reviews
Electrochemical Sensors
Graphene-Based Electrochemical Sensors
Shixin Wu, Qiyuan He, Chaoliang Tan, Yadong Wang, and Hua Zhang*
From the Contents
1. Introduction .......................................... 1161
2. Preparation of Graphene-Based
Electrochemical Electrodes ................... 1161
3. Graphene-Based Electrochemical
Sensors ................................................1165
4. Summary ...............................................1169
1160 wileyonlinelibrary.com
Graphene, one kind of emerging carbon nanomaterial,
has attracted increasing attention recently. Due to its
fascinating physical and electrochemical properties,
graphene as a promising electrode material has been
widely used in electrochemical sensing applications. In
this review, different approaches for the fabrication of
graphene and the preparation of graphene-modified
electrodes for electrochemical sensors are introduced.
Moreover, recent research results on different graphene-
based materials as an electrochemical platform for the
detection of various biomolecules and chemicals are
reviewed and compared. More electrochemical studies on
this novel material should show up in the near future.
© 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim small 2013, 9, No. 8, 1160–1172
Graphene-Based Electrochemical Sensors
1. Introduction
Graphene is a two-dimensional (2D), single-layer sheet of
sp2-hybridized carbon atoms that are closely packed into a
hexagonal lattice structure.[1] As a newly developed form of
carbon, it has been extensively explored in the field of elec-
trochemistry owing to its unique physical and electrochem-
ical properties.[2] Graphene can be distinguished from other
carbon-based materials by the following promising physical
properties. First, graphene is a semiconductor with a zero-
bandgap and hence it can be referred to as semimetal.[3]
Second, it demonstrates a striking ambipolar electric field
effect and hence the type of charge carriers can be tuned by
adjusting gate voltage.[4a] The charge carriers in graphene
with concentration of up to 1013 cm−2 exhibit high room-tem-
perature mobility of ∼10 000 cm2 V−1 s−1.[4b] Third, the charge
carrier transport in graphene is more naturally described by
the Dirac (relativistic) equation, hence the charge carriers
are identified as massless Dirac fermions[5] and can move
for micrometers without scattering under room temperature
conditions.[6] Besides, graphene can be considered as an ideal
electrode material[7] because of its large theoretical surface
area (2630 m2 g−1)[8a] and superior electrical conductance
(64 mS cm−1).[8b] Moreover, graphene exhibits remarkable
electrochemical properties, such as large potential window,
low charge-transfer resistance, excellent electrochemical
activity, fast electron transfer rate, etc.[9,10] The aforemen-
tioned extraordinary physical and electrochemical properties
of graphene enhance its electrochemical sensing application.
For example, the large surface area and superior electrical
conductance of graphene promises the efficient attachment
of analyte molecules,[11a] leading to the high sensitivity and
signal-to-noise ratio of graphene-based electrochemical
sensors.[11] In addition, the fast electron transfer between
graphene and analyte molecules promotes the direct rather
than mediated electrochemical reaction.[11b]
The attempts to synthesize graphene started from 1859 by
Brodie, who treated the graphite with strong acids to obtain
the exfoliated graphitic oxide.[12] After that, many methods
have been developed to separate individual graphene sheets
from the bulk graphite by overcoming the large interlayer
cohesive van der Waals energy of 5.9 kJ mol−1 carbon[2,13] in
graphite. These methods are top-down approaches. One of
the most popular top-down methods to obtain single-layer
graphene sheets is the mechanical exfoliation of highly-ori-
ented pyrolytic graphite (HOPG).[4b] However, this method
is limited by its low yield.[14] Alternatively, the bottom-up
approach is more attractive for the growth of graphene due
to its capability to obtain high-quality graphene, such as epi-
taxial growth on SiC,[15] chemical vapour deposition (CVD)
on Ni,[16] Cu[17] and Ru.[18] Another exceptional bottom-up
method, synthesis from organic precursors,[19] is different
from the aforementioned methods in terms of the growth of
large-area graphene, since it can synthesize graphene with
well-controlled structure, adjustable solubility and good
processability.
However, the solution-chemistry based methods are
more practical for high-volume and massive production of
graphene at low cost.[20] These methods generally involve the
small 2013, 9, No. 8, 1160–1172 © 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
oxidation of graphite to graphite oxide, the subsequent exfo-
liation to graphene oxide (GO) and the final reduction to
reduced graphene oxide (rGO, also referred to as graphene
in some papers). The oxidation and exfoliation can be
achieved by the Hummers method[21] with the aid of strong
acids and oxidizers. Many methods have been employed
for the reduction of GO, such as chemical reduction using
reducing agents (hydrazine,[22–24] dimethylhydrazine,[25] hyd-
roquinone,[26] vitamin C,[27] strong alkaline media,[28] bovine
serum albumin,[29] etc.), and electrochemical,[30,31] photo-
chemical,[32,33] thermal[34] and hydrothermal[35] reduction
approaches. Although both GO and rGO contains oxygen
functional groups, such as epoxy, hydroxyl and carboxyl
groups,[36] rGO contains less amount of oxygen functional
groups after the reduction of GO. These oxygen-containing
groups affect their electrochemical performance in terms of
electron transfer rate or adsorption/desorption of molecules,
and provide anchoring sites to enzymes or other specific spe-
cies for sensing applications.[10]
Possessing the exceptional physical and electrochemical
properties as well as the well-developed methods for the
production, graphene and its derivatives have been widely
applied in electrochemical studies, especially in electro-
chemical sensors. In the following content, the preparation of
graphene-based electrochemical electrodes and application
of different graphene-based materials for the electrochemical
detection of biomolecules and chemicals will be introduced
and discussed.
2. Preparation of Graphene-Based
Electrochemical Electrodes
2.1. Preparation of Electrodes Using GO
In most graphene-based electrochemical sensing experiments,
the GO aqueous solution was first prepared by solution-chem-
istry based methods, mostly the modified Hummers method.[22]
The GO-modified electrode can be fabricated by directly
dropping the GO dispersion onto various electrodes such as Pt
disk electrode,[37] Au electrode,[38] and glassy carbon electrode
(GCE).[39,40] To improve the immobilization of enzyme onto
the GO-coated electrode, the electrode can be immersed into
the buffer solution containing 1-ethyl-3-(3-dimethylamino-
prophy) carbondiimide hydrochloride (EDC) and N-hydroxyl
succinimide (NHS) in order to activate the carboxylic acid
Prof. H. Zhang, Dr. S. X. Wu, Q. Y. He, C. L. Tan
School of Materials Science and Engineering
Nanyang Technological University
50 Nanyang Avenue, Singapore 639798, Singapore
Website: http://www.ntu.edu.sg/home/hzhang/
E-mail: HZhang@ntu.edu.sg;
hzhang166@yahoo.com
Dr. Y. D. Wang
School of Engineering, Nanyang Polytechnic
180 Ang Mo Kio Avenue 8, Singapore 569830
DOI: 10.1002/smll.201202896
www.small-journal.com 1161
 reviews
(-COOH) groups on GO, through which the covalent bonding
between GO and the enzyme can be achieved.[37] Alternatively,
the addition of NaOH and chloroacetic acid into GO suspen-
sion could also produce the GO-COOH solution.[41]
As GO contains excessive oxygen functional groups, it
can be functionalized with various functional materials for
preparation of electrodes, such as nanoparticles, polymers
and organometallic compounds. For example, Qiu et al.
mixed GO with ferrocene branched chitosan (Fc-chitosan)
and enzyme for the coating of GCE to improve the stability
of GO and immobilization of enzyme.[39a] Lu et al. deposited
Ag nanoparticles (AgNP) onto NH2-functionalized silica
(F-SiO2) coated GO nanosheets via the direct adsorption of
AgNP or in-situ chemical reduction of Ag+.[40]
2.2. Preparation of Electrodes Using Chemically Reduced
Graphene Oxide (CrGO)
As mentioned above, graphene can be prepared by chemical
reduction of GO using various reducing agents, referred to
as CrGO. The most commonly used agent is hydrazine. The
rGO-modified electrodes can be fabricated by casting suspen-
sion of CrGO onto the GCE[42–45] or Au electrode.[46] Prior
to immobilizing CrGO onto the GCE, the electrode can be
modified by electrochemical polymerization of pyrrole, which
forms a stable matrix to enhance the encapsulation of CrGO
(Figure 1).[47] Similarly, Bo et al. modified GCE by using the
oxidized CrGO, which was obtained by oxidation of CrGO
with sulphuric acid and nitric acid, and polyaniline nanow-
ires formed by the electrochemical polymerization.[48] To
improve the immobilization of the enzyme and the electro-
catalytic activity of the electrode, metal nanoparticles (NPs)
were anchored onto the CrGO-modified GCE. For example,
Hu et al. used electrodeposition to grow gold nanoparticles
(AuNPs) on the CrGO-modified electrode.[49] Chen et al. pre-
pared the CrGO-AuNPs hybrid material through the in-situ
reduction method and then dropped its solution onto GCE.[50]
Zheng et al. used DNA as a linker to induce the formation
and self-assembly of AuNPs on the CrGO-modified electrode
in the presence of the enzyme.[51] Lu et al. used chemical
reduction of Pd2+ ions adsorbed on the GCE modified by the
mixture of CrGO and nafion (i.e. CrGO-nafion).[52]
To improve the dispersibility of CrGO in water, poly-
vinylpyrrolidone (PVP) was added into the solution during the
hydrazine reduction to protect CrGO from aggregation. Shan
Figure 1. Representation of graphene (CrGO)-glucose oxidase (GOD)
entrapped within a porous polypyrrole (Ppy) matrix. Reproduced with
permission.[47] Copyright 2010, American Chemical Society.
1162 www.small-journal.com © 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
S. X. Wu et al.
Hua Zhang obtained his BS (1992) and MS
(1995) degrees at Nanjing University, and
completed his PhD with Prof. Zhongfan Liu
at Peking University in 1998. As a Postdoc-
toral Fellow, he joined Prof. Frans C. De
Schryver’s group at Katholieke Universiteit
Leuven (Belgium) in 1999, and then Prof.
Chad A. Mirkin’s group at Northwestern
University in 2001. After working at NanoInk
Inc. (USA) and the Institute of Bioengineer-
ing and Nanotechnology (Singapore), he
joined Nanyang Technological University in
July 2006. His current research interests are
2D nanomaterials (such as graphene, transition metal dichalcogenides, etc.), and their
applications.
Shixin Wu received her Bachelor degree in
2008, and her PhD under the supervision
of Prof. Hua Zhang in 2012 at Nanyang
Technological University in Singapore. She is
currently a research scientist in the Institute
of Materials Research and Engineering of
A*STAR in Singapore. Her current research
interest focuses on the synthesis of graphene-
based composites and their application in
electrochemical sensors.
et al. prepared the nanocomposites of CrGO and AuNPs
through the sodium borohydride (NaBH4) reduction of
HAuCl4 onto PVP-protected CrGO, which mixed with chi-
tosan for the modification of Au electrode.[38] In addition,
ionic liquids, such as polyethleneimine-functionalized ionic
liquid (PFIL)[53,54] and 1-butyl-3-methylimidazolium hexafluo-
rophosphate ([bmim][PF6]),[55,56] are widely used for better
dispersion of CrGO and immobilization of enzyme.
Moreover, the dispersibility of CrGO can also be improved
by functionalization of CrGO through three steps: (1) pre-
reduction of GO by NaBH4, (2) reaction with diazonium salt
to introduce sulfonic groups onto the partially reduced GO,
and (3) post-reduction with hydrazine.[57] GCE modified with
the mixture of sulfonated CrGO-nafion, AuNPs and enzyme
solution showed superior electrochemical sensing perfor-
mance.[57] Zhang et al. used similar procedures to produce
functionalized CrGO for GCE modification except they used
polymeric ionic liquid of poly(1-vinyl-3-butylimidazolium
bromide) (poly(ViBuIm+Br−)) in the second step.[58] Other
functionalized CrGO for electrode modifications includes the
silanized CrGO (Figure 2),[59] 3,4,9,10-perylene tetracarbox-
ylic acid (PTCA)[60] and COOH-functionalized CrGO.[61]
It is worth mentioning that the CrGO-chitosan composite
is a promising material for electrodes since chitosan is used
to produce well dispersed CrGO and provide a good bio-
compatible environment for enzyme immobilization.[62–64] In
addition, chitosan is a good reducing agent for the prepara-
tion of CrGO dispersion,[65] and it can be covalently grafted
to CrGO, which offers a platform to attach other nanomate-
rials, e.g. Pd NPs, through the in-situ decoration.[66]
small 2013, 9, No. 8, 1160–1172
Graphene-Based Electrochemical Sensors

Figure 2. Schematic illustration of silanization of graphene (CrGO). Reproduced with permission.[59] Copyright 2010, American Chemical Society.

As known, the commonly adopted drop-casting method
for preparation of electrodes usually produces a non-
uniform coating of rGO thin film onto the electrodes and
shows the poor control over the film thickness. Hence, an
unconventional layer-by-layer (LbL) assembly method to
fabricate multilayer CrGO film-modified electrode was
developed by Zeng et al.[67] Various intermolecular inter-
actions can be utilized during the assembly process, such
as electrostatic interactions, hydrophobic interactions and
hydrogen bonds. In this work, CrGO was firstly modified
by pyrene-grafted poly(acrylic acid) (PAA) through the
π–π interaction and van der Waals force. The electrode was
then prepared by alternating immersion
of GCE in poly(ethyleneimine) (PEI)
and PAA-CrGO solution, and the multi-
layer CrGO film was formed due to the
electrostatic attraction between the posi-
tively charged PEI and the negatively
charged PAA-CrGO. In addition, the
negatively charged enzyme, e.g. glucose
oxidase and glucoamylase, can be immo-
bilized onto the PEI/PAA-CrGO modi-
fied GCE by alternating immersion of
the electrode into the positively charged
PEI and the negatively charged enzyme
solutions.

2.3. Electrode Preparation Using Graphene

Produced by Other Methods

The graphene-based electrode can be pre-

pared using graphene suspension obtained
by solvothermal reduction of GO, referred
to as SrGO. For example, Cao et al. reported
the synthesis of SrGO-CdS quantum dot
composite through a one-pot reaction,
where the reduction of GO and deposi-
tion of CdS NPs on SrGO occurred simul-
taneously in dimethyl sulfoxide (DMSO)
at a high temperature (Figure 3).[68] Wang
et al. then used the mixture of SrGO-CdS
nanocomposite, nafion and enzyme for
Figure 3. a) Scheme of one-step synthesis of graphene (SrGO)-CdS in dimethyl sulfoxide
(DMSO). b) Scheme of solvothermal reduction of GO. C) Bottle I, GO suspension in DMSO;
the modification of GCE.[69] Similarly,
bottle II, completion of reaction as SrGO-CdS settles down; bottle III, SrGO-CdS after washing Zhang et al. used the one-pot solvothermal
with acetone and ethanol; bottle IV, resuspension of SrGO-CdS in ethanol. Reproduced with method to synthesize SrGO-Cu2O nano-
permission.[68] Copyright 2010, Wiley-VCH. composite for the modification of GCE.[70]

small 2013, 9, No. 8, 1160–1172 © 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim www.small-journal.com 1163
 reviews S. X. Wu et al.

Figure 4. Schematic illustration of preparation of ErGO-modified electrode through electrochemical reduction of graphene oxide (GO) adsorbed
on the 3-aminopropyltriethoxysilane (APTES) modified glassy carbon electrode (GCE) and the subsequent modification of the electrode with
polymerization of N-succinimidyl acrylate (pNSA) and glucose oxidase (GOx). Reproduced with permission.[30a] Copyright 2009, American Chemical
Society.

Recently, our group has prepared graphene-modified
electrode through the direct electrochemical reduction of
GO adsorbed on the 3-aminopropyltriethoxysilane (APTES)-
modified GCE (GCE-APTES), referred to as ErGO.[30a,71] To
bond the enzyme covalently and hence improve the enzyme
immobilization, N-succinimidyl acrylate (NSA) was electro-
grafted onto the GCE-APTES-ErGO (Figure 4).[30a] Gao
et al. fabricated the ErGO-modified electrode through the
direct ultrasonic-electrodeposition, by which the electrochem-
ical reduction of GO-modified GCE and electrodeposition of
PtNi NPs occurred simultaneously, referred to as ErGO-PtNi
NPs (Figure 5).[72] Moreover, Unnikrishnan et al. casted the
mixture of GO and enzyme on GCE, which was then elec-
trochemically reduced to produce the electrode for glucose
sensing.[73] Similarly, Zhang et al.[74] and Du et al.[75] con-
structed the ErGO-modified electrodes by dropping GO, NiO
nanofibers (NiONFs) and nafion suspensions or dropping pol-
yaniline and GO suspensions sequentially on GCE, respec-
tively, followed by the electrochemical reduction, referred to
as ErGO-NiONF-nafion[74] or ErGO-polyaniline.[75]

Figure 5. Schematic illustration of formation of reduced graphene oxide (ErGO)-PtNi NPs by the direct ultrasonic-electrodeposition method.
Reproduced with permission.[72] Copyright 2011, American Chemical Society.

1164 www.small-journal.com © 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim small 2013, 9, No. 8, 1160–1172
Graphene-Based Electrochemical Sensors

Alternatively, Liu et al. prepared the ErGO-modified elec-
trode by electrochemical reduction of GO casted on GCE,
followed by drop-casting of PVP on the electrode, referred
to as ErGO-PVP.[76] Specifically for the DNA sensor, Dong
et al. fabricated the ErGO-based electrode by drop-casting
of thiol-group-DNA strand (d(GT)29SH) and probe-labeled
gold nanoparticles (AuNPs-ssDNA) after electrochemical
reduction of GO casted on GCE, referred to as ErGO-
d(GT)29SH-AuNPs-ssDNA.[77] To produce amplified detec-
tion signal, the signal tag of streptavidin (SA)-horseradish
peroxidase (HRP) functionalized carbon spheres (referred
to as SA-HRP-CNS) was dropped onto the electrode after
hydrization with biotinylated target DNA.[77]
Different from the aforementioned methods, Shang
et al. fabricated multilayer graphene nanoflake films (MGNFs)
by microwave-assisted plasma chemical vapour deposition
(MPCVD) on Si substrate, which can be directly used as a
working electrode for electrochemical sensing applications.[78]
Similarly, Lim et al. used the epitaxial graphene, first grown
on silicon carbide substrates and subsequently anodized by
electrochemical treatment, as the working electrode.[79]
Most recent advances include using the 3D graphene
foam fabricated on Ni foam by CVD (CVD-3D-GF) as the
electrochemical electrode to increase the active surface area
and create multiplexed charge transport pathways and hence
improve the sensitivity of the electrochemical sensor.[80a]
Afterwards, they integrated the 3D graphene foam with
cobalt oxide (Co3O4) nanowires, which showed electrocata-
lytic behavior towards the glucose oxidation, to obtain the
superior enzymeless glucose sensor, referred to as CVD-
3D-GF-Co3O4.[80b] Differently, Penmatsa et al. fabricated
3D graphene structure with large surface area through the
electrostatic spray deposition of graphene solution onto 3D
carbon micropillars.[81]
Furthermore, graphene with alternative morpholo-
gies has also been applied for electrochemical sensors. For
example, Zhao et al. utilized graphene quantum dots (GQD)
synthesized by hydrothermal cutting of thermally reduced
GO sheets as a smart sensor platform for DNA and pro-
tein detections.[82] Wu et al. prepared the sensing electrode
with the composite of graphene nanoribbon (GNR) and
nafion for the selective detection of cysteine.[83a] GNR was
obtained through oxidation of multiwalled carbon nanotubes
(MWCNTs) followed by the hydrazine reduction.[83b] The
as-obtained GNR contained abundant oxygen-containing
groups that were beneficial for detection of thiols based on
either the 1,4 Michael addition or cycling addition reaction
between thiols and carbonyl groups present on GNR.[83a]
3. Graphene-Based Electrochemical Sensors
3.1. Enzyme Biosensors
As mentioned in the Introduction part, graphene possesses
outstanding physical and electrochemical properties, such as
large surface area, high conductivity, abundant defect sites,
superior electrocatalytic activity and fast electron transfer
rate, hence various enzyme biosensors based on this attrac-
tive material have been fabricated recently. One of the
most extensively studied examples is the graphene-based
glucose sensor as the determination of glucose is highly
important in diagnosis of diabetes.[84] To detect glucose, the
graphene-based electrode is usually modified by glucose oxi-
dase (GOD) in the final step of electrode preparation, i.e.
casting of the solution containing GOD onto the electrode.
The glucose sensing performances of different graphene-
based materials are compared and summarized in Table 1.

Table 1. Performance of glucose sensors with graphene-based electrodes. RSD: relative standard deviation.

Graphene-based materials Linear range Detection limit Sensitivity Reproducibility: RSD for Stability,% of initial Ref.
[mM] [μM] [μA mM−1 cm−2] (No. of electrodes) response after (days)
GO-Fc-chitosan 0.02–6.78 7.6 10 4.3% (5) >90% (1 month) [39a]
GO-F-SiO2-AgNP 2–12 310 4.1% (5) 83% (4 days) [40]
CrGO 0.1–10 10 ± 2 110 ± 3 2.5% (6) No obvious decrease [43]
(2 days)
CrGO-chitosan 0.08–12 20 37.93 5.3% (6 experiments) 95% (1 week) [62]
CrGO-poly(ViBuIm+Br−) 0.8–20 267 7.67 × 105 92% (2 weeks) [58]
CrGO-chitosan-Pd NPs 0.0–011 0.2 31.2 5.1% (5) 80% (3 weeks) [66]
CrGO-nafion-Pd NPs 0.010–5 1 3.7% (10) 98% (35 days) [52]
CrGO-AuNPs 0.1–10 35 0.74% (3) 80% (4 months) [50]
CrGO-DNA-AuNPs 0.0008–0.05 0.3 2.44 × 104 2.1% (6) 95% (1 month) [51]
Sulfonated 0.015–5.8 5 5.4% (5) 90% (3 weeks) [57]
CrGO-nafion-AuNPs
SrGO-CdS 2–16 700 1.76 4.2% (5) 93% (30 days) [69]
ErGO-PtNi alloy NPs Up to 35 10 20.42 < 5.0% (10) 90.5% (50 days) [72]
ErGO-NiONFs-nafion 0.002–0.6 0.77 1100 7.7% (6) 90.0% (1 month) [74]
CrGO-Ni(II)-quercetin 0.003–0.9 0.5 187 μAmM−1 5.1% (7) 92.1% (20 days) [86a]
CVD-3D-GF-Co3O4/glass Up to 0.080 0.025 3390 [80b]

small 2013, 9, No. 8, 1160–1172 © 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim www.small-journal.com 1165
 reviews
All the electrodes in Table 1 are graphene-modified GCEs
except the electrode of CVD-3D-GF-Co3O4 on glass. Similar
graphene-based materials are listed in the table to give a
comparison.
It can be seen from Table 1 that the rGO-based glucose
biosensors are favoured over the GO-based ones in terms
of sensing performance. It is known that GO contains more
oxygen-containing groups than does rGO, while the con-
ductivity of rGO is much higher than that of GO due to the
recovery of conjugated graphitic network after the reduc-
tion process. Therefore, GO-based electrodes exhibit a lower
sensitivity than do most of rGO-based ones. Casero et al.
studied the electrochemical impedance spectra of GO and
rGO, showing that the charge transfer resistance of GO is
much higher than that of rGO.[85] In their study, it was dem-
onstrated that the presence of abundant oxygen-containing
groups would contribute to the finite-length Warburg element
in the impedance spectra, hence the GO-based electrode
showed the finite-length diffusion, while the rGO-modified
one showed the semi-infinite diffusion.[85]
Among the rGO-based electrodes, the electrode modified
with CrGO-chitosan-Pd NPs shows the lowest detection limit,
0.2 μM.[66] The superior performance can be attributed to the
covalent functionalization of CrGO with chitosan, which
improves the hydrophilicity and biocompatibility of CrGO;
and the well dispersed, high loading of Pd NPs with small size
(∼4–5 nm) and its high electrocatalytic activity.[66] Compared
to the CrGO-chitosan-Pd NPs, the CrGO functionalized with
nafion and decorated with Pd NPs (CrGO-nafion-Pd NPs)
shows a higher detection limit but much better reproduc-
ibility and long-term stability. It is known that nafion has a
hydrophobic backbone while chitosan is hydrophilic. Such a
difference would result in different interactions with CrGO
and produce Pd NPs with different morphologies. Obviously,
the resulted Pd NPs (size of 30–40 nm) in CrGO-nafion-Pd
NPs is larger than those in CrGO-chitosan-Pd NPs, which
may explain the different sensing behaviors of these two
electrodes.
In addition, the sensor made by CrGO-DNA-AuNPs
showed a much lower detection limit and much higher sensi-
tivity compared to other CrGO-based electrodes containing
AuNPs.[50,57] It was ascribed to the robust self-assembly of
SH and NH2 of the DNA strand with AuNPs.[51] Moreover,
it could be explained by the synergistic effects from the
DNA functionalized CrGO and AuNPs in terms of electron
transfer ability and signal amplification from materials in
nanoscale.[51]
Furthermore, CrGO-poly(ViBuIm+Br−) shows the highest
sensitivity in glucose detection compared to other CrGO-
based electrodes since CrGO modified with the specific ionic
liquid exhibits the improved conductivity and gives the direct
electron transfer between the immobilized GOD and the
CrGO-modified electrode surface.[58]
Recently, several nonenzymatic glucose biosensors based
on graphene-modified GCE have been developed[72,74,86,87]
such as ErGO-PtNi alloy NPs,[72] ErGO-NiONFs,[74] CrGO-
Ni(II)-quercetin[86a] and CVD-3D-GF-Co3O4.[80b] Surpris-
ingly, the glucose sensor based on 3D graphene-Co3O4
composite shows the lowest detection limit of 25 nM[80b]
1166 www.small-journal.com © 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
S. X. Wu et al.
among all the graphene-based electrodes. Moreover, it also
shows a high sensitivity of 3.39 mA mM−1 cm−2. The elec-
trocatalytic activity and large electrochemical capacitance
of Co3O4 nanowires as well as the large surface area and
high conductivity of 3D graphene foam contribute to the
impressive sensing performance towards glucose detec-
tion. In addition, it is obvious that the sensor prepared with
ErGO-NiONFs-nafion shows a much lower detection limit
and higher sensitivity than those with ErGO-PtNi alloy NPs,
which could be attributed to the large microscopic surface
area and good catalytic activity of NiONFs as well as to the
superior electrochemical properties of ErGO.[74] Interest-
ingly, the sensor constructed with CrGO-Ni(II)-quercetin
exhibits similar sensing performance to that with ErGO-
NiONFs-nafion. It is believed that the quercetin, which can
form stable complexes with various metal cations,[88] such as
Ni(II), may contribute to the steady and strong electrocata-
lytic activity of Ni(II) for glucose detection.
In addition to GOD, other enzymes may be immobilized
onto graphene-based electrodes for construction of various
enzyme biosensors, such as horseradish peroxidase (HRP),[89]
alcohol dehydrogenase (ADH),[90] catalase[91] and urease.[92]
For example, very recently, Prasannakumar et al. fabricated an
alcohol biosensor using graphene-carbon nanotubes (CNTs)
modified graphite electrode immobilized with ADH.[90a] The
as-fabricated electrode showed a linear range of 25–200 μM, a
sensitivity of 82.5 nA μM−1 cm−2 (i.e. 82.5 μA mM−1 cm−2) and
a detection limit of 10 μM.[90a] The sensitivity is a bit higher
than that using the ionic liquid-functionalized graphene-based
electrode fabricated by Shan et al. (37.43 μA mM−1 cm−2).[90b]
The higher sensitivity of graphene-CNT modified electrode
could be attributed to the high conductivity of graphene-
CNT composite resulted from the interconnections between
graphene and CNTs which bridge the gaps among graphene
sheets.[93]
3.2. Nonenzymatic Sensors for Small Biomolecules
Electrochemical sensing of small biomolecules, such as dopa-
mine, ascorbic acid and uric acid, is another important appli-
cation of graphene-based electrodes in electrochemistry due
to the fast electron transfer kinetics and superior electro-
catalytic activity of graphene-based materials. Dopamine is
one of the most studied small biomolucules using graphene-
based biosensors. Dopamine measurement is crucial since
its change in the concentration is closely linked to one's
health status.[78] However, it is difficult to be detected selec-
tively and sensitively in the presence of its coexisting species,
ascorbic acid (AA) and uric acid (UA), due to their overlap-
ping voltammetric response.[78] Recently, graphene-based
electrodes have shown great performance as electrochemical
sensors towards dopamine[94–100] even in the presence of AA
or/and UA due to its excellent physical and electrochemical
properties and the feasible electron transfer between gra-
phene and dopamine through the π–π interaction.[45a,64,94,95]
Table 2 summarizes the dopamine sensing performances
from different graphene-based electrodes. All the electrodes
in Table 2 are graphene-modified GCE except the electrodes
small 2013, 9, No. 8, 1160–1172
Graphene-Based Electrochemical Sensors

Table 2. Performance of dopamine sensors with graphene-based electrodes. RSD: relative standard deviation.

Graphene-based Linear range Detection limit Reproducibility: RSD Stability,% of initial Detection limit Ref.
materials [μM] [μM] for (No. of electrodes) response after (times obtained in the pres-
of experiments (days) ence of interfering
compounds
MPCVD-MGNFs/Si 1–100 (two ranges) 0.17 80% (300 scans) 1 mM AA, 0.1 mM UA [78]
CVD-3D-GF/glass Up to 25 0.025 [80a]
CrGO 4–100 2.64 2.1% (4) 90% (5 measurements) 1 mM AA [45a]
CrGO-β-cyclodextrin 0.009–12.7 (two 0.005 [96]
ranges)
CrGO-chitosan 1.0–24 1.0 0.1 mM AA, 0.02 mM [64]
UA
Silanized CrGO-nafion 0.20–25 0.01 1 mM AA [59]
CrGO-poly (p-amin- 0.03–1.16 or 0.05–10 0.01 or 0.02 4.2% (5) 98.5% (14 days) Without AA or With 0.1 [97]
obenzoic acid) (two ranges) mM AA
CrGO-Congo red- 0.1–830 0.1 3.77% (6 detections) 95.3% (3 weeks) [100]
molecular imprinted
polymers
CrGO-Pt NPs 0.03–8.13 0.03 [98]
CrGO-Zn/Al layered 1.019–9 0.3 5.4% (8 88.4% (5 weeks) 0.1 mM AA [99]
double hydroxide films measurements)
SrGO-Cu2O NPs 0.11–0 0.01 or 0.2 3.5% (10) Without UA or With 0.5 [70]
mM UA
ErGO-PVP 0.0005–1130 0.0002 2.16% (5) 90.1% (10 days) 1 mM AA [76]

of MPCVD-MGNFs on Si and CVD-3D-GF on glass. Sim-
ilar graphene-based materials are listed in the table to give a
comparison.
From Table 2, it can be seen that MGNFs grown on Si
by MPCVD showed a lower detection limit compared to
the CrGO-modified GCE. The superior sensing perfor-
mance from MGNFs could be explained by its abundant
edge defects that have different electrochemical interaction
potential with dopamine and its negative charge from struc-
tural motifs, which repels anionic AA and UA but favourably
interacts with cationic dopamine.[78] It is emphasized that the
oxygen-containing groups on MGNFs are not the reason for
distinguishing dopamine from AA and UA.[78]
Moreover, the sensor based on ErGO-PVP shows the
lowest detection limit of 0.2 nM and largest linear range from
0.0005 to 1130 μM in the presence of 1 mM AA. The impres-
sive sensing performance from ErGO-PVP is obtained by
optimizing the concentration of GO and PVP and the pH.[76]
In addition, the high selectivity towards DA in the presence
of AA from ErGO-PVP could be explained by the strong
adsorption property of PVP to phenolic compounds in DA
but week interaction with AA as well as the particular elec-
trode preparation method.[76] Besides, CrGO-β-cyclodextrin
shows the second lowest detection limit of 0.005 μM in the
absence of interfering compounds. One reason for its supe-
rior performance is that the addition of β-cyclodextrin could
improve the dispersion of CrGO, which results in more acces-
sible active sites and enhanced catalytic activity.[96]
In addition to the CrGO-β-cyclodextrin, the silanized
CrGO-nafion, CrGO-poly (p-aminobenzoic acid) and SrGO-
Cu2O NPs also show very low detection limit of 0.01 μM
in the absence of AA and UA. The silanized CrGO-nafion
combined the advantages from both nafion and silanized
CrGO.[59] Nafion can improve the selectivity of the electrode
towards dopamine due to its sulphuric groups that act as an
anion barrier.[59] The silanized CrGO has the large active
electrode surface area and more active functional groups due
to the chemical modification of CrGO.[59] Both can accelerate
the electron transfer, catalyze the dopamine oxidation and
concentrate dopamine from solutions containing anionic spe-
cies.[59] The excellent sensing performance from CrGO-poly
(p-aminobenzoic acid)-modified GCE can be attributed to
the good conductivity and high catalytic ability of CrGO-poly
(p-aminobenzoic acid).[97] More importantly, the negatively
charged p-aminobenzoic acid, which contains high density of
carboxyl groups, could enhance its electrostatic interaction
with dopamine.[97] From the study of SrGO-Cu2O NPs in the
dopamine detection, it is found that the superior sensitivity
of the electrode is mainly because of the highly dispersed
Cu2O NPs on SrGO, that lead to the improved electron
transfer rate of SrGO and increased electrocatalytic ability
towards dopamine.[70] It is worthy to mention that the sensor
made by CVD-3D-GF with macroporous structure and high
conductivity shows a low detection limit of 25 nM based
on the signal to noise ratio of 5.6 and a high sensitivity of
619.6 μA mM−1 cm−2.[80a] The superior sensing performance
could be attributed to the novel architecture of CVD-3D-GF,
which could provide large surface area for interaction with
dopamine and multiplexed conductive pathways for the elec-
tron transport between graphene and dopamine.[80a]
In addition to dopamine, graphene-based electrodes have
been fabricated as nonenzymatic sensors to detect other

small 2013, 9, No. 8, 1160–1172 © 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim www.small-journal.com 1167
 reviews
small biomolecules, such as hydrogen peroxide (H2O2).[101]
For example, the Sun group has recently studied the nonen-
zymatic detection of H2O2 using AgNPs and rGO compos-
ites (AgNPs/rGO).[101] The AgNPs/rGO synthesized with
a reducing agent of diethylenetriamine (AgNPs/rGO-1)
showed a linear detection range from 0.1 to 100 mM and a
detection limit of 3.6 μM.[101a] Comparatively, AgNPs/rGO
synthesized under alkaline condition without any reducing
agent (AgNPs/rGO-2) showed a linear range from 0.1 to
60 mM and a detection limit of 1.8 μM.[101b] Their electro-
chemical sensing performances are quite similar since both
used the composite of AgNPs and rGO. The slight differ-
ence could be attributed to the different morphologies of
AgNPs formed under different synthesis conditions. AgNPs
in AgNPs/rGO-1 had sizes ranging from 10 to 150 nm while
those in AgNPs/rGO-2 had a bimodal size distribution
at 5 nm and 40 nm, respectively.[101] The smaller AgNPs in
AgNPs/rGO-2 with a larger surface area may have a higher
electrocatalytic property, resulting in a lower detection limit.
However, the detection limit of such a graphene-based non-
enzymatic sensor is still lower than that of the enzymatic
sensor such as 9 nM from the sensor using graphene impreg-
nated with HRP multimer.[102]
3.3. DNA Sensors
With the development of graphene-based electrodes in electro-
chemical sensors, the application of graphene-based materials
has been further explored for detection of DNA[103–105]
and the single-nucleotide polymorphisms (SNPs) without
any hybridization or labelling process since the electrode can
detect each base in the oligonucleotides quantitatively.[42b]
Zhou et al. reported the CrGO-modified GCE could be used
to detect four free bases of DNA simultaneously, which was
impossible to achieve on the GCE or graphite electrode.[42b]
It could be explained by the abundant edge-plane-like defec-
tive sites, antifouling properties and high electron transfer
kinetics of CrGO in addition to its unique physical and elec-
trochemical properties.[42b] Table 3 lists the performances of
some graphene-based materials for DNA detection. All the
electrodes in Table 3 are graphene-modified GCE. Similar
graphene-based materials are listed in the table to give a
comparison.
By comparing the sensing performances of graphene-
based electrodes in Table 3, it can be seen that ErGO-
polyaniline exhibits a lower detection limit than does Oxidized
CrGO-polyaniline. The different sensing performance may
be explained by the different graphene-based materials used
and different methods adopted for deposition of polyaniline
onto the electrodes. In addition, ErGO-d(GT)29SH-AuNPs-
ssDNA produces the lowest detection limit of 5 aM. Such
an extremely low detection limit is resulted from the triplex
signal amplification strategy, which utilizes the high conduc-
tivity of AuNPs-ssDNA and signal amplification from a signal
tag of SA-HRP-CNS that relates each target hybridization
event to multiple enzyme reaction.[77] The widest detection
range is achieved by GCE modified with PTCA functional-
ized CrGO-IL-AuNPs, which also shows a very low detection
1168 www.small-journal.com © 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
S. X. Wu et al.
Table 3. DNA sensing performance from different graphene-based
electrodes. RSD: relative standard deviation; IL: amine-terminated
ionic liquid, 1-(2-aminoethyl)-3-methylimidazolium bromide.
Graphene-based Dynamic range Detection Reproducibility: RSD for Ref.
materials [nM] limit [pM] (No. of experiments)
ErGO-polyaniline 0.0001–100 0.032 5.4% (10) [75]
Oxidized 0.00212–2120 0.325 1.15% (7) [48]
CrGO-polyaniline
CrGO-DNA-AuNPs- 0.2–500 72 [105]
Ag
PTCA functionalized 0.001–1000 0.5 [60]
CrGO
PTCA functionalized 0.0001–1000 0.034 6.04% (4) [106]
CrGO-IL-AuNPs
ErGO-d(GT)29SH- 1E-8–1E-4 5E-6 [77]
AuNPs-ssDNA
limit of 0.034 pM. The small size of AuNPs (mean diameter of
∼3 nm) in PTCA functionalized CrGO-IL-AuNPs was mainly
due to the presence of IL, which could control the size and
structure of NPs.[106] Compared to GCE modified with PTCA
functionalized CrGO, the lower detection limit can be attrib-
uted to the addition of AuNPs, which can increase the active
surface area and conductivity of CrGO and improve the
immobilization of probe DNA and magnify DNA hybridi-
zation signal.[106] In addition, the abundant imidazolium
cations at the outer layer of AuNPs from IL could increase
the binding of negatively charged probe DNA and hence
improve the sensitivity of the electrode.[106]
However, the sensor made by GQD only showed a linear
range of 200–500 nM and a detection limit of 100 nM.[82] The
poor sensing performance of GQD could be attributed to the
design of the sensing experiment which used the [Fe(CN)6]3-/4−
as the electrochemical active species for the sensing signal.
Theoretically, GQD with small size would have more edge
defects for the interactions with DNA or other analyte mole-
cules, and hence it could produce enhanced signal and exhibit
superior sensing performance. Therefore, it is highly expected
to construct electrochemical sensors using GQD based on
the well-designed sensing mechanism.
3.4. Immunosensors
By immobilizing the antibodies to capture the corresponding
antigens on graphene-based electrodes, graphene-based
electrochemical immunosensors can be achieved. The high
selectivity and sensitivity of the immunosensors can be real-
ized based on the specific interaction between antibodies
and antigens. For example, Mao et al. fabricated an immu-
nosensor using graphene sheet-methylene blue (GS-MB)
nanocomposite to detect a model analyte of prostate specific
antigen (PSA).[107] Due to the efficient absorption of anti-
bodies on MB and improved electroactivity of MB in the
presence of graphene which possesses a large surface area
and excellent conductivity, the sensor showed a linear range
of 0.05–5.00 ng/mL and a detection limit of 13 pg/mL.[107] The
small 2013, 9, No. 8, 1160–1172
Graphene-Based Electrochemical Sensors
sensitivity can be further improved by using nanomaterials
entrapped with antibodies to amplify the electrochemical
signals of the immunological reactions, such as quantum dot,
CNTs and metal NPs. For example, Yang et al. constructed
a sandwich-type immunosensor using graphene sheets (GS)
and quantum dot functionalized graphene (QD-GS) to
immobilize primary antibody (Ab1) and secondary antibody
(Ab2), respectively. The as-constructed immunosensor was
applied for the detection of PSA and showed a linear range
of 0.005-10 ng/mL and a detection limit of 3 pg/mL.[108] Lu
et al. built a sandwich-type immunosensor with AuNPs
dotted CNTs-graphene composite to detect the human chori-
onic gonadotrophin (hCG).[109] They particularly emphasized
the fixation of AuNPs onto the composite of thionine and
mesoporous nanoparticles MCM-41, in which thionine could
provide a strong linkage between MCM-41 and AuNPs and
enhance the loading of the secondary antibody.[109] In addi-
tion, MCM-41 with a high surface-to-volume ratio could also
improve the conjugation of biomolecules.[109] In the AuNPs
dotted CNTs-graphene composite, AuNPs were used to pro-
vide effective electron transport and ideal microenvironment
for the attachment of biomolecules. The coupling between
CNTs and graphene was used to improve the electron transfer
efficiency and immobilization of primary antibody.[109] The as-
built sensor showed a linear range from 0.005 to 500 mIU/mL
(about 0.0003–30 ng/mL) and a detection limit of 0.0026 mIU/mL
(about 0.000156 ng/mL).[109] The sensing performance is
much superior to the immunosensor fabricated by Li et al.
using nanoporous Au foil and graphene for the detection of
hCG with a linear range of 0.5–40.0 ng/mL and a detection
limit of 0.034 ng/mL.[110]
3.5. Other Sensors
In addition to biomolecules, graphene-based electrodes have
been applied for the detection of chemicals.[111–113] Due to the
large surface area and high conductivity of graphene, it can
sensitively detect heavy metal ions,[114] toxic chemicals,[115]
organic molecules[116] and so on. For example, Gao et al. syn-
thesized the AlOOH-rGO nanocomposites for the electro-
chemical analysis of Cd(II) and Pb(II) simultaneously in one
solution.[114a] Since AlOOH shows a strong adsorption and
accumulation capacity toward the heavy metal ions, and rGO
possesses the excellent conductivity for efficient charge trans-
port between electrode surface and metal ions, the nanocom-
posites combine the advantages of the two materials and show
a detection limit of 352 nM for Cd(II) and 932 nM for Pb(II)
during the detection of two metal ions in one solution.[114a]
Moreover, the detection of other meal ions simultaneously
can be achieved by the composite, such as Zn(II), Cu(II), and
Hg(II), based on different detection potentials for different
metal ions.[114a] Lei et al. used the MnO2/GO composite for
hydrazine detection, which showed a linear range of 3 μM to
1.12 mM, with a detection limit of 0.16 μM and a sensitivity of
1.007 mA mM−1 cm−2.[115a] The high electrochemical sensing
performance can be attributed to the abundant oxygen-
containing groups and large surface area of GO for the MnO2
absorption, and the superior catalytic properties of MnO2 for
small 2013, 9, No. 8, 1160–1172 © 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
hydrazine oxidation.[115a] Li et al. realized the determination
of p-aminophenol based on the ErGO-modified electrode,
which showed a linear range of 0.01–10 μM and a detection
limit of 2.9 nM based on the signal to noise ratio of 3.[116a]
Such a sensing electrode takes the advantages of ErGO in
terms of large surface area, fast electronic transport kinetics
and good π–π interaction with p-aminophenol.[116a]
4. Summary
This review presents a brief introduction on the advanta-
geous properties of graphene and briefly summarizes various
graphene preparation methods. The superior electrochemical
sensing performances of graphene-based electrodes towards
the detection of various biomolecules and chemicals have
been demonstrated in this review, especially the recent pro-
gress of applications of graphene in electrochemical sensors
has been addressed. Nonetheless, there is still much room
for the exploration of graphene-based electrodes in electro-
chemical sensors and challenges remain in the understanding
and developing of graphene in the area of electrochemistry.
For example, methods to obtain graphene with the desired
morphology (e.g. graphene nanoribbon, quantum dot, 3D
network), structure (e.g. amount of oxygen functional groups,
presence of other specific functional groups), and properties
(e.g. catalysis, conductivity) should be developed. Further-
more, the interactions between graphene and analyte mol-
ecules, such as the absorption mechanism of molecules on
graphene and the charge transport kinetics at the graphene
interface, should be explored. In addition, the construction
of electrochemical sensors with different graphene-based
materials, different sensor structures and different sensing
mechanisms is also a great challenge. In addition to graphene,
other 2D nanomateirals, such as transition metal dichalco-
genides,[117] can also be applied for electrochemical sensing
applications as well. Recently, our group has synthesized
single-layer MoS2 through an electrochemical lithiation pro-
cess[118] and applied it for glucose and biomolecules detec-
tions.[119] The electrochemically reduced MoS2 demonstrates
the high electrochemical activity and good sensing perfor-
mance, which offers an alternative platform for the electro-
chemical sensor.
Acknowledgements
This work was supported by MOE under AcRF Tier 2 (ARC 10/10,
No. MOE2010-T2-1-060), Singapore National Research Foun-
dation under CREATE programme: Nanomaterials for Energy
and Water Management, and NTU under the Start-Up Grant
(M4080865.070.706022) in Singapore.
[1] a) N. O. Weiss, H. L. Zhou, L. Liao, Y. Liu, S. Jiang, Y. Huang,
X. F. Duan, Adv. Mater. 2012, 24, 5782; b) X. Huang, X. Y. Qi,
F. Boey, H. Zhang, Chem. Soc. Rev. 2012, 41, 666.
www.small-journal.com 1169
 reviews
[2] D. Chen, L. H. Tang, J. H. Li, Chem. Soc. Rev. 2010, 39, 3157.
[3] X. Huang, Z. Y. Yin, S. X. Wu, X. Y. Qi, Q. Y. He, Q. C. Zhang,
Q. Y. Yan, F. Boey, H. Zhang, Small 2011, 7, 1876.
[4] a) J. F. Tian, L. A. Jauregui, G. Lopez, H. Cao, Y. P. Chen, Appl.
Phys. Lett. 2010, 96, 263110; b) K. S. Novoselov, A. K. Geim,
S. V. Morozov, D. Jiang, Y. Zhang, S. V. Dubonos, I. V. Grigorieva,
A. A. Firsov, Science 2004, 306, 666.
[5] K. S. Novoselov, A. K. Geim, S. V. Morozov, D. Jiang,
M. I. Katsnelson, I. V. Grigorieva, S. V. Dubonos, A. A. Firsov,
Nature 2005, 438, 197.
[6] A. K. Geim, Science 2009, 324, 1530.
[7] X. Huang, Z. Y. Zeng, Z. X. Fan, J. Q. Liu, H. Zhang, Adv. Mater.
2012, 24, 5979.
[8] a) M. D. Stoller, S. J. Park, Y. W. Zhu, J. H. An, R. S. Ruoff, Nano
Lett. 2008, 8, 3498; b) C. Liu, S. Alwarappan, Z. F. Chen,
X. X. Kong, C. Z. Li, Biosens. Bioelectron. 2010, 25, 1829.
[9] M. Pumera, A. Ambrosi, A. Bonanni, E. L. K. Chng, H. L. Poh,
Trends Anal. Chem. 2010, 29, 954.
[10] a) D. A. C. Brownson, C. E. Banks, Analyst 2010, 135, 2768;
b) Y. Y. Shao, J. Wang, H. Wu, J. Liu, I. A. Aksay, Y. H. Lin, Electro-
anal. 2010, 22, 1027.
[11] a) B. Pérez-López, A. Merkoçi, Anal. Bioanal. Chem. 2011, 399,
1577; b) D. Chen, H. Feng, J. Li, Chem. Rev. 2012, 112, 6027.
[12] B. C. Brodie, Philos. Trans. R. Soc. London 1859, 149, 249.
[13] R. Zacharia, H. Ulbricht, T. Hertel, Phys. Rev. B 2004, 69,
155406.
[14] M. J. Allen, V. C. Tung, R. B. Kaner, Chem. Rev. 2010, 110, 132.
[15] R. Zhang, Y. L. Dong, W. J. Kong, W. P. Han, P. H. Tan, Z. M. Liao,
X. S. Wu, D. P. Yu, J. Appl. Phys. 2012, 112, 104307.
[16] a) R. S. Weatherup, B. C. Bayer, R. Blume, C. Baehtz,
P. R. Kidambi, M. Fouquet, C. T. Wirth, R. Schlogl, S. Hofmann,
ChemPhysChem 2012, 13, 2544; b) D. Nezich, A. Reina,
J. Kong, Nanotechnol. 2012, 23, 015701; c) X. H. Cao, Y. M. Shi,
W. H. Shi, G. Lu, X. Huang, Q. Y. Yan, Q. C. Zhang, H. Zhang,
Small 2011, 7, 3163; d) X. H. Cao, Z. Y. Zeng, W. H. Shi,
P. R. Yep, Q. Y. Yan, H. Zhang, Small 2013, DOI: 10.1002/
smll.201200683.
[17] a) L. Tao, J. Lee, M. Holt, H. Chou, S. J. McDonnell, D. A. Ferrer,
M. G. Babenco, R. M. Wallace, S. K. Banerjee, R. S. Ruoff,
D. Akinwande, J. Phys. Chem. C 2012, 116, 24068;
b) T. Terasawa, K. Saiki, Carbon 2012, 50, 869.
[18] P. W. Sutter, J.-I. Flege, E. A. Sutter, Nat. Mater. 2008, 7, 406.
[19] X. Yang, X. Dou, A. Rouhanipour, L. Zhi, H. J. Rader, K. Mullen,
J. Am. Chem. Soc. 2008, 130, 4216.
[20] T. Kuila, S. Bose, A. K. Mishra, P. Khanra, N. H. Kim, J. H. Lee,
Prog. Mater Sci. 2012, 57, 1061.
[21] W. S. Hummers, R. E. Offeman, J. Am. Chem. Soc. 1958, 80,
1339.
[22] a) D. Li, M. B. Muller, S. Gilje, R. B. Kaner, G. G. Wallace, Nat.
Nanotechnol. 2008, 3, 101; b) J. T. Han, J. I. Jang, B. H. Jeong,
B. J. Kim, S. Y. Jeong, H. J. Jeong, J. H. Cho, G.-W. Lee, J. Mater.
Chem. 2012, 22, 20477.
[23] X. Y. Qi, K. Y. Pu, H. Li, X. Z. Zhou, S. X. Wu, Q. L. Fan, B. Liu,
F. Boey, W. Huang, H. Zhang, Angew. Chem. Int. Ed. 2010, 49,
9426.
[24] X. Z. Zhou, X. Huang, X. Y. Qi, S. X. Wu, C. Xue, F. Y. C. Boey,
Q. Y. Yan, P. Chen, H. Zhang, J. Phys. Chem. C 2009, 113,
10842.
[25] S. Stankovich, D. A. Dikin, G. H. B. Dommett, K. M. Kohlhaas,
E. J. Zimney, E. A. Stach, R. D. Piner, S. T. Nguyen, R. S. Ruoff,
Nature 2006, 442, 282.
[26] a) W. Chen, L. Yan, Nanoscale 2011, 3, 3132; b) G. Wang,
J. Yang, J. Park, X. Gou, B. Wang, H. Liu, J. Yao, J. Phys. Chem. C
2008, 112, 8192.
[27] V. Dua, S. P. Surwade, S. Ammu, S. R. Agnihotra, S. Jain,
K. E. Roberts, S. Park, R. S. Ruoff, S. K. Manohar, Angew. Chem.
Int. Ed. 2010, 49, 2154.
1170 www.small-journal.com © 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
S. X. Wu et al.
[28] a) S. Yang, W. Yue, D. Huang, C. Chen, H. Lin, X. Yang, RSC Adv.
2012, 2, 8827; b) X. B. Fan, W. C. Peng, Y. Li, X. Y. Li, S. L. Wang,
G. L. Zhang, F. B. Zhang, Adv. Mater. 2008, 20, 4490.
[29] J. B. Liu, S. H. Fu, B. Yuan, Y. L. Li, Z. X. Deng, J. Am. Chem. Soc.
2010, 132, 7279.
[30] a) Z. Wang, X. Zhou, J. Zhang, F. Boey, H. Zhang, J. Phys.
Chem. C 2009, 113, 14071; b) Y. Harima, S. Setodoi, I. Imae,
K. Komaguchi, Y. Ooyama, J. Ohshita, H. Mizota, J. Yano, Electro-
chim. Acta 2011, 56, 5363.
[31] a) M. Zhou, Y. L. Wang, Y. M. Zhai, J. F. Zhai, W. Ren, F. A. Wang,
S. J. Dong, Chem. Eur. J. 2009, 15, 6116; b) Z. J. Wang, S. X. Wu,
J. Zhang, P. Chen, G. C. Yang, X. Z. Zhou, Q. C. Zhang, Q. Y. Yan,
H. Zhang, Nanoscale Res. Lett. 2012, 7, 161.
[32] X. Huang, X. Zhou, S. Wu, Y. Wei, X. Qi, J. Zhang, F. Boey,
H. Zhang, Small 2010, 6, 513.
[33] G. Williams, B. Seger, P. V. Kamat, ACS Nano 2008, 2, 1487.
[34] H. A. Becerril, J. Mao, Z. Liu, R. M. Stoltenberg, Z. Bao, Y. Chen,
ACS Nano 2008, 2, 463.
[35] Y. Zhou, Q. Bao, L. A. L. Tang, Y. Zhong, K. P. Loh, Chem. Mater.
2009, 21, 2950.
[36] a) A. Lerf, H. He, M. Forster, J. Klinowski, J. Phys. Chem. B 1998,
102, 4477; b) W. Gao, L. B. Alemany, L. Ci, P. M. Ajayan, Nat.
Chem. 2009, 1, 403.
[37] Y. Liu, D. S. Yu, C. Zeng, Z. C. Miao, L. M. Dai, Langmuir 2010,
26, 6158.
[38] C. S. Shan, H. F. Yang, D. X. Han, Q. X. Zhang, A. Ivaska, L. Niu,
Biosens. Bioelectron. 2010, 25, 1070.
[39] a) J.-D. Qiu, J. Huang, R.-P. Liang, Sens. Actuators B 2011,
160, 287; b) Z. J. Wang, J. Zhang, Z. Yin, S. X. Wu, D. Mandler,
H. Zhang, Nanoscale 2012, 4, 2728.
[40] W. B. Lu, Y. L. Luo, G. H. Chang, X. P. Sun, Biosens. Bioelectron.
2011, 26, 4791.
[41] X. M. Sun, Z. Liu, K. Welsher, J. T. Robinson, A. Goodwin, S. Zaric,
H. J. Dai, Nano Res. 2008, 1, 203.
[42] a) B. Ntsendwana, B. B. Mamba, S. Sampath, O. A. Arotiba, Int.
J. Electrochem. Sci. 2012, 7, 3501; b) M. Zhou, Y. Zhai, S. Dong,
Anal. Chem. 2009, 81, 5603.
[43] P. Wu, Q. A. Shao, Y. J. Hu, J. A. Jin, Y. J. Yin, H. Zhang, C. X. Cai,
Electrochim. Acta 2010, 55, 8606.
[44] S. Alwarappan, A. Erdem, C. Liu, C. Z. Li, J. Phys. Chem. C 2009,
113, 8853.
[45] a) Y. R. Kim, S. Bong, Y. J. Kang, Y. Yang, R. K. Mahajan, J. S. Kim,
H. Kim, Biosens. Bioelectron. 2010, 25, 2366; b) Q. X. Wang,
M. X. Zheng, J. L. Shi, F. Gao, Electroanal. 2011, 23, 915.
[46] S. L. Yang, B. F. Xu, J. Q. Zhang, X. D. Huang, J. Ye, C. Z. Yu,
J. Phys. Chem. C 2010, 114, 4389.
[47] S. Alwarappan, C. Liu, A. Kumar, C. Z. Li, J. Phys. Chem. C 2010,
114, 12920.
[48] Y. Bo, H. Y. Yang, Y. Hu, T. M. Yao, S. S. Huang, Electrochim. Acta
2011, 56, 2676.
[49] Y. J. Hu, J. A. Jin, P. Wu, H. Zhang, C. X. Cai, Electrochim. Acta
2010, 56, 491.
[50] Y. Chen, Y. Li, D. Sun, D. B. Tian, J. R. Zhang, J. J. Zhu, J. Mater.
Chem. 2011, 21, 7604.
[51] J. B. Zheng, Y. P. He, Q. L. Sheng, H. F. Zhang, J. Mater. Chem.
2011, 21, 12873.
[52] L. M. Lu, H. B. Li, F. L. Qu, X. B. Zhang, G. L. Shen, R. Q. Yu, Bio-
sens. Bioelectron. 2011, 26, 3500.
[53] C. S. Shan, H. F. Yang, J. F. Song, D. X. Han, A. Ivaska, L. Niu,
Anal. Chem. 2009, 81, 2378.
[54] F. H. Li, J. Chai, H. F. Yang, D. X. Han, L. Niu, Talanta 2010, 81,
1063.
[55] C.-H. Wang, C.-H. Wu, J.-W. Wu, M.-T. Lee, J.-K. Chang, M.-D. Ger,
C.-L. Sun, Analyst 2013, 138, 576.
[56] M. H. Yang, B. G. Choi, H. Park, W. H. Hong, S. Y. Lee, T. J. Park,
Electroanal. 2010, 22, 1223.
[57] K. F. Zhou, Y. H. Zhu, X. L. Yang, C. Z. Li, Electroanal. 2010, 22, 259.
small 2013, 9, No. 8, 1160–1172
Graphene-Based Electrochemical Sensors
[58] Q. Zhang, S. Y. Wu, L. Zhang, J. Lu, F. Verproot, Y. Liu, Z. Q. Xing,
J. H. Li, X. M. Song, Biosens. Bioelectron. 2011, 26, 2632.
[59] S. F. Hou, M. L. Kasner, S. J. Su, K. Patel, R. Cuellari, J. Phys.
Chem. C 2010, 114, 14915.
[60] Y. W. Hu, F. H. Li, X. X. Bai, D. Li, S. C. Hua, K. K. Wang, L. Niu,
Chem. Commun. 2011, 47, 1743.
[61] K. J. Huang, D. J. Niu, J. Y. Sun, C. H. Han, Z. W. Wu, Y. L. Li,
X. Q. Xiong, Colloids Surf. B 2011, 82, 543.
[62] X. H. Kang, J. Wang, H. Wu, I. A. Aksay, J. Liu, Y. H. Lin, Biosens.
Bioelectron. 2009, 25, 901.
[63] a) S. Yang, S. Luo, C. Liu, W. Wei, Colloids Surf. B 2012, 96,
75; b) Y. Wang, Y. M. Li, L. H. Tang, J. Lu, J. H. Li, Electrochem.
Commun. 2009, 11, 889.
[64] D. X. Han, T. T. Han, C. S. Shan, A. Ivaska, L. Niu, Electroanal.
2010, 22, 2001.
[65] S. Liu, J. Q. Tian, L. Wang, Y. L. Luo, W. B. Lu, X. P. Sun, Biosens.
Bioelectron. 2011, 26, 4491.
[66] Q. Zeng, J. S. Cheng, X. F. Liu, H. T. Bai, J. H. Jiang, Biosens. Bio-
electron. 2011, 26, 3456.
[67] G. H. Zeng, Y. B. Xing, J. A. Gao, Z. Q. Wang, X. Zhang, Langmuir
2010, 26, 15022.
[68] A. N. Cao, Z. Liu, S. S. Chu, M. H. Wu, Z. M. Ye, Z. W. Cai,
Y. L. Chang, S. F. Wang, Q. H. Gong, Y. F. Liu, Adv. Mater. 2010,
22, 103.
[69] K. Wang, Q. A. Liu, Q. M. Guan, J. Wu, H. N. Li, J. J. Yan, Biosens.
Bioelectron. 2011, 26, 2252.
[70] F. Y. Zhang, Y. J. Li, Y. E. Gu, Z. H. Wang, C. M. Wang, Microchim.
Acta 2011, 173, 103.
[71] Z. Wang, J. Zhang, P. Chen, X. Zhou, Y. Yang, S. Wu, L. Niu, Y. Han,
L. Wang, P. Chen, F. Boey, Q. Zhang, B. Liedberg, H. Zhang, Bio-
sens. Bioelectron. 2011, 26, 3881.
[72] H. C. Gao, F. Xiao, C. B. Ching, H. W. Duan, ACS Appl. Mater.
Interfaces 2011, 3, 3049.
[73] B. Unnikrishnan, S. Palanisamy, S. M. Chen, Biosens. Bioelec-
tron. 2013, 39, 70.
[74] Y. Q. Zhang, Y. Z. Wang, J. B. Jia, J. G. Wang, Sens. Actuators B
2012, 171, 580.
[75] M. Du, T. Yang, X. Li, K. Jiao, Talanta 2012, 88, 439.
[76] Q. Liu, X. Zhu, Z. H. Huo, X. L. He, Y. Liang, M. T. Xu, Talanta
2012, 97, 557.
[77] H. F. Dong, Z. Zhu, H. X. Ju, F. Yan, Biosens. Bioelectron. 2012,
33, 228.
[78] N. G. Shang, P. Papakonstantinou, M. McMullan, M. Chu,
A. Stamboulis, A. Potenza, S. S. Dhesi, H. Marchetto, Adv. Funct.
Mater. 2008, 18, 3506.
[79] C. X. Lim, H. Y. Hoh, P. K. Ang, K. P. Loh, Anal. Chem. 2010, 82,
7387.
[80] a) X. C. Dong, X. W. Wang, L. H. Wang, H. Song, H. Zhang,
W. Huang, P. Chen, ACS Appl. Mater. Interfaces 2012, 4, 3129;
b) X. C. Dong, H. Xu, X. W. Wang, Y. X. Huang, M. B. Chan-Park,
H. Zhang, L. H. Wang, W. Huang, P. Chen, ACS Nano 2012, 6,
3206.
[81] V. Penmatsa, T. Kim, M. Beidaghi, H. Kawarada, L. Gu, Z. F. Wang,
C. L. Wang, Nanoscale 2012, 4, 3673.
[82] J. Zhao, G. F. Chen, L. Zhu, G. X. Li, Electrochem. Commun. 2011,
13, 31.
[83] a) S. Wu, X. Lan, F. Huang, Z. Luo, H. Ju, C. Meng, C. Duan, Bio-
sens. Bioelectron. 2012, 32, 293; b) A. Sinitskii, A. Dimiev,
D. V. Kosynkin, J. M. Tour, ACS Nano 2010, 4, 5405.
[84] H. D. Jang, S. K. Kim, H. Chang, K. M. Roh, J. W. Choi, J. Huang,
Biosens. Bioelectron. 2012, 38, 184.
[85] E. Casero, A. M. Parra-Alfambra, M. D. Petit-Domínguez,
F. Pariente, E. Lorenzo, C. Alonso, Electrochem. Commun. 2012,
20, 63.
[86] a) J. Y. Sun, K. J. Huang, Y. Fan, Z. W. Wu, D. D. Li, Microchim.
Acta 2011, 174, 289; b) N. Q. Qiao, J. B. Zheng, Microchim.
Acta 2012, 177, 103; c) W. Lv, F. M. Jin, Q. G. Guo, Q. H. Yang,
F. Y. Kang, Electrochim. Acta 2012, 73, 129.
small 2013, 9, No. 8, 1160–1172 © 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
[87] a) J. Luo, S. S. Jiang, H. Y. Zhang, J. Q. Jiang, X. Y. Liu, Anal. Chim.
Acta 2012, 709, 47; b) J. Luo, H. Y. Zhang, S. S. Jiang, J. Q. Jiang,
X. Y. Liu, Microchim. Acta 2012, 177, 485; c) M. Mallesha,
R. Manjunatha, G. S. Suresh, J. S. Melo, S. F. D’Souza,
T. V. Venkatesha, J. Solid State Electrochem. 2012, 16, 2675.
[88] a) P.-G. Pietta, J. Nat. Prod. 2000, 63, 1035; b) L. Zheng,
J. F. Song, J. Solid State Electrochem. 2010, 14, 43.
[89] a) L. L. Zhang, H. H. Cheng, H. M. Zhang, L. G. Qu, Electrochim.
Acta 2012, 65, 122; b) Q. Zhang, Y. Qiao, L. Zhang, S. Y. Wu,
H. Zhou, J. W. Xu, X. M. Song, Electroanal. 2011, 23, 900.
[90] a) S. Prasannakumar, R. Manjunatha, C. Nethravathi, G. S. Suresh,
M. Rajamathi, T. V. Venkatesha, J. Solid State Electrochem. 2012,
16, 3189; b) C. S. Shan, H. F. Yang, D. X. Han, Q. X. Zhang,
A. Ivaska, L. Niu, Biosens. Bioelectron. 2010, 25, 1504.
[91] a) K. J. Huang, D. J. Niu, X. Liu, Z. W. Wu, Y. Fan, Y. F. Chang,
Y. Y. Wu, Electrochim. Acta 2011, 56, 2947; b) S. W. Ting,
A. P. Periasamy, S. M. Chen, R. Saraswathi, Int. J. Electrochem.
Sci. 2011, 6, 4438.
[92] a) R. K. Srivastava, S. Srivastava, T. N. Narayanan, B. D. Mahlotra,
R. Vajtai, P. M. Ajayan, A. Srivastava, ACS Nano 2011, 6,
168; b) G.-P. Nikoleli, M. Q. Israr, N. Tzamtzis, D. P. Nikolelis,
M. Willander, N. Psaroudakis, Electroanal. 2012, 24, 1285.
[93] V. C. Tung, L. M. Chen, M. J. Allen, J. K. Wassei, K. Nelson,
R. B. Kaner, Y. Yang, Nano Lett. 2009, 9, 1949.
[94] a) X. Y. Ma, M. Y. Chao, Z. X. Wang, Anal. Methods 2012, 4,
1687; b) X. Liu, L. L. Xie, H. L. Li, J. Electroanal. Chem. 2012,
682, 158.
[95] a) Z. H. Sheng, X. Q. Zheng, J. Y. Xu, W. J. Bao, F. B. Wang,
X. H. Xia, Biosens. Bioelectron. 2012, 34, 125; b) S. J. Li,
D. H. Deng, Q. Shi, S. R. Liu, Microchim. Acta 2012, 177, 325.
[96] L. Tan, K. G. Zhou, Y. H. Zhang, H. X. Wang, X. D. Wang, Y. F. Guo,
H. L. Zhang, Electrochem. Commun. 2010, 12, 557.
[97] K. J. Huang, Q. S. Jing, Z. W. Wu, L. Wang, C. Y. Wei, Colloids Surf.
B 2011, 88, 310.
[98] C. L. Sun, H. H. Lee, J. M. Yang, C. C. Wu, Biosens. Bioelectron.
2011, 26, 3450.
[99] Y. L. Wang, W. Peng, L. Liu, M. Tang, F. Gao, M. G. Li, Microchim.
Acta 2011, 174, 41.
[100] Y. Mao, Y. Bao, S. Y. Gan, F. H. Li, L. Niu, Biosens. Bioelectron.
2011, 28, 291.
[101] a) Q. Z. Li, X. Y. Qin, Y. L. Luo, W. B. Lu, G. H. Chang, A. M. Asiri,
A. O. Al-Youbi, X. P. Sun, Electrochim. Acta 2012, 83, 283;
b) X. Y. Qin, Y. L. Luo, W. B. Lu, G. H. Chang, A. M. Asiri,
A. O. Al-Youbi, X. P. Sun, Electrochim. Acta 2012, 79, 46.
[102] Y. Umasankar, B. Unnikrishnan, S.-M. Chen, T.-W. Ting, Anal.
Methods 2012, 4, 3653.
[103] a) L. Y. Feng, Y. Chen, J. S. Ren, X. G. Qu, Biomater. 2011, 32,
2930; b) O. Akhavan, E. Ghaderi, R. Rahighi, ACS Nano 2012, 6,
2904; c) L. M. Zhu, L. Q. Luo, Z. X. Wang, Biosens. Bioelectron.
2012, 35, 507.
[104] M. Giovanni, A. Bonanni, M. Pumera, Analyst 2012, 137, 580.
[105] L. Lin, Y. Liu, L. H. Tang, J. H. Li, Analyst 2011, 136, 4732.
[106] Y. W. Hu, S. C. Hua, F. H. Li, Y. Y. Jiang, X. X. Bai, D. Li, L. Niu,
Biosens. Bioelectron. 2011, 26, 4355.
[107] K. X. Mao, D. Wu, Y. Li, H. M. Ma, Z. Z. Ni, H. Q. Yu, C. N. Luo,
Q. Wei, B. Du, Anal. Biochem. 2012, 422, 22.
[108] M. H. Yang, A. Javadi, S. Q. Gong, Sens. Actuators B 2011, 155,
357.
[109] J. J. Lu, S. Q. Liu, S. G. Ge, M. Yan, J. H. Yu, X. T. Hu, Biosens.
Bioelectron. 2012, 33, 29.
[110] R. Li, D. Wu, H. Li, C. X. Xu, H. Wang, Y. F. Zhao, Y. Y. Cai, Q. Wei,
B. Du, Anal. Biochem. 2011, 414, 196.
[111] a) T. Gan, S. S. Hu, Microchim. Acta 2011, 175, 1; b) A. Prakash,
S. Chandra, D. Bahadur, Carbon 2012, 50, 4209.
[112] W. M. Si, W. Lei, Y. H. Zhang, M. Z. Xia, F. Y. Wang, Q. L. Hao,
Electrochim. Acta 2012, 85, 295.
[113] Z. J. Li, X. L. Sun, Q. F. Xia, R. Y. Li, Y. J. Fang, S. P. Yang, J. K. Liu,
Electrochim. Acta 2012, 85, 42.
www.small-journal.com 1171
 reviews
[114] a) C. Gao, X. Y. Yu, R. X. Xu, J. H. Liu, X. J. Huang, ACS Appl. Mater.
Interfaces 2012, 4, 4672; b) B. Wang, Y. H. Chang, L. J. Zhi, New
Carbon Mater. 2011, 26, 31.
[115] a) J. Y. Lei, X. F. Lu, W. Wang, X. J. Bian, Y. P. Xue, C. Wang, L. J. Li,
RSC Adv. 2012, 2, 2541; b) Y. P. He, J. B. Zheng, S. Y. Dong, Ana-
lyst 2012, 137, 4841.
[116] a) S. J. Li, D. H. Deng, H. Pang, L. Liu, Y. Xing, S. R. Liu, J. Solid
State Electrochem. 2012, 16, 2883; b) Y. Fan, J. H. Liu, C. P. Yang,
M. Yu, P. Liu, Sens. Actuators, B 2011, 157, 669.
[117] a) X. Huang, Z. Y. Zeng, H. Zhang, Chem. Soc. Rev. 2013,
42, 1934; b) Q. H. Wang, K. K. Zadeh, A. Kis, J. N. Coleman,
M. S. Strano, Nat. Nanotechnol. 2012, 7, 699; c) M. S. Xu,
1172 www.small-journal.com © 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
S. X. Wu et al.
T. Liang, M. M. Shi, H. Z. Chen, Chem. Rev. 2013, DOI: 10.1021/
cr300263a; d) M. Chhowalla, H. S. Shin, G. Eda, L. J. Li, K. Loh,
H. Zhang, Nat. Chem. 2013, DOI: 10.1038/nchem.1589.
[118] Z. Y. Zeng, Z. Y. Yin, X. Huang, H. Li, Q. Y. He, G. Lu, F. Boey,
H. Zhang, Angew. Chem. Int. Ed. 2011, 50, 11093.
[119] S. X. Wu, Z. Y. Zeng, Q. Y. He, Z. J. Wang, S. J. Wang, Y. P. Du,
Z. Y. Yin, X. P. Sun, W. Chen, H. Zhang, Small 2012, 8,
2264.
Received: November 21, 2012
Revised: January 8, 2013
Published online: March 13, 2013
small 2013, 9, No. 8, 1160–1172