and U87 MG cells treated with DHLA-Ag2 S QD/Erbitux conjugates (A, C)
and their corresponding optical images (B, D); NIR-II PL images (1100–1700 nm) of MDA-MB-468 and U87 MG cells treated with DHLA-Ag2 S QD/RGD conjugates (E, G) and
their corresponding optical images (F, H). Erbitux ligand specifically binds to MDA-MB-468 cells, and RGD peptide ligand specifically binds to U87 MG cells. NIR-II images
were taken with exposure time of 300 ms, and optical images with exposure time of 2 ms. Scale bars are 25 ␮m (Reprinted with permission from Ref. [20], Copyright 2012,
American Chemical Society). (B) Bright-field image (a), NIR PL image acquired immediately upon 808 nm irradiation (b), NIR PL image acquired 3 h after 808 nm irradiation
(c), and dark-field image without irradiation (d) of L929 cells incubated with 0.1 mg/mL Ag2 S-CS-SNO nanospheres for 5 h. CLSM images (488 nm excitation) of NO detection
of CuFL stained cells without Ag2 S-CS-SNO nanospheres (e) and containing Ag2 S-CS-SNO nanospheres (f). NIR image (g) and merged image (CLSM and NIR) (h) of CuFL stained
cells containing Ag2 S-CS-SNO nanospheres (Reprinted with permission from Ref. [56], Copyright 2013, American Chemical Society).

addition, time-course NIR-II PL imaging of the blood flow was con-
ducted in nude mice after injecting PEGylated Ag2 S QDs, which
allowed deep organs such as the heart, lungs, liver, spleen, and
kidney to be observed clearly. To allow the in vivo real-time visu-
alization of tumor-induced angiogenesis, NIR-II PL images of the
4T1 mammary tumor-bearing mice were acquired 30 min after post
tail-vein injection of the QDs on days 5, 8, 15, and 21 after 4T1 tumor
transplantation. In the early tumor stages, an increase in the PL
signal occurred mainly at the periphery of the tumor. With the con-
tinuous growth of the 4T1 tumor, abundant irregularly branched
blood vessels were formed around the tumor, which exhibited the
typical characteristics of tumor blood vessels.
Furthermore, NIR-II-emissive Ag2 S QDs were employed for
dynamically tracking human mesenchymal stem cells (hMSCs) in
vivo with high sensitivity and high spatiotemporal resolution [48].
First, Ag2 S QDs were conjugated with Tat peptide as ligands for
targeting hMSCs. Fig. 11 shows the time-course of in vivo NIR PL
imaging. In mice with acute liver failure, bright NIR PL was observed
clearly in the lung and liver, without requiring laparotomy, after
the transplantation of Ag2 S QD-labeled hMSCs via tail vein injec-
tion. The NIR PL images could be obtained with an exposure time of
100 ms, thereby allowing real-time in vivo imaging of Ag2 S QDs.
Heparin helps the hMSCs to pass through the capillaries in the
lung and to accumulate in liver, which contributes to liver failure
during treatment, so long-term monitoring of the translocation of
hMSCs in mice was performed for up to 14 days. PL imaging in the
NIR-II region allowed penetration to the desired tissue depth due
to negligible photon scattering and minimal autofluorescence. The
experimental results demonstrated the potential use of Ag2 S QDs in
long-term, noninvasive, in vivo stem cell tracking in living animals
with high spatiotemporal resolution and high sensitivity, which
may encourage further clinical applications in imaging-guided cell
therapies.
4.1.1.4. In vivo imaging of Ag2 Se QDs. Pang et al. described
the quasi-biosystem synthesis of NIR-emitting Ag2 Se QDs and
studied the potential use of NIR Ag2 Se QDs in bioimaging
[49]. The results obtained using 3-[4,5-dimethylthiazol-2-yl]-2,5-
diphenyltetrazolium bromide (MTT) in a standard cell viability
assay demonstrated that the Ag2 Se QDs were relatively low cyto-
toxicity and environmentally friendly NIR nanomaterials (Fig. 12A).
After injecting the Ag2 Se QDs into the abdominal cavities of
108 R. Gui et al. / Coordination Chemistry Reviews 296 (2015) 91–124

Fig. 10. (A) Time-dependent NIR PL imaging in vivo. U-87 MG tumor bearing mice were intravenously injected with antiVEGF-Ag2 S QDs (A) or BSA stabilized Ag2 S QDs (B).
The normal nude mice were intravenously injected with antiVEGF-Ag2 S QDs (C). The pink circle in the image indicates the tumor site (Reprinted with permission from Ref.
[46], Copyright 2013, The Royal Society of Chemistry). (B) NIR-II PL imaging of a xenograft 4T1 tumor with high uptake of 6PEG-Ag2 S QDs. (a–e) Time course of NIR-II PL
images of the same mouse injected with 6PEG-Ag2 S QDs. These results were reproduced with a total of three mice. (f) A white-light optical image of the same mouse at 24 h
p.i. The tumor mass was visibly darkened owing to high uptake of 6PEG-Ag2 S QDs (Reprinted with permission from Ref. [42], Copyright 2012, Wiley-VCH).

living nude mice, NIR images could be obtained from the back of
the mouse, where the QDs allowed a penetration depth of ≥1 cm.
In addition, little autofluorescence was observed in the nude mice.
C18-PMH-PEG conjugated Ag2 Se QDs have bright PL, good water
solubility, high colloidal photostability, and good biocompatibil-
ity [51], so Wang et al. employed these QDs for the deep in vivo
imaging of organs and vascular structures with high spatial resolu-
tion (Fig. 12B) [51]. The in vivo images of C18-PMH-PEG capped
Ag2 Se QDs were obtained from live mice in a supine position
after injecting QDs via the tail. The liver, spleen, and vascular net-
work in whole mice were visualized clearly within a few minutes
post-injection under 808-nm light illumination. The Ag2 Se QDs
preferentially associated throughout the large and small vessels.
Due to the NIR-II PL emission (at 1300 nm), the minimal autoflu-
orescence, and low absorption and scattering yielded an adequate
maximum penetration depth for deep tissue imaging with high fea-
ture fidelity, thereby allowing the imaging of organs located deep in
body, such as the liver and spleen. Furthermore, the high-ordered
branches of blood vessels could be well defined with high spatial
resolution. Thus, C18-PMH-PEG capped Ag2 Se QDs are very promis-
ing for the real-time visualization of in vivo vascular structures
and vascular-related disease imaging, especially for evaluating the
ischemic necrosis of tissues and organs after transplantation and
for screening antiangiogenic drugs.
Recently, Tan et al. reported the aqueous synthesis of multiden-
tate polymer-capped Ag2 Se QDs, which were employed for in vivo
imaging in nude mice (Fig. 12C) [102]. The Ag2 Se QDs were admin-
istered to anesthetized nude mice via tail vein injection. Under
irradiation with an 808 nm laser, the NIR-II PL signals derived from
the QDs were observed to be distributed in several body regions via
the blood circulation. The readily detectable NIR-II signals and the
good contrast in the images obtained may facilitate applications
in diagnosis and treatment monitoring. Most of the injected QDs
were accumulated in the liver, spleen, and blood at 7 days post-
injection. There were no noticeable differences between the mice
treated with QDs and untreated mice, so the Ag2 Se QDs were con-
firmed to have ultralow toxicity, and thus they could be applied
safely to the in vivo imaging of small living animals.
4.1.2. Toxicity assessment of silver chalcogenide QDs
During the past few years, concerns about the toxicity of
QDs have been a major obstacle to the translation of QDs into
 R. Gui et al. / Coordination Chemistry Reviews 296 (2015) 91–124 109

Fig. 11. In vivo tracking of intravenously injected hMSCs in mice. (A) The time course of the in vivo NIR PL images of a healthy mouse after transplantation of Ag2 S QDs-
labeled hMSCs and a mouse with acute liver failure after transplantation of Ag2 S QDs-labeled hMSCs in combination with heparin at different times (20 min–14 days). (B)
Higher magnification NIR PL image of mice transplanted with hMSCs only after 2 h. (C) Higher magnification NIR PL image of liver failure mice transplanted with hMSCs in
combination with heparin after 2 h.
Reprinted with permission from Ref. [48], Copyright 2014, Wiley-VCH.

clinical research and applications [71]. In vitro nanotoxicity eval-
uations assess toxicity based on the effect of nanomaterials on
cultured cells, and it is extremely important to determine the
potential toxicity and underlying mechanism before administer-
ing QDs to any animal subjects [71]. Thus, QDs must exhibit a
degree of biocompatibility and safety prior to in vivo studies. In
general, in vitro cytotoxicity refers to toxicity at the cellular level
due to the interaction of QDs with the cell membrane, intracel-
lular constituents, or organelles [28]. The intracellular uptake of
QDs could disrupt the oxidative balance in cells and cause oxidative
stress, where the reactive oxygen species (ROS, such as superoxide,
hydroxyl radicals, peroxide radicals, hydrogen peroxide, and singlet
oxygen) produced can have adverse effects on cellular functions. At
a high level of oxidative stress, the antioxidant defense system is
overwhelmed by excessive ROS, thereby leading to mitochondrial
malfunction and apoptosis. High ROS levels can disrupt the func-
tion of DNA, as well as causing DNA fragmentation, double-strand
DNA breakage, and the suppression of DNA functions (e.g., replica-
tion and transcription) due to oxidative stress, as well as causing
genotoxicity.
In vivo studies using small animal models must consider the
entire spectrum of biological interactions in living organisms. These
are the natural next step (after in vitro testing) when evaluating
and understanding the toxicity of QDs. Related experiments can
measure the overall effect (e.g., cytotoxicity and organo-toxicity)
on an entire organism. In vivo toxicity can be organ-specific and its
manifestation may depend on the mode of introduction for QDs,
or the specific organs targeted [71]. During systemic delivery, QD
formulations are introduced into the bloodstream directly. High
blood flow organs (e.g., the liver and spleen) are the main sites of
QD uptake [71]. In addition, the translocation of QDs to secondary
organs and tissues (not targeted) may also cause toxicity.
4.1.2.1. In vitro toxicity assessment of silver chalcogenide QDs. Many
studies have addresses the in vitro toxicity of silver chalcogenide
QDs before their biomedical applications. Thus, the viabilities of
MC3T3-EI cells after incubation for 24 or 48 h with different concen-
trations (5–50 ␮g mL−1 ) of GSH-capped Ag2 S QDs in cell medium
were determined in standard MTT assays [45]. The viability of the
MC3T3-EI cells remained >80% after 48 h incubation with QDs, even
at concentrations up to 50 ␮g mL−1 . This is much higher than the
concentration used during incubation and the time required for
cellular imaging.
Cell proliferation reflects the increase in cell numbers due to cell
growth and division, and this is a fundamental method for assessing
the impact of toxicants on cell health and genotoxicity [20]. Dai et al.
determined the effects of DHLA or PEGylated-DHLA capped Ag2 S
QDs on L929 cell proliferation after treatment for 72 h [20], which
showed that the two types of QDs did not interfere with cell prolif-
eration, and thus they are suitable for use during in vitro labeling. By
contrast, the proliferation of L929 cells was disrupted severely by
the addition of CdSe@ZnS QDs in the same conditions used for Ag2 S
QDs. These results illustrate the biocompatible nature of Ag2 S and
the lack of side effects on cell proliferation. In addition, flow cytom-
etry data showed that the Ag2 S QDs (6.25–100 ␮g mL−1 ) exhibited
negligible cytotoxicity in terms of apoptosis and necrosis induction
in L929 cells after treatment for 72 h, while negligible amounts of
ROS were produced compared with the control groups. The geno-
toxicity induced by Ag2 S QDs was detected with a single-cell gel
electrophoresis assay (comet assay), which is a well-established,
simple, versatile, and sensitive tool for the quantitative assessment
of DNA damage in individual cell populations [141]. There were
no statistically significant differences in both the tail length and
tail moment when L929 cells were treated with Ag2 S QDs. These
results show that Ag2 S QDs are highly biocompatible because the
110 R. Gui et al. / Coordination Chemistry Reviews 296 (2015) 91–124

Fig. 12. (A) MTT assay and NIR images of a living nude mouse after injection of Ag2 Se QDs: (a) MTT assay on A549, Vero, and MDCK cells exposed to Ag2 Se QDs at different
concentrations from 0 to 47.4 ␮g mL−1 for 24 h; (b) PL image of nude mouse; (c) PL imaging from abdominal cavity of nude mouse with Ag2 Se QDs injected into abdominal
cavity; (d) PL imaging on the back side of nude mouse with Ag2 Se QDs injected into abdominal cavity; (e, f) merged images of bright-field and threshold false color of (c) and
(d) (Reprinted with permission from Ref. [49], Copyright 2012, American Chemical Society). (B) Scheme for C18-PMH-PEG polymer coating on the surface of DT-Ag2 Se QDs.
PL image of C18-PMH-PEG-Ag2 Se QDs suspended in water at a concentration of 0.6 mg/mL, absorbance and PL spectra of the QDs in water, and in vivo imaging of live mice
in supine position by tail injection of 200 ␮L of the QDs (0.6 mg/mL) (Reprinted with permission from Ref. [51], Copyright 2013, American Chemical Society). (C) Bright-field
images (a), in vivo PL images (b), and overlay images (c) of a nude mouse at 12 h after tail vein injection of MDP-capping Ag2 Se QDs. (d) ICP-MS analysis of blood, lymph, and
four major organs of the mice sacrificed at different time points after injection of the QDs. The error bars indicate plus and minus 1 standard deviation of the measurements
for five treated mice. (e) Body mass of the mice treated with the QDs (red) and of untreated mice (black) over 20 days (Reprinted with permission from Ref. [98], Copyright
2014, American Chemical Society).

experimental results in terms of cell proliferation, apoptosis, necro-
sis, ROS, and DNA damage demonstrated the negligible toxicity of
Ag2 S QDs, even at a concentration of 100 ␮g mL−1 .
Cytotoxicity assays of Tat-Ag2 S QDs for hMSCs were performed
by Wang et al. [48], where Fig. 13 shows that there were no
significant differences in hMSCs treated with Tat-Ag2 S QDs at con-
centrations ranging from 0 to 50 ␮g mL−1 . No observable delay
effect of Ag2 S QDs on the long-term proliferation of hMSCs was
observed at up to 14 days, which indicates the lack of side
effects from Tat-Ag2 S QDs on cell proliferation. The hMSCs treated
with ROS as the positive control exhibited high intensity 20,70-
dichlorofluorescein (DCF) fluorescence, whereas hMSCs treated
with Tat-Ag2 S QDs produced much less DCF fluorescence, thereby
demonstrating that minimum ROS levels were induced by treat-
ment with Tat-Ag2 S QDs. There were also no marked increases
in apoptosis and necrosis in Tat-Ag2 S QDs-treated hMSCs, which
further supports the good biocompatibility of Ag2 S QDs. Further-
more, the tail DNA length and moment levels in the Tat-Ag2 S
QD-treated or untreated hMSCs were quite similar, and they were
both much lower than those in the positive control treated with
H2 O2 . These results indicate the negligible genotoxicity of Tat-Ag2 S
QDs in hMSCs.
Pang et al. evaluated the cytotoxicity of GSH-capped Ag2 Se QDs
obtained by quasi-biosystem synthesis [49], where MDCK cells
(normal kidney cells from a cocker spaniel), Vero cells (normal
kidney cells from an African green monkey), and A549 cells (lung
carcinoma cells) were exposed to Ag2 Se QDs (0–47.4 ␮g mL−1 ),
thereby examining the effects of Ag2 Se QDs on cell viability.
Approximately 97% of the MDCK cells, 96% of the Vero cells, and
100% of the A549 cells remained viable after being exposed to
the QDs for 24 h, which suggests that these QDs were relatively
less cytotoxic, and thus they are environmentally friendly NIR
nanomaterials. Wang et al. performed cytotoxicity assays with C18-
PMH-PEG-Ag2 Se QDs [51] using mouse fibroblast L929 cells and
hMSCs, where MTT assays showed that both the L929 cells and
hMSCs remained viable after culture with C18-PMH-PEG-Ag2 Se
QDs at different concentrations. The populations of L929 cells and
hMSCs affected by apoptosis and necrosis remained constant, and
they did not differ significantly from those in the control group,
which was not treated with Ag2 Se QDs, thereby demonstrating the
negligible cytotoxicity of C18-PMH-PEG-Ag2 Se QDs.
The bioimaging of photoluminescent Ag2 Te QDs has not been
reported previously, but cytotoxicity measurements using Ag2 Te
QDs were obtained by Chen et al. [41]. The cytotoxicities of the as-
prepared Ag2 Te QDs and Ag2 Te/ZnS core/shell QDs were evaluated
in HeLa cells using MTT assays. Negligible effects on the viability of
HeLa cells were observed after incubation for 24 h with two types of
QDs at different concentrations (50, 100, or 200 nM). These results
confirm that the Ag2 Te QDs are nontoxic to human cells and they
may be useful for bioimaging applications.
4.1.2.2. In vivo toxicity assessments of silver chalcogenide QDs. Wang
et al. investigated the long-term in vivo biodistribution and phar-
macokinetics of PEGylated-Ag2 S QDs and performed a systematic
evaluation of the potential toxicity of Ag2 S QDs over time [127].
PEGylated-Ag2 S QDs were distributed extensively in different
organs and tissues at 1 day post-injection (Fig. 14). The reticu-
loendothelial system (RES) (including the liver and spleen) retained
 R. Gui et al. / Coordination Chemistry Reviews 296 (2015) 91–124
Fig. 13. Cytotoxicity assays of Tat-Ag2 S QDs for hMSCs. (A) Cell proliferation, (B) ROS generation, (C) apoptosis and necrosis, and (D) DNA damage assays of hMSCs treated
with 0, 6.25, 12.5, 25, and 50 ␮g mL−1 of Tat-Ag2 S for 24 h. Rosup (50 ␮g mL−1 ) and H2 O2 (10 ␮M) treated cells were used as positive controls in ROS and DNA damage assays,
respectively. Data are expressed as mean ± standard error of three determinations.
Reprinted with permission from Ref. [48], Copyright 2014, Wiley-VCH.
higher concentrations of QDs. The retention of QDs in most organs
and tissues reduced monotonically after injection, but the QDs were
retained in the liver and spleen, where the concentration of Ag2 S
QDs peaked at about 7 days post-injection. Most of the QDs injected
into mice were cleared from the body at 60 days post-injection
and only small amounts of Ag2 S remained in the liver, spleen, skin,
bones, and intestine. These accumulations in the liver and spleen
may have been due to the high initial uptake of QDs because of
their RES localization, and the slow metabolism of QDs. In par-
ticular, the initial concentration of QDs in the intestine was low
but it increased gradually until the third week, which may have
been due to the excretion of Ag2 S QDs via the biliary pathway. To
understand the pharmacokinetics of Ag2 S QDs, their concentrations
were measured in the blood over time after the intravenous injec-
tion of QDs into Balb/c mice at a dose of 15 mg kg−1 . The blood
circulation curve indicated that the QDs had a blood circulation
half-life of 3.66 h, thereby suggesting that PEGylated-Ag2 S QDs
provided better surface passivation, and thus the Ag2 S QDs had
optimal biological inertia to resist opsonization and nonspecific
binding with proteins in vivo [142–144]. Measurable concentra-
tions of the QDs were detected in urine and fecal samples, which
suggests that Ag2 S QDs clearance probably occurs via renal and fecal
excretion routes. The QD concentrations in the feces were always
much higher than those in the urine, so the excretion of QDs via the
biliary pathway into the feces was the main clearance pathway after
accumulation in the RES. Necropsies were performed to assess the
toxicity of PEGylated-Ag2 S QDs in treated mice, where the experi-
mental results confirmed the absence of obvious hydropic damage
or lesions in slices (stained with H&E) obtained at different time
111
points post-injection with QDs. Overall, there was no evidence of
histopathological abnormalities or lesions in the PEGylated-Ag2 S
QD-treated mice even at a dose of 30 mg kg−1 .
Serum biochemistry analysis also plays an important role in
the evaluation of organ functions. To estimate the potential toxic
effects of PEGylated-Ag2 S QDs in treated mice, blood biochemistry
analysis was performed by Zhang et al. [127] based on 10 differ-
ent parameters. Mice were injected with QDs (15 and 30 mg kg−1 )
and sacrificed at 1–60 days post-injection to collect blood samples.
The experimental results suggested that all of the biochemistry
parameters determined in two sets of treated mice exhibited sim-
ilar trends compared with the control groups of untreated mice,
and thus they remained normal. No obvious hepatic or renal toxic-
ity was observed after treatment with PEGylated-Ag2 S QDs, even at
an overloaded dose of 30 mg kg−1 . Moreover, a series of hematol-
ogy markers were used to perform hematological assessments of
mice treated with PEGylated-Ag2 S QDs, where declines in platelets
and white blood cells could be attributable to macrophages inhibit-
ing or damaging platelets during the acute immune reaction after
the administration of Ag2 S QDs. Based on hematological assays, it
was concluded that PEGylated-Ag2 S QDs had no appreciable toxic
effects in Balb/c female mice at doses of 15 and 30 mg kg−1 . Similar
in vivo toxicity assays of Ag2 S QDs (in Ref. [127]) have been reported
(e.g., [42,48]). Related experimental analyses of in vivo pharmacoki-
netics, biodistribution, and toxicology have shown that Ag2 S QDs
should be sufficiently safe and efficient for in vivo imaging in the
NIR-II biological window.
The distributions of multidentate polymer-capped Ag2 Se QDs in
the major organs, blood, and lymph of nude mice were evaluated
112 R. Gui et al. / Coordination Chemistry Reviews 296 (2015) 91–124

Fig. 14. (A) Long-term biodistribution of PEGylated-Ag2 S QDs in female Balb/c mice injected at a dosage of 15 mg kg−1 body weight. Error bars were based on standard
deviations of 3 mice per group. Pharmacokinetics of the QDs. (B) Blood circulation curve of the QDs. Circulation half-life is determined to be 3.66 h by fitting the data to a
first-order exponential decay. (C) Concentrations of the QDs in urine and feces over two months after injection. Error bars were based on standard deviations of 3 mice per
group. (D) Representative H&E stained images of major organs including liver, spleen, and kidney collected from the control untreated mice and the injected mice at various
time points p.i. Dose of the QDs was 30 mg kg−1 . No obvious organ damage or lesion was observed for the QDs treated mice.
Reprinted with permission from Ref. [115], Copyright 2013, Elsevier.

over 2 weeks [102], which showed that most of the injected Ag2 Se
QDs accumulated in the liver, spleen, and blood at 7 days post-
injection. As the time increased, the QDs were metabolized and the
silver levels decreased in the bodies of mice. The weights of nude
mice injected with QDs and untreated mice were also traced over
the course of 20 days, which showed that the two groups of mice
had similar weights with no noticeable differences. The treated
mice did not exhibit other toxicity responses (e.g., abnormal behav-
ior), thereby demonstrating the ultralow toxicity of multidentate
polymer-capped Ag2 Se QDs. No other studies have reported in vivo
toxicity assessments.
4.1.3. Bioimaging of Ag2 S QDs in drug delivery
Recently, Chen et al. reported the simultaneous use of photolu-
minescent Ag2 S QDs in therapeutic and imaging applications [129].
DOX and cyclic RGD peptide (cRGD) were covalently attached to
the synthesized Ag2 S QDs to fabricate Ag2 S-cRGD-DOX conjugates,
which overcame the unfavorable differences in the biodistribu-
tion and selectivity of distinct imaging and therapeutic agents
(Fig. 15A). U87 cells were subjected to in vitro imaging after incuba-
tion with Ag2 S-DOX or Ag2 S-DOX-cRGD for 1, 2, and 4 h. Compared
with Ag2 S-DOX, Ag2 S-DOX-cRGD exhibited stronger PL in U87 cells
(which have high expression levels of ˛v ˇ3 receptors). In addition,
in vivo imaging of Ag2 S-cRGD or Ag2 S-DOX-cRGD was performed
regularly in MDA-MB-231 tumor-bearing mice. The effective inhi-
bition of tumors was demonstrated using Ag2 S-DOX-cRGD at
both the cell and whole animal levels. These experimental results
confirm that Ag2 S QDs have potential applications in imaging,
including visible nano-therapeutics and other therapeutic appli-
cations.
Tan et al. designed photoluminescent Ag2 S QDs-based nanocar-
riers as nitric oxide (NO) delivery systems. As shown in Fig. 15B,
GSH-capped Ag2 S QDs were conjugated with S-nitrosothiols (SNO)
to generate Ag2 S-GSH-SNO hybrid NPs [61]. These NPs could
release NO under UV or visible light irradiation, as well as emit-
ting NIR PL under NIR light excitation (for bioimaging). Cell (in vitro)
and whole-mouse imaging (in vivo) experiments showed that Ag2 S-
GSH-SNO could emit readily observable NIR PL, as well as releasing
NO in living cells and small animals. This suggests possible new
applications for multifunctional nanomaterials in diagnostic and
imaging applications. Tan et al. prepared nanoscale light-triggered
NO delivery vehicles, which comprised CS-based SNO and encapsu-
lated Ag2 S QDs (Fig. 15C) [60]. It was shown that the as-synthesized
Ag2 S-CS-SNO nanospheres could readily emit bright NIR PL and
release NO in living cells. Similarly, Tan et al. fabricated biofunc-
tional Ag2 S QDs@CS-RBS nanospheres with ultralow toxicity for
biomedical applications (Fig. 15D) [130]. The nanospheres were
capable of releasing NO under visible light irradiation and emitting
NIR PL when excited by a NIR laser in physiological environments.
These interesting findings provide insights into silver chalcogenide
QDs, particularly their diagnostic and bioimaging applications.
4.2. Silver chalcogenide QDs for chemo-/bio-detection
Given their narrow bandgap and ultralow toxicity, nanoscale
Ag2 S and Ag2 Se QDs are potential candidates for NIR-emitting
QDs, which are desirable for bioimaging applications. In addition,
small Ag2 S and Ag2 Se QDs have large surface area to volume ratios
and they are sensitive to heterogeneous redox chemistry in the
surrounding environment. Photoelectrochemical detection is a
promising analytical technique for biological assays. Due to the
use of separate excitation and detection sources, the sensitivity
of analytical methods based on photoelectrochemistry (PEC)
can potentially match that of electrochemiluminescence (ECL)
 R. Gui et al. / Coordination Chemistry Reviews 296 (2015) 91–124 113

Fig. 15. (A) Synthesis routine of the nano-conjugates (Ag2 S-DOX-cRGD) (Reprinted with permission from Ref. [117], Copyright 2014, The Royal Society of Chemistry). (B)
Schematic presentation of light-triggered NO release and NIR PL imaging of Ag2 S-GSH-SNO NPs (Reprinted with permission from Ref. [57], Copyright 2013, American Chemical
Society). (C) Light-triggered NO release mechanism of Ag2 S-CS-SNO nanospheres (Reprinted with permission from Ref. [56], Copyright 2013, American Chemical Society).
(D) Synthetic strategy and light-triggered NO release mechanism of NIR PL Ag2 S QDs@CS-RBS nanospheres (Reprinted with permission from Ref. [118], Copyright 2014, The
Royal Society of Chemistry).

methods. Zhang et al. first investigated the applications of Ag2 S the PEC detection targets to demonstrate the potential use of Ag2 S
and Ag2 Se QDs as PEC biosensors [145], where Ag2 S QDs were QDs in PEC biosensors (Fig. 16A and C). PEC biosensors are sensitive
assembled on an ITO electrode and used as an optoelectronic to oxygen, which can act as an electron acceptor during the PEC
platform. Glucose and the cancer cell line MCF-7 were selected as process and produce a cathodic photocurrent. The density of the

Fig. 16. (A) Schematic illustration for glucose detection of at GOx/Ag2 S/SnO2 /ITO electrode. (B) Photocurrent responses of the electrode in air-saturation (a), N2 -saturation
with 400 ␮M H2 O2 (b), N2 -saturation (c), and air-saturation with 10.2 mM glucose (d). (C) PEC cytosensor using 3-APBA modified Ag2 S/SnO2 /ITO electrode and the function
of sialidase to remove SA moiety from glycans. (D) Photocurrent responses for (a) ITO/Ag2 S QD; (b) ITO/Ag2 S QD/3-APBA; (c) ITO/Ag2 S QD/3-APBA/BSA; and (d) ITO/Ag2 S
QD/3-APBA/BSA/3000 cells/mL MCF-7. PEC measurement was carried out in 0.1 M PBS (pH7.4) containing 0.1 MAA (A–D, Reprinted with permission from Ref. [133], Copyright
2014, Elsevier). (E) Schematic illustration of working mode for Ag2 S QD modified glassy carbon electrode toward phenol detection. (F) Cyclic voltammograms showing the
current intensity variation by addition of varying amounts of phenol with Ag2 S QD/GC electrode in 0.1 M PBS (pH 7, 40 ◦ C) at a scan rate of 0.1 V s−1 . Inset is the plot showing
the current increase as a function of phenol concentration of (E and F, Reprinted with permission from Ref. [134], Copyright 2014, The Royal Society of Chemistry).
114 R. Gui et al. / Coordination Chemistry Reviews 296 (2015) 91–124
photocurrent from a GOx/Ag2 S/SnO2 /ITO electrode changed
markedly with the addition and exclusion of oxygen (Fig. 16B).
When the electrode was exposed to glucose solution, the cova-
lently attached GOx could catalyze the conversion of glucose
into gluconic acid and hydrogen peroxide with the consumption
of dissolved oxygen, thereby suppressing the photocurrent. The
PEC-based detection of glucose was achieved in this manner.
Zhang et al. also designed a PEC cytosensor to detect MCF-7
breast cancer cells based on the overexpression of sialic acid (SA)
on cell membranes. When 3-aminophenylboronic acid (3-APBA)
was bound to the Ag2 S/SnO2 /ITO electrode surface, the interaction
between boronic acid and the terminal SA moiety present on cell
membranes could capture MCF-7 cells via this low-toxicity photo-
electric interface. Fig. 16D shows that the immobilization of cells
on the electrode surface blocked the diffusion of the sacrificial
electron donor ascorbic acid, thereby reducing the photocurrent.
These properties suggest that this photoelectron interface could
be applied to the detection of bioactive substances. In optimal
conditions, the detection limits were 3.2 × 10−5 M for glucose and
98 cells mL−1 for MCF-7 cell. Hence, the use of Ag2 S QDs in this pho-
toelectric active interface could serve as an excellent and promising
photoelectric active material in the PEC biosensor.
Zhao et al. immobilized Ag2 S QDs on a glassy carbon (GC)
electrode to allow the electrochemical sensing of phenol using
this Ag2 S QDs/GC electrode (Fig. 16E) [146]. There was a signif-
icant cyclic voltammetry (CV) response from the electrode after
the successive addition of phenol to phosphate-buffered saline,
which indicated the clear electrocatalytic oxidation of phenol by
the electrode (Fig. 16F). This nonenzymatic amperometric sen-
sor was constructed by coating Ag2 S QDs on the GC electrode,
which obtained a linear detection range for phenol (1 ␮M–16 mM)
and a low detection limit of 0.015 ␮M, as well as good sensitiv-
ity (61.2 ␮A mM−1 cm−2 ). The significant electrocatalytic activity
of Ag2 S QDs suggests that they may have promising applications in
functional nanomaterials, especially in the construction of efficient
sensors. Moreover, Ag2 S QD-based assemblies also have potential
uses in the fields of energy conversion, biomedical applications, and
electronic devices in the near future.
Pang et al. first developed NIR-electrogenerated ECL from
Ag2 Se QDs [52]. The Ag2 Se QDs produced a strong and efficient
cathodic ECL signal when using K2 S2 O8 as the co-reactant on a
GC electrode (GCE) in aqueous solution. An electron in the highest
occupied molecular orbital (HOMO) of the reduced Ag2 Se QDs was
transferred to SO4 •− via SO4 •− + e− → SO4 2− . Finally, the radiative
recombination between the electron from LUMO and the hole in
HOMO caused the QDs to emit light. The ECL signal remained almost
constant during consecutive cycles of potential scanning (Fig. 17A).
This energy-level related mechanism and the stable ECL signals
facilitated the design of an ECL sensor (Fig. 17B). After the addition
of dopamine (DA, which is usually employed as a model analyte to
study the ECL properties of new materials), the cathodic ECL emis-
sions on the Ag2 Se QDs/poly(ethylenediamine)/multi-wall carbon
nanotubes-modified GCE exhibited a linear decrease as the DA con-
centration increased from 0.5 to 19 ␮M, with a detection limit of
0.1 ␮M (Fig. 17C and D). This ECL system had acceptable accuracy
and precision for the detection of DA in phosphate-buffered saline
and practical drugs. Therefore, Ag2 Se QDs may be a promising can-
didate material for use in ECL biosensors in the future.
Lv et al. produced a CCl4 gas sensor with strong catalumi-
nescence (CTL) responses using Ag2 Se nanomaterials [148]. A
cylindrical heater was inserted into hollow Ag2 Se-deposited Al
foil sealed in a quartz tube. The temperature of the Al foil could
be controlled by adjusting the voltage of a ceramic rod heater.
Air was employed as the carrier gas to drive CCl4 vapor through
the quartz tube. The CTL emissions were then monitored by a
BPCL ultra-weak luminescence analyzer (Fig. 17E). As the CCl4
concentration increased, the magnitude of the CTL response also
increased within a linear range of 0.9–228 ␮g mL−1 (Fig. 17F), and
the detection limit was 0.3 ␮g mL−1 . Based on the strong CTL emis-
sion due to the catalytic oxidation of CCl4 on the Ag2 Se surface,
a sensitive and selective CCl4 CTL gas sensor was obtained, which
had a long lifetime and good reproducibility. This mild electrode-
position approach may be extended to other nanomaterials for
applications as CTL gas sensors with improved properties.
Recently, Lv et al. also conjugated concanavalin A (ConA) with
thioglycollic acid (TGA)-stabilized Ag2 Se QDs via hydrogen bonds,
which led to the adsorption of ConA to Ag2 Se QDs and the forma-
tion of an aggregate, thereby leading to the generation of resonance
Rayleigh scattering (RRS) as a readout signal for sensing events
(Fig. 17G and H) [147]. This RRS sensor allowed the detection of
ConA with a detection limit close to 0.08 ␮g mL−1 and a wide linear
range of 0.27–35 ␮g mL−1 (Fig. 17I). In summary, a novel RRS bioas-
say for ConA determination was established via the assembly of the
as-prepared Ag2 Se QDs. This method had satisfactory selectivity
and sensitivity, and it could be employed for the determination of
ConA in human serum samples. Thus, Ag2 Se QDs may be utilized
as excellent scaffolds for RRS-based protocols that detect targeted
molecules directly. No other studies have addressed silver chalco-
genide QD-based chemo-/bio-detection, but this may be a highly
promising new strategy for practical detection applications.
4.3. Silver chalcogenide QDs in QDSSCs
QDSSCs are interesting energy devices because of their high
capacity for harvesting sunlight and generating multiple electron-
hole pairs, as well as their simple fabrication and low cost. However,
the power conversion efficiency (PCE) of QDSSCs (commonly <4%)
is less than that of dye-sensitized solar cells (up to 12%), which
is mainly because of the narrow absorption ranges and charge
recombination that occurs at QDs- and TiO2 -electrolyte interfaces
[164,165]. Therefore, new types of working electrodes, sensitiz-
ers, counter electrodes, and electrolytes should be developed to
improve the PCE of QDSSCs. The features, size, morphology, and
quality of newly developed nanomaterials all affect the efficiency
of electron injection and light harvest. Among the new types of
functional nanomaterials developed during the past decade, silver
chalcogenide QDs have been synthesized and applied in biomedical
areas due to their excellent NIR-emitting PL. Due to their narrow
bandgap energy (Eg ), silver chalcogenide QDs also have the poten-
tial for further applications in QDSSCs. In this section, we highlight
the application of silver chalcogenide QDs in QDSSCs and we sum-
marize most of the relevant research in this area, as described in
Table 4. To better understand their contribution to QDSSCs, we clas-
sified these studies according to the QDs (Ag2 S or Ag2 Se) used in
assemblies, the device fabrications, short-circuit current (Jsc ), and
PCE. There have been no reports of Ag2 Te QDs-based QDSSCs so
they are excluded from the table.
Ag2 S was utilized as the main light absorber and sensitizer, and
CdS was introduced as an intermediate layer to complete the cas-
cade band structure of ZnO/CdS/Ag2 S heterojunction [149]. When
light irradiated this cell, the electrons in the valence band (VB) of
Ag2 S and CdS were photo-excited into the conduction band (CB).
The photo-excited electrons could transfer efficiently to the CB of
ZnO and finally to the ZnO/CdS/Ag2 S photoanode. In addition, holes
in the VB of Ag2 S and CdS collected in the VB of Ag2 S to oxidize the
polysulfide electrolyte. Next, the electrons on the anode moved to
the cathode via an external circuit and participated in the reduc-
tion reaction at the cathode-electrolyte interface (Fig. 18A). The
heterostructure of ZnO/CdS/Ag2 S is a cascade-shaped band, which
facilitated the transfer of photo-excited electrons from CdS and
Ag2 S to the CB of ZnO, as well as the transfer of the generated holes
from ZnO and CdS to the VB of Ag2 S. When using a narrow bandgap
 R. Gui et al. / Coordination Chemistry Reviews 296 (2015) 91–124 115

Fig. 17. (A) Time-dependent ECL signals collected at −1.22 V of Ag2 Se QDs/PEI/MWCNTs modified GCE in 0.1 M PBS (pH 7.5) containing 0.1 M K2 S2 O8 and 0.1 M KCl. (B)
Scheme of energy-level related mechanism of DA quenching Ag2 Se QDs ECL; (C) Quenching effect of dopamine at 0, 0.5, 1.0,1.9, 3.8, 9.5, and 19 ␮m; (D) Linear relationship
between DA concentration and ECL intensity ratio of I0 /I of Ag2 Se QDs/PEI/MWCNTs modified GCE in 0.1 M PBS (pH7.5) containing 0.1 M K2 S2 O8 and 0.1 M KCl (A–D, Reprinted
with permission from Ref. [52], Copyright 2012, American Chemical Society). (E) Schematic diagram of CTL detection system. (F) Calibration curve between CTL intensity and
carbon tetrachloride concentration. Wavelength, 460 nm; temperature, 240 ◦ C and air flow rate, 250 mL min−1 (E and F, Reprinted with permission from Ref. [136], Copyright
2011, Elsevier). (G) Schematic illustration for fabricating TGA and glycine modified Ag2 Se QDs for RRS detection of ConA. (H) Structure of Ag2 Se QD-ConA and the model of
hydrogen bonds between Ag2 Se QDs and ConA. (I) Validation of Ag2 Se QDs as probes for ConA detection, Ag2 Se QDs, 5 × 10−4 mol L−1 ; pH = 6.0; SCBS buffer, 300 ␮L (G–I,
Reprinted with permission from Ref. [135], Copyright 2014, The Royal Society of Chemistry).

Table 4
Comparisons of Ag2 S and Ag2 Se QDs systems assembling with different substrates for QDSSCs applications.

Ag2 S(Se) QDs assemblies Device fabrications Jsc and PCE Ref.

Ag2 S-CdS heterostructure FTO/ZnO/CdS/Ag2 S electrode 27.6 mA cm−2 , 2.4% [149,150]

Ag2 S/CdS heterodimers FTO/TiO2 /Ag2 S/CdS electrode ∼1.67 mA cm−2 , no report [151]
Ag2 S NPs Ti/TNAs/Ag2 S photoelectrode 1.23 mA cm−2 , 1.21% [152]
Ag2 S QDs TiO2 /Ag2 S QDs electrode ∼1.5 mA cm−2 , 0.067% [153,154]
Ag2 S QDs FTO/Ti/TNAs/Ag2 S-N3 electrode 10.2 mA cm−2 , 4.4% [155]
˛-Ag2 S NCs SnO2 /Ag2 S, TiO2 /Ag2 S heterojunction 9.04, 0.24 mA cm−2 [156]
Ag2 S QDs Ti/TNAs/Ag2 S photoelectrode 0.12 mA cm−2 , no report [157]
Ag2 S QDs FTO/TiO2 /Ag2 S/N3 electrode 1.32 mA cm−2 , 0.07% [158]
Ag2 S QDs FTO/TNAs/Ag2 S electrode 11.7 mA cm−2 , 0.87% [159]
Ag2 S QDs WO3 /Ag2 S electrode 5.81 mA cm−2 , 0.31% [160]
Ag2 S QDs FTO/TiO2 NRAs/Ag2 S electrode 1.028 mA cm−2 , 0.136% [161]
Ag2 S QDs Ag2 S/mp-TiO2 /FTO electrode ∼0.36 mA cm−2 , 0.29% [162]
Ag2 Se QDs TiO2 /Ag2 Se/ZnS/polysulfide 33.3 mA cm−2 , 1.21% [163]

sensitizer (e.g., Ag2 S) in solar cells, fast electron-hole pair recombi-
nation is caused by a strong exciton binding energy. This problem
was overcome by introducing an efficient cascade-shaped band
alignment, which minimized photocurrent loss from the electron-
hole pair recombination path, thereby yielding an extraordinarily
improved Jsc of ca 30 mA cm−2 with an acceptable high PCE of 2.4%
(Fig. 18B). These results confirm that the co-sensitization of CdS
and Ag2 S was efficient. Further enhancement of the open-circuit
voltage (Voc ) could allow the development of CdS/Ag2 S QDSSCs to
obtain a highly efficiently solar cell.
Fig. 18C shows the typical fabrication of Ag2 S QDs-sensitized
TiO2 nanotube arrays (TNAs) based on FTO glasses for solar cells
using sequential chemical bath deposition [155]. The resulting
Ag2 S-TNAs complexes were immersed in a dye N3 in methanol
solution for 12 h. The co-sensitized solar cells (Ag2 S-N3-TNAs sys-
tem) were assembled in a sandwich form using Pt coated onto
the other FTO as a counter electrode (Fig. 18D). Compared with
N3-TNAs solar cells, the Jsc of Ag2 S-N3-TNAs increased from 8.5
to 10.2 mA cm−2 , whereas there were no significant changes in Voc
and the fill factor. The corresponding PCE reached 4.4%, which was
1.2 times that of the N3-TNAs (3.64%) and 1.6 times that of the
CdS QDs/dye co-sensitized system (Fig. 18E). In summary, due to
the potential gradient induced by the coupling of N3 dye, Ag2 S,
and TiO2 , the photogenerated excitons were dissociated rapidly,
and thus the interfacial charges were separated, transferred, and
passed through rapidly, with an enhanced PCE.
Fig. 19A shows energy band diagrams of Ag2 S with respect to
TiO2 and WO3 . The CB level of Ag2 S is about 0.2 eV higher than TiO2
and the CB level of WO3 is 0.3 V lower than that of TiO2 , thereby
yielding an offset of Ec = 0.5 eV between the CB values of Ag2 S
and WO3 . The higher CB offset in the Ag2 S/WO3 system facilitates
more efficient photoelectron injection from the CB of Ag2 S into
that of WO3 , which can yield higher efficiency. Lee et al. reported
a new architecture for Ag2 S QDSSCs fabricated from Ag2 S QDs
116 R. Gui et al. / Coordination Chemistry Reviews 296 (2015) 91–124

Fig. 18. (A) Schematic illustration of ZnO/CdS/Ag2 S QDSSC. (B) J–V curves of the fabricated QDSSCs for each electrode. The band structures of ZnO, CdS, and Ag2 S are shown
in the inset (A and B, Reprinted with permission from Ref. [137], Copyright 2013, AIP Publishing LLC). (C) Schematic of Ag2 S sensitized FTO-based TiO2 nanotube arrays.
(D) Charge-transfer mechanism of Ag2 S-N3-TNAs solar cell. (E) Current-voltage characteristics of Ag2 S-N3-TNAs (a) and pristine N3-TNAs (b) under AM 1.5 G illumination
(100 mW cm−2 ) (C–E, Reprinted with permission from Ref. [142], Copyright 2013, ELSEVIER).

Fig. 19. (A) Energy band diagrams for Ag2 S QDs coated on a TiO2 electrode and Ag2 S QDs coated on a WO3 electrode. (B) I–V characteristics of Ag2 S SSCs with various SILAR
cycles. (C) I–V characteristics of the best Ag2 S cell before and after treatment with Ti-iP and scattering layer (SL). (D) I–V characteristics of an Ag2 S SSC under various light
intensities. (E) EQE of an Ag2 S SSC (Reprinted with permission from Ref. [147], Copyright 2013, Springer).
 R. Gui et al. / Coordination Chemistry Reviews 296 (2015) 91–124 117

Fig. 20. Schematic energy-level diagrams of Ag2 Se QD-DSC (A) before, (B) after ZnS coating. Diagrams (C) and (D) show the reduced recombination of photoelectrons after
Ti-iP coating. Red-dash lines denote the route for recombination. (E) Current–voltage curves of Ag2 Se DSCs processed with various SILAR cycles. (F) Current–voltage curves
under various sun intensities. (G) External quantum efficiency spectra of Ag2 Se(4) QD-DSCs with ZnS and Ti-iP coatings. For comparison, the spectrum of N3 dye is also
shown.
Reprinted with permission from Ref. [150], Copyright 2011, Elsevier.

using the successive ionic layer adsorption and reaction (SILAR)
process [160]. The solar cell activity was affected dramatically
by the number of SILAR cycles (n), where the maximum perfor-
mance was obtained at n = 10, with Jsc = 4.74 mA cm−2 , Voc = 0.16 V,
and PCE = 0.2%. Increasing n enhanced the density of Ag2 S QDs on
WO3 , thereby improving the photoelectron production in Ag2 S QDs
and the injection of electrons into the CB of WO3 , which yielded a
higher PCE (Fig. 19B). After determining that the optimum value
of n was 10, the sample was treated with a Ti-iP layer and a
scattering layer. This treatment improved the cell performance to
Jsc = 5.81 mA cm−2 , Voc = 0.21 V, and PCE = 0.31% (Fig. 19C). Thus, the
Ti-iP blocking layer prevented the FTO glass from making direct
contact with the electrolyte, which reduced the loss of electrons via
recombination. The scattering layer supported the back-scattering
of incident light due to the increased optical path. The PCE increased
as the light intensity decreased. The Jsc < 10% at 1 sun was equal
to 1.11 mA cm−2 (Fig. 19D). The external quantum efficiency (EQE)
spectrum for the best Ag2 S(10) cell is shown in Fig. 19E. The spec-
trum covered the range of 350–900 nm (from visible light to the
NIR light region) with a maximum EQE of 29% (at  = 650 nm). The
average EQE over the entire spectral range was 17.2% and the upper
cutoff wavelength of the spectrum was 900 nm (ca 1.38 eV). This
study demonstrated the feasibility of this new configuration for
Ag2 S QDSCs fabricated on WO3 electrodes.
In Ag2 S QDs-based QDSSCs, the co-sensitization of dual-QDs
(e.g., Ag2 S and CdS QDs) [140,150], or QD-dyes (e.g., Ag2 S and N3)
systems [158], yielded a higher PCE. FTO-based TNAs are utilized
widely as substrates for the deposition of Ag2 S QDs during the
fabrication of QDSSCs [152,156,157,159]. Although Ag2 S QDSSCs
could also be fabricated on SnO2 and WO3 electrodes [156,160],
these QDSSCs have a lower PCE compared with that of FTO-based
TNAs. Only one previous study has described the production of
Ag2 Se QDs-based QDSSCs. Lee et al. first developed Ag2 Se QDSSCs
for full solar spectrum light harvesting [163]. In dye-sensitized solar
cells without a ZnS coating, the electrons are excited by photons
from the VB to the CB of Ag2 Se. The CB level is higher than the redox
potential of the electrolyte, so the photoelectrons can recombine
with holes in the I− /I3 − electrolyte (Fig. 20A). For a sample with a
ZnS coating, a barrier with a height of Ec = ECB (ZnS) − ECB (Ag2 Se)
was formed at the Ag2 Se/ZnS interface (Fig. 20B). The ZnS coating
only worked at long wavelengths (1000–2500 nm) and not short
ones (350–1000 nm). Prior to the Ti-iP coating, photoelectrons can
recombine with holes in the electrolyte at the FTO/electrolyte inter-
face (Fig. 20C). After applying the Ti-iP coating, a thin layer of TiO2
is formed on the FTO surface (Fig. 20D), which reduces the contact
area between the FTO glass and electrolyte, and thus recombina-
tion is reduced. This process does not involve the energy levels of
QDs, so the enhancement does not depend on the wavelength.
The optimal values of Jsc = 27.2 mA cm−2 and PCE = 1.45% were
obtained at n = 4 (Fig. 20E). When n > 4, the overload of QDs reduced
the pore spaces in the electrode, which impeded the flow of elec-
trolytes, thereby yielding smaller values for Jsc and PCE. Voc was ca
0.26 V and it was independent of n. Fig. 20F shows the I–V curves
of Ag2 Se(4) samples under various light intensities (Pin ). The PCE
increased as Pin decreased. At 9.7% of 1 sun, PCE was 3.12%, which
was much higher than the PCE (1.76%) at 99.4% of 1 sun. The best
118 R. Gui et al. / Coordination Chemistry Reviews 296 (2015) 91–124

Fig. 21. (A) Structure of Ag2 S QD-SPEC cell. (B) J–E curves for cells using Ag2 S (tp )/mp-TiO2 /FTO photoanodes in the dark (curve a) and under illumination of one sun (AM 1.5,
100 mW cm−2 ) (curve b, tp = 0.25 h; curve c, tp = 1 h; curve d, tp = 6 h). (C) Time courses for H2 generation in AgNP-SPEC cell (curve a) and Ag2 S QD-SPEC cells (curves b–d) under
illumination of one sun (AM 1.5, 100 mW cm−2 ) at E = −0.52 V (vs Ag/AgCl): (b) tp = 0.25 h, (c) tp = 1 h, (d) tp = 6 h (A–C, Reprinted with permission from Ref. [149], Copyright
2011, American Chemical Society). (D) A configuration model consisting of Ag2 S/TNAs photoelectrode and Pt cathode for H2 generation. (E) The rate of H2 generation from
pure TNAs and TNAs sensitized with Ag2 S NPs prepared from TNAs loaded with Ag NPs by electrodeposition for (a) 20 s, (b) 60 s, and (c) 90 s under illumination of visible
light (100 mW cm−2 ) (D and E, Reprinted with permission from Ref. [140], Copyright 2014, ELSEVIER). (F) Schematic diagrams for the possible photocatalytic mechanism of
Ag2 S NCs attaching over Ag8 W4 O16 nanorods under visible-light irradiation (Reprinted with permission from Ref. [153], Copyright 2014, Elsevier).

EQE spectra had the following average EQE values: 80% in the range
of 350–800 nm, 67% at 2200–2500 nm, and 56% over the entire
spectrum of 350–2500 nm (Fig. 20G). These results suggest that
Ag2 Se QDs can be used efficiently as a broadband sensitizer for solar
cells.
4.4. Silver chalcogenide QDs for photocatalysis
In addition to the potential applications of silver chalcogenide
QDs in bioimaging, chemo-/bio-detection, and QDSSCs, these QDs
also have promising uses in other fields such as photocatalysis
[152,162,166], and as antimicrobial [167–169] and thermoelectric
materials [39,40,119–121,18,122]. Only Ag2 S QDs (but not Ag2 Se
or Ag2 Te QDs) have reported applications as photocatalysts and
antimicrobials. Studies of the thermoelectric properties or other
applications of silver chalcogenide QDs have been reported for
Ag2 Te QDs (or as NCs, NPs, or assemblies). In this section, we high-
light the use of Ag2 S QDs as photocatalysts.
Tada et al. reported an in situ photodeposition technique
based on mesoporous (mp) TiO2 nanocrystalline films coated
onto fluorine-doped SnO2 (FTO) electrodes to allow the forma-
tion of Ag2 S QDs (Ag2 S/mp-TiO2 /FTO) [162]. Ag2 S QDs-sensitized
photoelectrochemical (SPEC) cells were fabricated using Ag2 S/mp-
TiO2 /FTO photoanodes. Under illumination of 1 sun, the Ag2 S
photoanode cell yielded H2 at a rate of 0.8 mL h−1 with a total con-
version efficiency of 0.29% (Fig. 21A). With visible light illumination
( > 430 nm) of the Ag2 S/mp-TiO2 /FTO photoanodes, electrons in
the VB(Ag2S) were excited to the CB(Ag2S) , where the electrons were
injected into the CB(TiO2) . In addition, holes in the VB(Ag2S) oxidized
S2− to S2 2− ions. The intimate coupling between TiO2 and Ag2 S is
preferable to interfacial electron transfer from Ag2 S to TiO2 . The
SO3 2− ions prevented the back reaction by reducing S2 2− back to
S2− ions. The electrons were transferred to the Pt counter electrode
via an external circuit, which reduced H+ to H2 via the high elec-
trocatalytic activity. Fig. 21B shows the J–E curves for cells using
Ag2 S(tp )/mp-TiO2 /FTO photoanode in the dark and under illumina-
tion of 1 sun. The photocurrent (Jph ) increased to E > ca −0.8 V, while
in the dark, the electrolytic current from the oxidation of S2− ions
started to flow at E ≈ −0.52 V (Edark ). Furthermore, the maximum
Jph was obtained for Ag2 S(tp = 1 h)/mp-TiO2 /FTO. Fig. 21C shows the
time course for H2 generation in the Ag2 S QDs-SPEC cells under
illumination of 1 sun at E = −0.52. The Ag2 S(tp )/mp-TiO2 /FTO pho-
toanode yielded H2 , where the amount was almost proportional to
tp when tp > 10 min. This indicates that S2− ions operate as good hole
(Ag2 S) scavengers to restrict photocorrosion. Therefore, this simple
in situ photodeposition technique for the preparation of Ag2 S-TiO2
heterojunctions may be useful for applications of SPEC nanodevices
and photocatalysts.
Due to the sensitizing of narrow bandgap materials (such as
Ag2 S) and the homogeneous distribution of Ag2 S NPs hetero-
junction structures over the surfaces of TNAs, the Ti/TNAs/Ag2 S
nanocomposites obtained have a high capacity for absorbing vis-
ible light, and thus they yield a remarkable enhancement in the
photocatalytic efficiency of H2 generation [152]. Under visible light
illumination (at 100 mW cm−2 ), the maximum PCE of 1.21% and the
highest H2 production rate of 1.13 mL cm−2 were obtained from
TNA electrodes sensitized with Ag2 S NPs (Fig. 21D and E). This flex-
ible and unique route is also suitable for the deposition of metals,
metal oxides, or metal compounds within TNAs for catalysis, pho-
tocatalysis, photoelectrochemical, and photovoltaic applications.
In addition, Yu et al. prepared narrow bandgap Ag2 S NCs
attached to the surfaces of wide bandgap Ag8 W4 O16 nanorods
 R. Gui et al. / Coordination Chemistry Reviews 296 (2015) 91–124 119

Fig. 22. (A) Preparation of f-MWCNTs-QDs nanohybrids. (B) Antibacterial activity of MWCNTs-COOH, f-MWCNTs, f-MWCNTs-QDs nanohybrids, PAMAM dendrimer, CdS and
Ag2 S QDs (number of experimental repetitions, n = 3) (A and B, Reprinted with permission from Ref. [154], Copyright 2012, Elsevier). (C) A proposed scheme of the formation
of Ag2 S-graphene composite: Firstly, absorption of Ag(DDTC) on GO sheets; and secondly, formation of graphene-supported Ag2 S particles by the reduction of GO sheets
and in situ crystal growth of Ag2 S. (D) Raman spectra of (a) GO and (b) Ag2 S-graphene in the range of 200–2000 cm−1 (C and D, Reprinted with permission from Ref. [156],
Copyright 2011, Elsevier).

using a facile in situ anion exchange method based on the reaction
between S2− and WO4 2− , where they studied the photocat-
alytic activity by analyzing the photocatalytic decolorization of
methyl orange solution under visible light irradiation (Fig. 21F)
[166]. The results showed that the Ag2 S/Ag8 W4 O16 composite
photocatalysts (with 2.16 wt% of Ag2 S) exhibited higher activ-
ity (k = 20.8 × 10−3 min−1 ) in the discoloration of methyl orange
under visible light illumination compared with the pure Ag8 W4 O16
(>20 times) and N-TiO2 photocatalysts (>10 times). However, the
photocatalytic process depended greatly on the quantum size
effect of Ag2 S NCs. This study provided novel insights into the
design of high efficiency narrow bandgap semiconductor NCs
coupled to wide bandgap semiconductor composite photocata-
lysts. Narrow bandgap semiconductor NCs with tunable bandgaps
provide new alternatives for harvesting solar light in the visible and
IR regions.
4.5. Silver chalcogenide QDs with antimicrobial and
surface-enhanced Raman scattering (SERS) activities
Oki et al. reported the antimicrobial activities of CdS and Ag2 S
QDs immobilized on poly(amidoamine) graft carbon nanotubes
[167]. To design the antimicrobial nanohybrids, f-multiwalled
carbon nanotubes (MWCNTs)-CdS and f-MWCNTs-Ag2 S were
developed by covalently grafting cationic hyperbranched dendritic
polyamidoamine (PAMAM) onto MWCNTs. CdS and Ag2 S QDs were
deposited successively in situ onto the PAMAM-grafted MWCNTs
instead of anchoring the pre-synthesized QDs (Fig. 22A). Amine-
terminated hyperbranched PAMAM was grafted onto the MWCNTs
by repetitive reactions involving Michael addition of methyl-
methacrylate onto the surface amine groups and amidation of
the terminal ester groups with ethylenediamine. The antibacterial
activities of these f-MWCNTs-CdS or f-MWCNTs-Ag2 S nanohy-
brid systems were evaluated systemically using Escherichia coli,
Pseudomonas aeruginosa, and Staphylococcus aureus. The results
obtained were compared with the activities of carboxylated MWC-
NTs, PAMAM-grafted MWCNTs, PAMAM dendrimers, CdS, and
Ag2 S QDs, which demonstrated that the antibacterial action of
MWCNTs was enhanced by grafting PAMAM, as well as being
improved further by the immobilization of CdS or Ag2 S QDs
(Fig. 22B). PAMAM dendrimers possess amine functional groups
on their periphery (e.g., the primary amine group) and they
can penetrate the bacterial cell membrane due to their strong
hydrogen bond donor properties toward biomolecules [170,171].
The inhibitory activities of f-MWCNTs are governed by PAMAM
dendrimers. Furthermore, the antibacterial activities of f-MWCNTs-
Ag2 S nanohybrids are higher than those of f-MWCNTs-CdS, which
suggests that the antibacterial ability of Ag2 S QDs is better than CdS
QDs.
In general, the f-MWCNTs-QDs nanohybrids had marked
antibacterial effects against all three of the bacterial species tested.
The penetration of PAMAM dendrimers via bacterial cell mem-
branes might facilitate the penetration of QDs, thereby allowing
the rapid destruction of bacterial cells. When DNA molecules
are in a relaxed state, the replication of DNA can be achieved
effectively. When DNA is in the condensed form, it loses its repli-
cation ability [172]. In this study, Ag2 S or CdS QDs penetrated the
bacterial cell membranes, which transformed the DNA into a con-
densed form and inhibited its ability to replicate, thereby killing
the bacterial cells. The f-MWCNTs-QDs nanohybrids had higher
antimicrobial activities against Gram-negative bacteria compared
with Gram-positive bacteria. These antibacterial agents might have
applications in medicine, public transportation, home appliances,
and sporting goods.
120 R. Gui et al. / Coordination Chemistry Reviews 296 (2015) 91–124

Fig. 23. Temperature dependent plots for (A) electrical resistivities, (B) Seebeck coefficients, (C) power factor, (D) thermal conductivity, and (E) of merit of pellet samples
prepared from ∼5 and ∼15 nm Ag2 Te NPs with sulfur doping, ∼1 ␮m Ag2 Te particles and bulk Ag2 Te ingot (A–E, Reprinted with permission from Ref. [40], Copyright 2012,
The Royal Society of Chemistry). (F) Time-resolved photocurrent switching between on and off states. (G) Photocurrent decay and the fitting curve using biexponential decay
function as described in text. The inset shows self-assembled superlattice of monodispersed 3.1 nm Ag2 Te NCs used for photoconductivity measurement (F and G, Reprinted
with permission from Ref. [39], Copyright 2011, American Chemical Society).

In addition, Liu et al. prepared Ag2 S-graphene nanocomposites
using a relatively facile hydrothermal method with Ag(DDTC) as
the Ag precursor and graphene sheets as the support materials
(Fig. 22C) [169]. The experimental results showed that the Ag2 S-
graphene nanocomposites exhibited a SERS activity with graphene
oxide and they had relatively superior PL properties compared
with pure Ag2 S QDs. It is known that Raman scattering is highly
sensitive to the microstructure of nanocrystalline materials.
Compared with graphene oxide, the D- or G-bands of graphene
were shifted slightly from 1355 or 1605 cm−1 to 1340 or 1586 cm−1 .
In addition, the relative intensity of D or G increased after the
hydrothermal reaction, which agreed with the reports of Lambert
and Stankovich et al. [173,174]. These results also demonstrated
that graphene oxide was reduced to graphene. Moreover, the
SERS activities of the Ag2 S-graphene composites were compa-
rable to those of the original graphene oxide in the same test
 R. Gui et al. / Coordination Chemistry Reviews 296 (2015) 91–124
conditions (Fig. 22D). The SERS activity may be attributable to a
chemical effect because the oxygen-containing functional groups
of graphene oxide can absorb positive Ag ions via electrostatic
attraction. Interactions between Ag2 S and graphene may produce
a charge-transfer complex that can absorb light at the excitation
frequency, thereby leading to the chemical SERS effect. In addi-
tion to Ag2 S, changes in the morphology and composition may
also produce the SERS effect [175–177]. In particular, TEM images
showed that the graphene sheets in the Ag2 S-graphene nanocom-
posite were exfoliated and decorated randomly with Ag2 S NPs.
Therefore, the graphene sheets played an important role in allow-
ing Ag2 S crystals to grow in a specific orientation to form spherical
NPs.
4.6. Silver chalcogenide QDs as thermoelectric materials
Ag2 Te QDs or NCs are enigmatic because of their anoma-
lous growth process, which yields unusual structures and optical
responses [25,38,178]. Ag2 Te is a rarely explored member of the
silver chalcogenide family [25,38,179] that possesses interesting
physical properties, including a transition from semiconductors
to ionic conductors [180,181], and high magnetic resistance in
nonstoichiometric samples [182]. Ag2 Te exhibits high electron
mobility and low thermal conductivity [183], which are desirable
for thermoelectric applications [53]. These features are useful for
studies at nanoscale dimensions because of the natural delocaliza-
tion lengths of electronic and thermal excitation.
Yan et al. prepared n-type Ag2 Te NPs with uniform and con-
trollable sizes (5–15 nm) via a solvothermal method. The usage
of dodecanethiol during synthesis introduced sulfur doping into
Ag2 Te, which optimized the charge carrier concentration of the NPs
to >1 × 1020 cm−3 , thereby obtaining the desired electrical resistiv-
ity of <5 × 10−6  m for 15-nm Ag2 Te NPs. Effective sulfur doping
yielded a maximum figure of merit (ZT) value of ca 0.62 at 550 K
(Fig. 23A–E) [40]. The increased ZT value was attributed mainly
to reduced thermal conductivity, which is expected to be closely
related to the increased interface scattering of phonons in Ag2 Te
NPs pellets.
Murray et al. reported the NIR absorption of monodis-
perse Ag2 Te NCs and the photoconductive response of their
self-assembled superlattices [39]. The distinct photoconductive
response supported the inherent semiconducting nature of the con-
stituent Ag2 Te NCs in the device, where the current increased from
2.43 to 4.01 nA under illumination within 25.6 s, followed by a slow
saturation behavior (Fig. 23F). Fig. 23G shows the photocurrent
decay, which could be fitted to a biexponential function. The two
characteristic time constants, t1 and t2 , may represent the bulk-
like rapid decay process and the slow decay process, respectively,
but they are more likely to be related to surface traps. The con-
stants A and B are the relative weighting factors of the two decay
mechanisms (A + B = 1). Fitting the parameters yielded A = 0.428,
B = 0.572, t1 = 1.1 s, and t2 = 17.2 s. The structural, chemical, opti-
cal, and optoelectronic properties of Ag2 Te NCs were investigated,
where photocurrent switching between “on” and “off” states pro-
vided more support for the semiconducting nature of Ag2 Te NCs.
In addition to the unusual physical properties of Ag2 Te, the func-
tionality provided by NCs makes them valuable material systems
for further exploration.
Thermoelectric materials have attracted great interest because
of their promising applications in power generation from waste
heat [184,185]. The energy conversion efficiency of the thermo-
electric modulus is closely related to the figure of merit [186],
ZT = S2 T/k, where T is the temperature in Kelvin, S is the Seebeck
coefficient,  is electrical conductivity, and k is thermal conductiv-
ity. Snyder et al. reported that the bandgap of Ag2 Te was increased
to yield a ZT of unity by forming alloys and composites with PbTe,
121
thereby demonstrating the importance of exploiting potentially
good thermoelectrics in small bandgap semiconductors, as well as
similar materials [111]. Cabot et al. reported that organic ligand
displacement by metal salts enhanced the thermoelectric prop-
erties of Ag2 Te. A sixfold increase in the thermoelectric figure of
merit for Ag2 Te was obtained when organic ligands were displaced
by AgNO3 [29]. The same procedure enhanced the performance
of NCs or NCs-based devices in a broad range of applications,
which was related to their photovoltaic and thermoelectric proper-
ties, and catalysis. In general, Ag2 Te is a technologically important
material, which exhibits high ionic conductivity at room temper-
ature [187]. The low temperature ˛-Ag2 Te phase is a very narrow
bandgap semiconductor (Eg = 0.025 eV), which has a low electron
effective mass, high electron mobility, and low lattice thermal
conductivity [188–191,181,192,193]. Ag2 Te also exhibits excellent
thermoelectric properties in both the bulk and nanocrystalline
forms [194,195]. Wu et al. reported the thermoelectric proper-
ties of a Ag2 Te-bismuth Te-nanowire heterostructure obtained
by site-selective conversion [115]. The thermoelectric properties
of nanocomposite pellets were investigated at 300–400 K, which
showed that the pellets were p-type with reduced lattice thermal
conductivity and a ZT of ca 0.41 at 400 K, and this is the best value
reported for p-type Ag2 Te.
5. Conclusions and outlooks
In the past decade, there have been great improvements in the
methods used to synthesize narrow bandgap silver chalcogenide
QDs and their potential applications. In this review, we considered
various methods used to synthesize these QDs, including organic
phase synthesis at high temperature, aqueous phase synthesis
using small or macromolecules as ligands, polar phase synthesis,
biomimetic synthesis, and cation-exchange synthesis. In addition
to their low cost, facile synthesis and ultra-small size, the as-
synthesized silver chalcogenide QDs exhibit high photo-/colloidal
stability, ultralow toxicity, and NIR-emitting PL, which make them
promising materials for various significant applications. The QDs
obtained using different synthetic methods are capped or stabi-
lized by small molecules, biomacromolecules, or polymer ligands,
surface-conjugated with biopolymers or inorganic–organic hybrid
composites, or deposited on inorganic substances to fabricate
QD-based assemblies. These directly synthesized QDs and their cor-
responding QD-based assemblies have been developed for uses in
bioimaging or PL tracking (e.g., in vitro/in vivo imaging and toxicity
assessment), chemo-/bio-detection (e.g., photo-/electrochemical,
electrochemiluminescent or cataluminescent detection), QDSSCs,
and photocatalysis, as well as antimicrobial and thermoelectric
materials.
Recent advances in the methods used to synthesize silver
chalcogenide QDs have indicated that the utilization of rich thiol-
based coatings as surface ligands (with shorter chain lengths),
a higher reaction temperature, a longer reaction time, a slower
release rate of sulfur resources, a lower Ag/chalcogenide ratio, and
a higher Ag/ligand ratio significantly favor the achievement of high
PLQYs. Silver chalcogenide QDs with high PLQYs (e.g., 15.5%) can be
synthesized in organic phases, but the synthesis is relatively tedious
and it requires harsh reaction conditions, as well as high costs
and hazardous solvents. The as-synthesized QDs are hydrophobic,
and thus they cannot be applied directly to biosystems before
additional ligand exchange or phase transfer. Aqueous synthesis
or direct synthesis in water-soluble media is highly desirable and
the resulting QDs can be used directly in biosystems, but previous
studies indicate that the as-synthesized QDs have relatively low
PLQYs (1–7%). This is due mainly to the slower nucleation and
growth processes in hydrothermal or room-temperature reactions.
122 R. Gui et al. / Coordination Chemistry Reviews 296 (2015) 91–124
Furthermore, the selection of surface-coating ligands (e.g., rich
thiol-based and water-soluble multidentate polymers) and the
release rate (slower) of sulfur resources are key factors in improving
the PLQYs of silver chalcogenide QDs synthesized in water-soluble
media. However, the PLQYs of silver chalcogenide QDs are generally
lower than those of other colloidal semiconductor NCs or QDs (e.g.,
Cd chalcogenide QDs, up to 50–70%) after silica coating [196]. Thus,
bright, highly water-soluble, silica-coated silver chalcogenide QDs
are expected to have excellent stability and higher PLQYs. Given
their many advantages (e.g., NIR-emitting PL, high photo-/colloidal
stability, and good brightness), high-quality silver chalcogenide
QDs will have significant applications, particularly for in vitro and
in vivo bioimaging, and chemical and biological detection.
Silver chalcogenide QDs also have other applications (e.g.,
QDSSCs, photocatalysts, antimicrobials, and thermoelectric mate-
rials) based on appropriate fabrications of QD-based assemblies
(e.g., surface capping, conjugation, and deposition). However, some
challenges remain, such as improving the power conversion effi-
ciency of silver chalcogenide QDSSCs, as well as their photocatalytic
and antimicrobial activities, and thermoelectric efficiency. Despite
these remaining challenges, research into silver chalcogenide QDs
is advancing rapidly throughout the world. The next few years
are sure to be exciting and rewarding for materials science where
improvements to narrow bandgap NCs will yield commercializable
optoelectronic applications and other uses. Nevertheless, current
research into photoluminescent silver chalcogenide QDs is at the
proof-of-concept stage and we expect that important systematic
research will follow (focusing mainly on their synthesis methods,
properties, structures, and assemblies) to obtain silver chalco-
genide QDs with a broad range of promising applications, which
can be extended to other fields (e.g., lasers, optical modulators, and
photodetectors).
Acknowledgments
This study was financially supported by the National Natu-
ral Science Foundation of China (21475071, 21405086, 21275082,
and 21203228), the Natural Science Foundation of Shandong
(ZR2014BQ001 and BS2014YY009), the National Key Basic Research
Development Program of China (2012CB722705), the Taishan
Scholar Program of Shandong, and the Natural Science Foundation
of Qingdao (13-1-4-128-jch and 13-1-4-202-jch).
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