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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, a b b a*
Accepted 00th January 20xx Shih-Wei Hao , Chia-Hao Hsu , Yang-Guang Liu , Bor Kae Chang
DOI: 10.1039/x0xx00000x As air pollution problems become increasingly serious and the environmental awareness continues to rise, a source of
www.rsc.org/ 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,


8 9 10 11
1. Introduction including bagasse, coconut shell, banana, corn cob, coffee
12 13
grounds, peanut hull, hemp, pine needles and oak.
The development of carbon materials has always been an
Applications for HTC-synthesized hydrochar include fuel,
attractive issue due to its excellent advantages such as less
electric capacitor, heavy metal adsorption, and activated
damage to the environment, low cost, and relative ease of 14
carbon synthesis.
commercialization. Hydrothermal carbonization (HTC) is a
Activated carbon can be obtained through activation of
synthesis method that transfers carbon precursors into useful
hydrochar precursor. A highly porous material with large
carbon materials under mild synthesis conditions. The basic
specific surface area will be formed and the resulting
process involves pre-configured solutions that are placed into
performance as adsorbents will be dramatically enhanced by
sealed Teflon-lined stainless steel autoclaves and heated to a
this process. The porosity and pore size of activated carbon
specified temperature for the duration of several hours.
depends on activation temperature, time, inert gas flow rate
The resulting hydrochar can be obtained from the bottom
during activation, and species of activated agent. Functions of
of the autoclave that display controllable pore size, 15, 16
such highly porous carbon material include adsorbents,
morphology, and specific chemical functionalities. The features 12, 17, 18 19
capacitor electrodes, electrocatalyst, hydrogen
of hydrochar are usually controlled with temperature, 20 21
storage, and carbon dioxide capture. In addition, modifying
concentration of carbon precursor, reaction time and acidic or
activated carbon by nitrogen-doping has been demonstrated
basic catalysis.1 Carbohydrates, such as sucrose,2, 3 glucose,4 22
to alter adsorption performance of the material. Although
cellulose,5-7 and natural biomass are the usual carbon
there are many applications of activated carbon, there have
precursors used in such a processes. On the other hand,
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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3 -1
carbon filters. However, the abovementioned products are not tubular furnace under nitrogen flow of 200 cm min . After
all manufactured in an eco-friendly fashion, leading to further cool down, still under N2, the activated carbon was then
costs to the environment and resources. In order to improve washed with distilled water until neutral pH was reached and
this problem, we designed an air filtration paper, which not dried in an oven overnight.
only purifies air pollution particles but is also an
environmentally friendly green product. The air filtration paper 2.2.2 Effect of pH and Nitrogen Doping on Hydrochar and
is made of all biodegradable components, including pulp and Activated Carbon Synthesis
activated carbon.
Studies were first performed on the underlying active Hydrothermal treatment
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material, leading to a comprehensive investigation of the 20 ml of 0.5M sucrose aqueous solution with addition of
effects of pH and nitrogen doping on the active material. pH- sulfuric acid for acidic conditions, sodium hydroxide for basic
modified and nitrogen source added in the hydrothermal conditions, or ammonium sulfate for nitrogen doping was

RSC Advances Accepted Manuscript


solution make hydrochars with distinct pore size, morphology, placed in a 45 ml Teflon-lined stainless steel autoclave and
and surface chemical functionalities, which were compared to heated to 200°C for 4 hours in an oven. The autoclave was
hydrochar obtained from aqeous conditions. Activated carbon naturally cooled to room temperature, and the resulting solid
from the pH-modified and nitrogen-doped hydrochar were product was washed with deionized water until neutral pH and
further produced by an activation process, and different pore dried in an oven overnight.
characteristics were determined.
Activation process
Sucrose-derived hydrochar was mixed with KOH in a mass ratio
2. Experimental of 1:4 in a ceramic mortar and the mixture was heated to
2.1 Chemical Compounds 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
The materials we used in this research include sucrose (CAS
activated carbon was then washed with deionized water until
number: 57-50-1, Showa, 99.5%), sulfuric acid (CAS number:
neutral pH was reached and dried in an oven overnight.
7664-93-9, Showa, 97%), sodium hydroxide (CAS number:
1310-73-2, Showa, 97%), ammonium sulfate (CAS number:
2.2.3 Application of Air Filtration with Resulting Activated Carbon
7783-20-2, Showa, 99.5%) and potassium hydroxide semi
pellets (CAS number: 1310-58-3, Aencore, 85%).
1g of activated carbon and 4g of pulp were mixed with 1.5
2.2 Experimental Procedure liters of water by a physical method, further assisted by
rigorous stirring with a homogenizer. Then the mixture was
In this work, experiments are divided into three parts: (i) the distributed uniformly in a container containing water. By using
effect of time, concentration and temperature on hydrochar a traditional papermaking process, we could obtain a wet
and activated carbon synthesis, (ii) the effect of pH and preliminary paper. The preliminary product was then heated
nitrogen doping on hydrochar and activated carbon synthesis, to 70°C for 4 hours to remove water content. Finally, dry
and (iii) the application of air filtration with resulting activated pieces of paper with activated carbon uniformly distributed in
carbon. it was obtained, which we called the air filtration paper.

2.2.1 Effect of Time, Concentration and Temperature on


Hydrochar and Activated Carbon Synthesis 3. Results and Discussion
3.1 Effect of Time, Concentration and Temperature on Hydrochar
Hydrothermal Treatment
and Activated Carbon Synthesis
20 ml of sucrose at varying concentrations in aqueous solution
were placed in a 45 ml Teflon-lined stainless steel autoclave 3.1.1 Morphology and Yield
and heated to chosen synthesis temperatures for several hours
in a conventional oven. The autoclave was naturally cooled to Scanning electron microscopy was performed at the National
room temperature, and the resulting solid product was Central University Precision Instruments Center. Figure 1
washed with deionized water and dried in an oven at 70°C shows SEM images of our sucrose-derived hydrochar with
overnight. different reaction parameters. It was observed that carbon
spheres (CSs) with different morphologies result due to
Activation process distinct synthesis parameters. However, we can roughly
Hydrochar with fused (C2) and separated (C6) structures were categorize them into two types: fused (Figure 1 a-e & g) and
selected for further activation because they are the most separated (Figure 1 f & h). Notation for samples created under
representative samples of eight hydrochars based on their varying conditions are listed in Table 1. We observed that
morphology (see section 3.1.1 for details). The hydrochar was reaction time affected particle size, yield and degree of fusing.
mixed with KOH in a mass ratio of 1:4 and 1:2 in a ceramic Particle size of CSs was measured by MB ruler program.23 From
mortar and the mixture was heated to 800°C for 1 hour in a 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 FTIR results for each sample were nearly the same. The results
samples. (a) C2K2, (b) C2K4, (c) C6K2, (d) C6K4.
suggest that even with different reaction conditions,
hydrochar with similar chemical characteristic can be obtained.
hydrochar precursor was not evident, as there was not much For the activated samples, the number of characteristic
difference between C2K4 and C6K4. Due to the high reaction peaks decreased due to the dramatic chemical reaction. Only
temperature and the addition of enough KOH, the two O-H stretching band, C=C vibration band, and C=O vibration
different types of morphology of carbon precursors were band were left, and a peak at around 2350 cm-1 formed which
eliminated. is identified with atmospheric carbon dioxide24 found in FTIR
results (absent or barely present in C6K4). Different KOH
3.1.2 Chemical Properties of Hydrochar and Activated Carbon
concentration and different morphologies of carbon precursor
seemed to have no significant impact on resulting samples.
Functional groups on the surface of various hydrochar samples The results show that hydrochar of all preparations were
16
have been investigated in detail. FTIR spectra of our sucrose- successfully transformed into activated carbon.
derived hydrochar samples are shown in Figure 3. Broad bands
-1
in the 3000-3700 cm range correspond to O-H stretching in

Figure 4. FTIR spectra of activated carbon derived from hydrochar samples.


Figure 3. FTIR spectra of hydrochar samples. Characteristic peaks can be identified in
the spectra of samples under various synthesis parameters. 3.1.3 Nitrogen Adsorption Isotherms and Related Surface Area
Results
water, and the bands at around 2900 cm-1 were assigned to
stretching vibrations of aliphatic C-H. The bands at 1620 cm-1 Nitrogen adsorption isotherms of hydrochar and activated
together with the band at 1510 cm-1 were attributed to C=C carbon, performed at the National Central University Precision
vibrations, and the band at 1710 cm-1 was assigned to C=O Instruments Center, are shown in Figure 5 and the related
vibration. Another broad band at the 1000-1450 cm-1 region textural properties are summarized in Table 3. Pressure ranges
correspond to C-O stretching. Two bands at 800 and 750 cm-1 used for BET specific surface area determination were chosen
were attributed to aromatic C-H out-of-plane bending according to selection rules suggested by Rouquerol et al.
25

vibrations. No matter the change of synthesis parameters, the 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 Much lower levels of HMF were found in nitrogenated
Activated Carbon Synthesis samples compared to non-nitrogenated ones, as summarized
in Table 5, and the result corresponds to higher yields achieved
3.2.1 Yield and Supernatant Liquid 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
All information related to hydrothermal treatment of sucrose
liquid and a corresponding elevation in the hydrochar yield.
are listed in Table 4, including hydrothermal condition, yield of
Additionally, we found no regular relationship between
hydrochar, pH value of solution and average particle size of
levulinic acid and yield. Levulinic acid results from GC-MS did
carbon spheres. Particle size of CSs was measured in the same
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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. not observed (Figure 9). The C=O stretching bands of
nitrogenated and non-nitrogenated seem to have same
3.2.3 Chemical Properties of Hydrochar and Activated Carbon -1
intensity. While the absence of the 621 cm peak indicates
that SO4 is not found in the structure for nitrogenated samples
A reduced peak in FTIR spectra of nitrogenated samples at 2-
of this work, which should be the case since SO4 in its ion
-1
1705 cm has been previously described in literature, state would have been removed by deionized water described
suggesting that nitrogenated samples contains reduced in the experimental procedure. FTIR spectra cannot prove
30 -1
formation of C=O groups. Another band at 621 cm related nitrogen doping of samples because all samples showed the
to SO4 stretching was observed by the authors in each same results. Additionally, there are two different results
nitrogenated samples because of the addition of ammonium compared to reference paper. Therefore, elemental analysis
sulfate. Other evidence that proves nitrogen doping was (National Chung Hsing University Instrument Center) was
-1
successful include N-H stretching bands at 3000-3500 cm , but employed to provide definitive answer as to whether nitrogen
this was indistinguishable due to the overlapped region of O-H doping was successful in the samples.
stretching bands.

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Figure 10. FTIR spectra of activated carbon.

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

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

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