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Activated carbon derived from hydrothermal treatment of

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sucrose and its air filtration application

RSC Advances Accepted Manuscript

Received 00th January 20xx,
Accepted 00th January 20xx
DOI: 10.1039/x0xx00000x
www.rsc.org/
a b b a*
Shih-Wei Hao , Chia-Hao Hsu , Yang-Guang Liu , Bor Kae Chang
As air pollution problems become increasingly serious and the environmental awareness continues to rise, a source of
cheap and simple air filtration active material is also required. Here, we demonstrated the use of hydrothermal
carbonization-derived activated carbon for such an application. By doing so, we hope to develop a biodegradable filtering
material which can combine filtering capability with biodegradable functionalities. To this end, an air filtration paper using
activated carbon and pulp as materials was synthesized. Activated carbon was prepared by hydrothermal carbonization of
sucrose and further activation. Hydrochar synthesis parameters including reaction time, reaction temperature, sucrose
concentration, pH effect of hydrothermal solution, and nitrogen doping were investigated. Air filtration application was
demonstrated using activated carbon obtained from a dramatic chemical reaction with KOH at 800°C as the biodegradable
active filler material. The morphology of hydrochar and activated carbon was characterized by scanning electron
microscopy (SEM). Gas chromatography-mass spectrometry (GC-MS) was used to investigate the mechanism of hydrochar
formation with different pH of hydrothermal solution. Fourier-transform infrared spectrometer (FTIR) was used to confirm
activation. The results of elemental analysis showed evidence of nitrogen doping. Surface area and pore size analysis
results allow for comparison of the degree of activation. The highest surface area of activated sample obtained in this
study is up to 3026 m2/g and filtering ability of our samples were measured by TSI model 8130 testing method with results
of filtering efficiency achieving a quarter of commercial air filter product.

various biomass materials have been used in HTC synthesis,

1. Introduction
The development of carbon materials has always been an
attractive issue due to its excellent advantages such as less
damage to the environment, low cost, and relative ease of
commercialization. Hydrothermal carbonization (HTC) is a
synthesis method that transfers carbon precursors into useful
carbon materials under mild synthesis conditions. The basic
process involves pre-configured solutions that are placed into
sealed Teflon-lined stainless steel autoclaves and heated to a
specified temperature for the duration of several hours.
The resulting hydrochar can be obtained from the bottom
of the autoclave that display controllable pore size,
morphology, and specific chemical functionalities. The features
of hydrochar are usually controlled with temperature,
concentration of carbon precursor, reaction time and acidic or
basic catalysis.1 Carbohydrates, such as sucrose,2, 3 glucose,4
cellulose,5-7 and natural biomass are the usual carbon
precursors used in such a processes. On the other hand,
8 9 10 11
including bagasse, coconut shell, banana, corn cob, coffee
12 13
grounds, peanut hull, hemp, pine needles and oak.
Applications for HTC-synthesized hydrochar include fuel,
electric capacitor, heavy metal adsorption, and activated
14
carbon synthesis.
Activated carbon can be obtained through activation of
hydrochar precursor. A highly porous material with large
specific surface area will be formed and the resulting
performance as adsorbents will be dramatically enhanced by
this process. The porosity and pore size of activated carbon
depends on activation temperature, time, inert gas flow rate
during activation, and species of activated agent. Functions of
15, 16
such highly porous carbon material include adsorbents,
12, 17, 18 19
capacitor electrodes, electrocatalyst, hydrogen
20 21
storage, and carbon dioxide capture. In addition, modifying
activated carbon by nitrogen-doping has been demonstrated
22
to alter adsorption performance of the material. Although
there are many applications of activated carbon, there have
been very few studies that emphasize its biodegradable
functions in air filtration, with the possible exception of
commercial surgery masks that are popular in Taiwan.
Air pollution particles form naturally from volcanic
eruptions, dust storms, forest fires and from emissions of
industrial, traffic, agricultural, and residential origins. To purify
the air, there are already many products on the markets
nowadays, such as electrostatic filters, HEPA filter, activated

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carbon filters. However, the abovementioned products are not
all manufactured in an eco-friendly fashion, leading to further
costs to the environment and resources. In order to improve
this problem, we designed an air filtration paper, which not
only purifies air pollution particles but is also an
environmentally friendly green product. The air filtration paper
is made of all biodegradable components, including pulp and
activated carbon.
Studies were first performed on the underlying active
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material, leading to a comprehensive investigation of the
effects of pH and nitrogen doping on the active material. pH-
modified and nitrogen source added in the hydrothermal
solution make hydrochars with distinct pore size, morphology,
and surface chemical functionalities, which were compared to
hydrochar obtained from aqeous conditions. Activated carbon
from the pH-modified and nitrogen-doped hydrochar were
further produced by an activation process, and different pore
characteristics were determined.
2. Experimental
2.1 Chemical Compounds
The materials we used in this research include sucrose (CAS
number: 57-50-1, Showa, 99.5%), sulfuric acid (CAS number:
7664-93-9, Showa, 97%), sodium hydroxide (CAS number:
1310-73-2, Showa, 97%), ammonium sulfate (CAS number:
7783-20-2, Showa, 99.5%) and potassium hydroxide semi
pellets (CAS number: 1310-58-3, Aencore, 85%).
2.2 Experimental Procedure
In this work, experiments are divided into three parts: (i) the
effect of time, concentration and temperature on hydrochar
and activated carbon synthesis, (ii) the effect of pH and
nitrogen doping on hydrochar and activated carbon synthesis,
and (iii) the application of air filtration with resulting activated
carbon.
2.2.1 Effect of Time, Concentration and Temperature on
Hydrochar and Activated Carbon Synthesis
Hydrothermal Treatment
20 ml of sucrose at varying concentrations in aqueous solution
were placed in a 45 ml Teflon-lined stainless steel autoclave
and heated to chosen synthesis temperatures for several hours
in a conventional oven. The autoclave was naturally cooled to
room temperature, and the resulting solid product was
washed with deionized water and dried in an oven at 70°C
overnight.
Activation process
Hydrochar with fused (C2) and separated (C6) structures were
selected for further activation because they are the most
representative samples of eight hydrochars based on their
morphology (see section 3.1.1 for details). The hydrochar was
mixed with KOH in a mass ratio of 1:4 and 1:2 in a ceramic
mortar and the mixture was heated to 800°C for 1 hour in a
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3 -1
tubular furnace under nitrogen flow of 200 cm
min . After
cool down, still under N2, the activated carbon was then
washed with distilled water until neutral pH was reached and
dried in an oven overnight.
2.2.2 Effect of pH and Nitrogen Doping on Hydrochar and
Activated Carbon Synthesis
Hydrothermal treatment
20 ml of 0.5M sucrose aqueous solution with addition of
sulfuric acid for acidic conditions, sodium hydroxide for basic
conditions, or ammonium sulfate for nitrogen doping was
RSC Advances Accepted Manuscript
placed in a 45 ml Teflon-lined stainless steel autoclave and
heated to 200°C for 4 hours in an oven. The autoclave was
naturally cooled to room temperature, and the resulting solid
product was washed with deionized water until neutral pH and
dried in an oven overnight.
Activation process
Sucrose-derived hydrochar was mixed with KOH in a mass ratio
of 1:4 in a ceramic mortar and the mixture was heated to
800°C for 1 hour in a tubular furnace under nitrogen flow of
3 -1
200 cm
min . After cool down while still under N2, the
activated carbon was then washed with deionized water until
neutral pH was reached and dried in an oven overnight.
2.2.3 Application of Air Filtration with Resulting Activated Carbon
1g of activated carbon and 4g of pulp were mixed with 1.5
liters of water by a physical method, further assisted by
rigorous stirring with a homogenizer. Then the mixture was
distributed uniformly in a container containing water. By using
a traditional papermaking process, we could obtain a wet
preliminary paper. The preliminary product was then heated
to 70°C for 4 hours to remove water content. Finally, dry
pieces of paper with activated carbon uniformly distributed in
it was obtained, which we called the air filtration paper.
3. Results and Discussion
3.1 Effect of Time, Concentration and Temperature on Hydrochar
and Activated Carbon Synthesis
3.1.1 Morphology and Yield
Scanning electron microscopy was performed at the National
Central University Precision Instruments Center. Figure 1
shows SEM images of our sucrose-derived hydrochar with
different reaction parameters. It was observed that carbon
spheres (CSs) with different morphologies result due to
distinct synthesis parameters. However, we can roughly
categorize them into two types: fused (Figure 1 a-e & g) and
separated (Figure 1 f & h). Notation for samples created under
varying conditions are listed in Table 1. We observed that
reaction time affected particle size, yield and degree of fusing.
Particle size of CSs was measured by MB ruler program.23 From
various SEM images of the same sample, we selected a
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representative area, then measured and averaged the When synthesis time was increased to 12h, CSs were
diameter of at least thirty carbon spheres. Yield for each joined together, forming a fused type structure. Concentration
synthesis was calculated from the following equation: of precursor influenced only yield rather than size of CSs and
    !"!#  # # $
degree of fusing, with C6 sample giving a yield of 24.0% and C8
Hydrochar Yield % 
%& ''# &#$! $

(a) C1 (c) C3 (e) C5 (g) C7

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RSC Advances Accepted Manuscript

(b) C2 (d) C4 (f) C6 (h) C8

Figure 1. SEM images of sucrose-derived hydrochar obtained by hydrothermal treatment.

Table 1. Notation, synthesis parameters, yield of hydrochar and average particle size of     . #'' $
Activated Carbon Yield % 
carbon spheres /"! $

Hydrochar Parameter Yield (%) Average Particle It can be observed that yield only depends on KOH amount
Size (μm) and is unaffected by hydrochar morphology. Higher KOH
C1 200°C, 1.5M, 12h 39.2 10.33 ± 2.07 concentration leads to lower yield of products. The effect of
C2 200°C, 1.5M, 5h 34.6 9.27 ± 2.79 KOH amount concentration can be seen in Figure 2. With lower
C3 200°C, 1M, 12h 36.1 5.18 ± 0.29
concentrations (Figure 2 a & c), spheres are still present in
C4 200°C, 1M, 5h 31.0 10.86 ± 3.72
parts of the structure (marked with solid line). However, with a
C5 190°C, 1.5M, 12h 36.6 6.69 ± 0.93
higher concentration of KOH (Figure 2 b & d), we could hardly
C6 190°C, 1.5M, 5h 24.0 11.41 ± 3.46
C7 190°C, 1M, 12h 32.2 4.48 ± 0.91 find spheres in the structure because the morphology is
C8 190°C, 1M, 5h 20.1 11.74 ± 2.22 dominated by porous fragments that have formed instead of
spheres. It could be deduced that at a 1:2 ratio of carbon
sample giving a yield of 20.1%. We found that higher precursor to KOH, the amount of activation agent was not
temperatures resulted in fused CSs and higher yield, even with enough to react with all spheres, resulting in a coexistent
a relatively small 10-degree difference between 190°C and structure of CSs and porous fragments. The effect of different
200°C, while particle size remained the same. Based on the morphologies of the starting
above discussion, we discuss how these two morphologies Table 2. Sample names, synthesis parameters and yield of activated carbon.
further differentiate upon activation. C2 and C6 were
Activated Carbon Parameter Yield
investigated further, which represent fused structure and
C2K2 C2 carbon precursor/KOH= 1:2, 800°C, 1hr 32.2%
separated structures, respectively.
C2K4 C2 carbon precursor/KOH= 1:4, 800°C, 1hr 20.1%
Table 2 shows the notation of activated carbon. Yield of
C6K2 C6 carbon precursor/KOH= 1:2, 800°C, 1hr 31.0%
activated carbon was calculated from C6K4 C6 carbon precursor/KOH= 1:4, 800°C, 1hr 18.7%

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(a) (b)
(c) (d)
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Figure 2. SEM images of activated carbon obtained through activation of hydrochar
samples. (a) C2K2, (b) C2K4, (c) C6K2, (d) C6K4.
hydrochar precursor was not evident, as there was not much
difference between C2K4 and C6K4. Due to the high reaction
temperature and the addition of enough KOH, the two
different types of morphology of carbon precursors were
eliminated.
3.1.2 Chemical Properties of Hydrochar and Activated Carbon
Functional groups on the surface of various hydrochar samples
16
have been investigated in detail. FTIR spectra of our sucrose-
derived hydrochar samples are shown in Figure 3. Broad bands
-1
in the 3000-3700 cm range correspond to O-H stretching in
Figure 3. FTIR spectra of hydrochar samples. Characteristic peaks can be identified in
the spectra of samples under various synthesis parameters.
water, and the bands at around 2900 cm-1 were assigned to
stretching vibrations of aliphatic C-H. The bands at 1620 cm-1
together with the band at 1510 cm-1 were attributed to C=C
vibrations, and the band at 1710 cm-1 was assigned to C=O
vibration. Another broad band at the 1000-1450 cm-1 region
correspond to C-O stretching. Two bands at 800 and 750 cm-1
were attributed to aromatic C-H out-of-plane bending
vibrations. No matter the change of synthesis parameters, the
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FTIR results for each sample were nearly the same. The results
suggest that even with different reaction conditions,
hydrochar with similar chemical characteristic can be obtained.
For the activated samples, the number of characteristic
peaks decreased due to the dramatic chemical reaction. Only
O-H stretching band, C=C vibration band, and C=O vibration
band were left, and a peak at around 2350 cm-1 formed which
is identified with atmospheric carbon dioxide24 found in FTIR
results (absent or barely present in C6K4). Different KOH
concentration and different morphologies of carbon precursor
seemed to have no significant impact on resulting samples.
The results show that hydrochar of all preparations were
successfully transformed into activated carbon.
Figure 4. FTIR spectra of activated carbon derived from hydrochar samples.
3.1.3 Nitrogen Adsorption Isotherms and Related Surface Area
Results
Nitrogen adsorption isotherms of hydrochar and activated
carbon, performed at the National Central University Precision
Instruments Center, are shown in Figure 5 and the related
textural properties are summarized in Table 3. Pressure ranges
used for BET specific surface area determination were chosen
according to selection rules suggested by Rouquerol et al.
25
Hydrochar samples displayed very low adsorption quantities
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no matter the fused (C2) or separated (C6) structure of CSs, as

seen from the nearly flat isotherm seen near the baseline in
Figure 5. The four activated samples exhibit a type I isotherm,
which implies the microporous nature of our samples as
adsorption amount quickly increased at low relative pressure
in nitrogen adsorption isotherms. It could be seen that higher
KOH concentrations resulted in samples with higher
adsorption quantities because of a more complete reaction,
which correlates with our observations using the SEM. Of note
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is the appearance of a hysteresis loop for samples obtained

from a hydrochar to KOH mass ratio of 1:4, nearly in the same
position for both C2K4 and C6K4 samples. The formation of the

RSC Advances Accepted Manuscript

hysteresis loop might be due to the existence of mesopore
26-28
structures of activated carbon. Specific surface area
followed the decreasing order of C2K4 > C6K4 > C6K2 for BET
determination and the BET result of C2K4 was up to 3036
2
m /g.

Figure 5. Nitrogen adsorption and desorption isotherms of fused (C2) and separated
(C6) hydrochar, and activated carbon derived from C2 and C6 with different KOH
amount.

Table 3. BET surface areas of carbon precursor and activated carbons.

Notation ABET (m2/g)

C2 3.06
C2K4 3036
C6 3.10
C6K2 1635
C6K4 2837

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3.2 The Effect of pH and Nitrogen Doping on Hydrochar and
Activated Carbon Synthesis
3.2.1 Yield and Supernatant Liquid
All information related to hydrothermal treatment of sucrose
are listed in Table 4, including hydrothermal condition, yield of
hydrochar, pH value of solution and average particle size of
carbon spheres. Particle size of CSs was measured in the same
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Much lower levels of HMF were found in nitrogenated
samples compared to non-nitrogenated ones, as summarized
in Table 5, and the result corresponds to higher yields achieved
with the addition of ammonium sulfate, except for a slight
discrepancy in HBN results. The clear decrease in HMF levels
upon addition of ammonium was measured in the supernatant
liquid and a corresponding elevation in the hydrochar yield.
Additionally, we found no regular relationship between
levulinic acid and yield. Levulinic acid results from GC-MS did

not reveal the trend described in the reference paper

way by using the MB ruler program as mentioned in section
mentioned above. Many organic acids can be produced during
3.1.1. Each set of data was obtained by averaging three 2
the hydrothermal treatment of sucrose, and we deduce that

RSC Advances Accepted Manuscript

separate experimental results. In this table, initial pH and final
levulinic acid may not have be the main acid product from our
pH represent the values for the solution before and after
experiments.
hydrothermal treatment, respectively. It is evident that yield,
pH value and particle size depend on pH value of hydrothermal
3.2.2 Structural Characteristics of Hydrochar and Activated Carbon
solution and nitrogen doping. For non-nitrogenated samples,
yields were nearly the same, but the yield of hydrochar was
Morphology of hydrothermally treated 0.5M sucrose under
observed to follow the order of water > acidic > basic
200°C with different chemical environments can be seen in the
conditions, a trend that is also found in nitrogenated samples.
SEM images of Figure 6. It is observed that a typical sample
With the addition of ammonium sulfate, the yield increased
consisted of spherical particles with a diameter ranging from 2-
expect for synthesis under basic conditions. Results suggest
8 μm. The mean diameter and standard deviations of
the addition of ammonium alters the nucleation mechanism by
hydrochar for distinct synthesis parameters are listed in Table
offering an easier path for hydrochar to nucleate and grow,
4. The particle size of HW and HB are smaller than that of HA,
leading to an increased yield and lager particle size (discuss in
and morphology of HB is different from HW and HA in that the
next section).
carbon spheres are joined together, forming a fused type
Table 4. Samples names, yield of hydrochar, pH value of solution and average structure promoted by the basic conditions during
particle size of carbon spheres.
hydrothermal treatment. When ammonium sulfate was added
for nitrogen doping, results suggest that CSs develop into
Hydrochar Initial pH Final pH Yield Average Particle Size (μm)
larger microspheres. Particle sizes of nitrogenated samples are
HW 6.50 2.06 27.3% 3.26±0.69
larger than non-nitrogenated samples in the same solution
HA 1.54 1.42 26.3% 6.66±2.27
HB 11.53 3.20 25.6% 2.89±0.96
condition. From these results, it is deduced that the addition of
HWN 5.41 1.56 33.9% 6.44±1.11 ammonium sulfate results in the promotion of nucleation and
HAN 1.62 1.41 30.1% 7.99±1.76 growth and makes the reaction of hydochar more complete as
HBN 10.33 2.31 24.2% 8.01±1.86 we could observe the apparent difference of particle sizes
between HB and HBN. Elemental analysis results prove that
Initial pH values of HW, HA and HB solutions confirm nitrogen exist in the structure, detailed in section 3.2.4.
neutral, acidic and basic conditions, respectively. When The above discussions conclude that: (i) basic solution for
ammonium sulfate was added to the reaction, starting pH hydrothermal treatment might limit the growth of CSs, leading
values changed slightly to lower acidity and basicity of HA and to smaller and more irregular shapes than HW and HA; (ii) with
HB solutions, respectively. All final pH data are lower than the addition of ammonium, hydrochar develop to CSs of larger
initial pH values, as expected from the formation of organic sizes no matter in water, acidic or basic conditions because of
acids such as acetic, lactic, propenoic, levulinic and formic more complete reaction occurring when ammonium is
acids or other soluble compounds such as 5- present.
hydroxymethylfurfural, furfural and 5-methylfurfural during Table 5. GC-MS results with quantitative analysis for supernatant liquid of
2
hydrothermal treatment of sucrose. Previous research has hydrothermal treatment.
demonstrated the importance of such organic acids and
2, 29, 30 Hydrochar HMF (mM) Levulinic acid (mM)
soluble compounds to hydrochar yield. Therefore, the
HW 6.3 18.4
supernatant liquid obtained from hydrothermal treatment
HA 0.8 47.4
were analyzed with gas chromatography-mass spectrometry
HB 18.2 8.6
(GC-MS, National Chiao Tung University Center for Advanced HWN 0.16 28.7
Instrumentation). Two target compounds, 5- HAN 0.03 35.8
hydroxymethylfurfural (HMF) and levulinic acid, were chosen HBN 11.97 1.69
for the reason that these two by-products are competitive
30
compounds within hydrothermal treatment of sucrose.

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(a) HW (b) HWN

(c) HA (d) HAN

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Figure 7. Activated carbon was composed of spherical structure (marked with solid
line), sponge-like fragments (marked with dashed line) and fine pore fragments
(marked with dotted line)

(e) HB (f) HBN

(a) HW-AC (b) HWN-AC

Figure 6. SEM images of hydrochar obtained by hydrothermal treatment in six

synthesized conditions.
(c) HA-AC (d) HAN-AC

After the activation process, particles of entirely different

morphology were obtained. Figure 8 shows SEM images of
activated carbon samples obtained from distinctly different
initial hydrochar precursors, but by undergoing the same
activation process, they all display porous fragments.
However, despite similarities in the morphology of these six
samples, there are still some differences. Activated carbon (e) HB-AC (f) HBN-AC
fragments can be categorized with the aid of BET results into
three types: spherical structure (marked with solid line),
sponge-like fragments (marked with dashed line) and fine pore
fragments (marked with dotted line) in Figure 7. Spherical
structures retained the original morphology of carbon spheres,
large holes existing in some fragments result in sponge-like Figure 8. SEM images of activated carbon obtained through activation of hydrochar
fragments, while fine pore fragments were defined as samples.
structure where the pores cannot be observed at the
magnification in Figure 7. These three structure types provide Hydrochar FTIR results here show that the C=O reduction
different specific surface areas because they contribute -1
band at 1705 cm and SO4 stretching band at 621 cm were
-1

varying degrees of adsorption capacities.
3.2.3 Chemical Properties of Hydrochar and Activated Carbon
A reduced peak in FTIR spectra of nitrogenated samples at
-1
1705 cm has been previously described in literature,
suggesting that nitrogenated samples contains reduced
30 -1
formation of C=O groups. Another band at 621 cm related
to SO4 stretching was observed by the authors in each
nitrogenated samples because of the addition of ammonium
sulfate. Other evidence that proves nitrogen doping was
-1
successful include N-H stretching bands at 3000-3500 cm , but
this was indistinguishable due to the overlapped region of O-H
stretching bands.
not observed (Figure 9). The C=O stretching bands of
nitrogenated and non-nitrogenated seem to have same
-1
intensity. While the absence of the 621 cm peak indicates
that SO4 is not found in the structure for nitrogenated samples
2-
of this work, which should be the case since SO4 in its ion
state would have been removed by deionized water described
in the experimental procedure. FTIR spectra cannot prove
nitrogen doping of samples because all samples showed the
same results. Additionally, there are two different results
compared to reference paper. Therefore, elemental analysis
(National Chung Hsing University Instrument Center) was
employed to provide definitive answer as to whether nitrogen
doping was successful in the samples.

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Figure 9. FTIR spectra of hydrochar samples. Two characteristic peaks at 621 cm-1 and
at 1705 cm-1 are marked in spectra.
There was no obvious difference between the six activated
samples in Figure 10. Peaks can be identified for O-H stretching
-1
band in the range of 3000-3700 cm , C=C vibration band in
-1
1630 cm , and C=O vibration band ranging from 1450 to 1000
-1
cm . The results demonstrated that functional groups on
activated carbon were the same after activation process no
matter distinct synthesis conditions of hydrochar, whether
formed in basic, acidic, or neutral conditions, with our without
nitrogen doping. Similar results happened in section 3.1.2,
which illustrate same FTIR results of activated carbon even
though different hydrochar precursor. It can be concluded that
KOH activation of hydrochar samples can result in the same
functional groups on the surface of activated carbon samples.
3.2.4 Elemental Analysis of Hydrochar and Activated Carbon
Table 6 and Table 7 report elemental analysis results of
hydrochar and activated carbon, respectively. Elemental
analysis of C, H, N, S, O, residue and empirical formula are
listed in detail. Residue was calculated by the difference of
initial sample weight and analyzed elements, and empirical
formula was calculated from elemental analysis results. Strong
evidence of nitrogen doping of hydrochar can be observed in
Table 6. Nitrogenated hydrochar displayed higher nitrogen
content than non-nitrogenated ones. Obvious elevation of
nitrogen content was also found in activated carbon in Table 7.
When comparing activated carbon with hydrochar, the
promotion of carbon
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Figure 10. FTIR spectra of activated carbon.
content and reduction of hydrogen and oxygen can be noted,
which is due to the activation process of the hydrochar.
Additionally, a relatively higher content of sulfur can be
observed in HW-AC, HA-AC and HB-AC, and the sulfur content
in nitrogenated activated carbon cannot be explained because
there were nearly no sulfur existing in the hydrochar
precursors used. Trace amounts can be found in the impurities
of sucrose with 0.003 wt% of SO4 and KOH with 0.001 wt% of
SO4. High residue amounts can be seen in HAN-AC and HBN-
AC, indicating unidentified impurities in the structure.
3.2.5 Nitrogen Adsorption Isotherms and Related Surface Area
Results
Nitrogen adsorption isotherms for samples synthesized in
water, acidic, and basic conditions are reported in Figure 11.
Hydrochars resulting from the three conditions exhibited a
non-porous structure, as evident from the flat isotherms found
near the baseline. Low surface area results of hydrochar (Table
8) suggest that hydrochar porosity and resulting specific
surface areas were not further optimized upon nitrogen
doping, as there was hardly any promotion of surface area
results. On the other hand, adsorption amounts for activated
carbon samples obtained from both nitrogenated and non-
nitrogenated hydrochar showed drastic improvements, as
seen from their isotherms.
The adsorption isotherms indicated that adsorption
capacities of HW-AC > HWN-AC, HAN-AC > HA-AC and HBN-AC
> HB-AC. With nitrogenated hydrochar precursors from acidic
and basic conditions, higher surface area of activated carbon
could be obtained. However, an opposite effect was found for
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Table 6. Elemental analysis of hydrochars.

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Notation C (wt %) H (wt %) N (wt %) S (wt %) O (wt %) Residue Empirical Formula

HW 67.30 4.425 0.085 0.64 27.50 0.05 CH0.789O0.306

RSC Advances Accepted Manuscript

HA 65.94 4.28 0.13 0.03 28.37 1.25 CH0.779O0.323
HB 66.035 4.77 0.095 0.115 28.65 0.335 CH0.867O0.325
HWN 66.50 4.195 1.59 0.535 27.04 0.14 CH0.757N0.0205O0.305
HAN 83.095 4.18 0.87 0.62 11.12 0.115 CH0.604N0.00897O0.100
HBN 74.045 3.775 1.055 0.345 19.96 0.82 CH0.612N0.0122O0.202

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Table 7. Elemental analysis of activated carbon.

Notation C (wt %) H (wt %) N (wt %) S (wt %) O (wt %) Residue Empirical Formula

HW-AC 87.16 0.855 0.48 1.94 8.635 0.93 CH0.118O0.0743
HA-AC 93.07 0.84 0.48 1.94 3.575 0.095 CH0.108O0.0288
HB-AC 87.935 0.87 0.54 3.075 7.415 0.165 CH0.119O0.0632
HWN-AC 88.035 2.165 0.94 0.95 7.69 0.22 CH0.295N0.00915O0.0662
HAN-AC 88.015 1.945 0.905 0.95 2.195 5.99 CH0.265N0.00881O0.0187
HBN-AC 89.215 2.945 0.78 0.775 3.78 2.505 CH0.396N0.00749O0.0318
neutral conditions. Surface area results followed the order of standard, at the Taiwan Textile Research Institute. In this
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HAN-AC > HBN-AC > HW-AC > HA-AC > HWN-AC > HB-AC. The method, carefully regulated test parameters include aerosol
same functional groups were found in all non-nitrogenated concentration, aerosol diameter, aerosol flow rate, aerosol

RSC Advances Accepted Manuscript

activated carbon samples, and likewise for all nitrogenated temperature and relative humidity of the environment. NaCl
samples as proven by using FTIR. Hence, we could eliminate with mass median diameter (MMD) of 0.26
the effect of different functional groups on the surface of the
samples. Pore size distribution for activated carbon samples
show mainly micropores with significant portion of pores with
diameters down to 5Å for non-nitrogenated samples. With
nitrogen doping, however, only samples processed in acidic
and basic environments showed a significant increase in
distribution of larger diameter pores (Figure S1).
Furthermore, material morphology has a great impact on
adsorption capacities. From SEM images, three morphology
types, described before as the spherical structure, sponge-like
fragments, and fine pore fragments, can thus be identified.
Spherical structure contributed the lowest adsorption as
hydrochar because of the limited surface area and pore
structure, while fine pore fragments were considered to
provide the most nitrogen adsorption sites because of the
micropores present in the broken structure. Sponge-like
fragments with large holes supplied a lower degree of
adsorption because such large cavities can be thought of as
flat surfaces which are not able to adsorb much nitrogen
internally.
It was observed that large areas of fine pore fragments
existed in HAN-AC and HBN-AC, leading to a relatively
increased surface area. Sponge-like fragments and spherical
structure occurred in HW-AC, HA-AC and HWN-AC, resulting in
moderate surface areas between the six activated samples.
The lowest surface area was found in the HB-AC sample, which
was composed of small pieces of porous fragments and
spherical structures. We deduce that hydrochar precursor
particle size affects the final form of the active material. The
nitrogenated hydrochar with larger particle sizes seemed to
obtain higher surface area after activation. Such large-sized
hydrochar tend to form larger porous fragments of activated
carbon via activation process.
The conclusion of nitrogen adsorption measurement was
that surface area of activated carbon synthesized from these
six conditions is significantly influenced by the three types of
morphologies, which are in turn influenced by hydrochar
particle size.

3.3 The Application of Air Filtration with Resulting Activated

Carbon
Figure 11. Nitrogen adsorption isotherms of hydrochar and activated carbon in water,
In this section, air filtration papers were tested by TSI model acidic and basic conditions.
8130 testing method, which is a commercial respirator mask

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the same pressure loss. Based on the above discussion, we can

see further potential in optimizing filtering mechanisms in
activated carbon for use in air filtration application.
Table 10. Filtration efficiency, pressure loss and thickness of air filtration paper, paper
Table 8. BET surface areas of hydrochars in the conditions of water, acidic, basic or and commercial air filter product.
nitrogen doping.
Filtration Solid Aerosol Filtration Pressure loss Thickness
Notation ABET (m2/g) Paper Efficiency (%) (mmH2O) (μm)
HW 4.75 (0.26μm, NaCl, MMD)
HA 1.44 C2K2 14.03 1.5 99 ± 2.9
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HB 2.60 C2K4 14.79 2.1 146 ± 18.1

HWN 1.31 C6K2 14.79 1.7 88 ± 10.4
HAN 2.34 C6K4 15.36 1.8 112 ± 15.6

RSC Advances Accepted Manuscript

HBN 3.54 Paper 5.00 1.6 Not Measured
Table 9. BET surface areas of activated carbons in the conditions of water, acidic, basic Commercial 57.99 0.6 150 ± 11.4
or nitrogen doping.

Notation ABET (m2/g) 4. Conclusions

HW-AC 2430
HA-AC 2392
HB-AC 2239
HWN-AC 2317
HAN-AC 2693
HBN-AC 2681
μm was used as solid aerosol that was actively filtered by test
samples. The testing model was chosen because of the
limitation of our sample size. The results of TSI model 8130
testing method include filtration efficiency and pressure loss
which together can determine the filtering capability. The
comparison of these two results between air filtration papers
and commercial air filter product are discussed in this section.
3.3.1 Filtration Efficiency and Pressure Loss
Higher filtration efficiency indicates higher capability of
intercepting dust particles. Low pressure loss represents that
air can flow through the filter with less resistance. Filters with
great functionality have results of both high filtration efficiency
and low pressure loss.
The filtration efficiency of air filtration paper created in this
work is about 14-15% regardless of different activated carbon
added (Table 10, additional information in Supporting
Information), and the value is around a quarter of
commercially available air filter product. Pressure loss of air
filtration papers is higher than commercial air filter product.
Although lower in performance, these samples serve to
demonstrate several key characteristics. These results
suggested that four different activated carbon has no
significant difference for air filter application. Hence, we can
speculate that the efficiency of filtering mechanism for
activated carbon is mainly a contribution from surface
interception which can capture particles within a gas flow
when particles touch the surface31 instead of material porosity
because of the close value of filtration efficiency for our
samples.
With addition of activated carbon, there is approximately
ten percent improvement on filtration efficiency while keeping
In this work, the effect of reaction time, reaction temperature,
sucrose concentration, pH effect of hydrothermal solution and
nitrogen doping that affected sucrose-derived hydrochar and
activated carbon were investigated. All reaction conditions
that affected yield, particle size of CSs, SEM morphology,
functional groups and BET surface area were discussed here.
These different reaction parameters make hydrochar a
controllable material. Through KOH activation process, highly
porous material was synthesized and one of the highest
2
specific surface area was up to 3026 m /g. Moreover, it was
shown that the amount of activation agent affected the pore
characteristics of activated carbon greatly. pH effect and
nitrogen doping of hydrochar precursor also had great
influence on surface area results of activated carbon. In our
results, nitrogenated activated carbon had larger surface area
than non-nitrogen activated carbon, but hydrochar displayed
similar surface area results.
The air filtration application of activated carbon was
performed by air filtration paper which used activated carbon
as adsorbent and pulp as substrate making it a biodegradable
material. The filtering ability of air filtration paper achieved
one quarter of commercial air filter product but different
synthesized activated carbon demonstrated similar filtration
efficiency. By determining material porosity is not a significant
factor in efficiency while surface trapping mechanism is
important, future optimization of active filler materials can
greatly increase the use of carbon materials for filtration.
Acknowledgements
The authors are grateful to the National Central University and
the Bureau of Energy, Ministry of Economic Affairs, Taiwan,
R.O.C. for funding (project title: Biodegradable Air Filter
Development). SWH thanks JM Huang and JD Lin at NCU
Precision Instruments Center for assistance in BET and SEM.
The authors also thank the National Chung Hsing University
and the National Chiao Tung University for elemental analysis
and GC-MS measurements, respectively. BKC thanks Prof AST

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