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org/acscatalysis Research Article

Fabrication of a Photocatalyst with Biomass Waste for H2O2

Synthesis
Liangpang Xu, Yang Liu, Lejing Li, Zhuofeng Hu,* and Jimmy C. Yu*
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ABSTRACT: Synthesis of the indispensable H2O2 in pure water

remains a challenge for current methods, which often require
organic solvents (anthraquinone method), sacrificial agents of
alcohols (traditional photocatalysis), or electrolyte of salts
(electrochemical synthesis). Here, various biomass (glucose,
sucrose, starch, cellulose, and paperboard) was converted to
hydrothermal carbonaceous carbon (HTCC) photocatalysts for
H2O2 synthesis in pure water. The apparent quantum yield and
synthesis rate could reach 18.2% (at 420 nm) and 1.16 mmol gcat−1
h−1, respectively. Importantly, HTCC can be prepared with
biomass waste such as paperboard. Mechanism study indicates that
H2O2 production on HTCC is dominantly via a two-step oxygen
reduction reaction with superoxide anions as an intermediate. Through theoretical calculation, it was found that the polyfuran
structure of HTCC is favorable for adsorption and activation of oxygen and exhibits superior electron transfer property. These are
the key steps for oxygen reduction and the subsequent H2O2 production. This work provides insights into activation of oxygen on
the emerging HTCC photocatalyst and highlights its appealing application for H2O2 synthesis in pure water.
KEYWORDS: biomass waste, hydrothermal carbonaceous carbon, photocatalyst, hydrogen peroxide, pure water

■ INTRODUCTION
Hydrogen peroxide (H2O2) is a common and useful eco-
is a promising approach for sustainable and green H2O2
synthesis in pure water. Furthermore, it could achieve in situ
friendly oxidant with extensive applications in wastewater applications of the synthesized H2O2, such as advanced
treatment and disinfection,1 organic synthesis,2 and pulp and oxidation process (AOP) and disinfection,10,11 thus avoiding
paper industry.3 The worldwide H2O2 yield has reached its loss in the transportation and storage period.
approximately 5.5 million tons per year.4 Recently, H2O2 has To date, various photocatalysts have been studied for H2O2
synthesis, such as metal oxide (TiO2, ZnO, etc.),12,13 g-C3N4,14
been even used as a liquid fuel in a compact and membrane-
BiVO4,15 CdS,16 and transition-metal complexes.17 H2O2 is
free fuel cell under ambient conditions.5,6 Currently, more than
dominantly generated via the oxygen reduction reaction
95% of commercial H2O2 is manufactured using the traditional
(ORR).18 However, the ORR in present photocatalysis is
anthraquinone (AQ) method.7 However, this method involves
highly restrained by (1) unfavorable adsorption of O2 on the
severe nongreen problems, including extensive energy
surfaces of normally used photocatalysts, such as the melon
consumption in the hydrogenation and oxidation processes,
plane of g-C3N4,11 (2) poor electron transfer from catalysts to
and generation of a large amount of wastewater, exhaust gas,
oxygen, and (3) difficult activation of oxygen to form
and solid waste in the AQ oxidation process.7 Hence, it is an
superoxide anions (•O2−) due to the requirement of strong
urgent need to produce H2O2 on a large scale in sustainable
reducing ability (−0.33 V vs normal hydrogen electrode
approaches.
(NHE) and even overpotential).19,20 As a result, the
The synthesis of H2O2 in pure water could offer advanced
photocatalytic performance on H2O2 synthesis in pure water
opportunities for its promising applications in terms of (1)
is extremely low [apparent quantum yield (ΦAQY) < 8% at λ =
convenient separation process, (2) in situ applications, and (3)
minimized synthesis cost. However, it is hard to be achieved
using present synthesis methods. For example, the H2O2 Received: August 14, 2021
produced via the AQ method or alcohol oxidation has to be Revised: November 4, 2021
separated from a large amount of organics.7,8 The electro- Published: November 17, 2021
chemical synthesis method to produce H2O2, although has
attracted much attention, requires electrolyte of salts, as well as
extra energy and equipment inputs.9 The photocatalytic route

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420 nm, synthesis rate <0.1 mmol gcat−1 h−1].21−27 This has led
to extensive usage of hole sacrificial agents (e.g., up to 90%
volume of ethanol),14,28 thus increasing the cost for H2O2
synthesis sharply and making the separation of H 2 O 2
inconvenient.
Fabrication of advanced photocatalysts and developing an
appropriate strategy for oxygen reduction are the key to
efficient H2O2 synthesis in pure water. Hydrothermal carbona-
ceous carbon (HTCC) is a kind of carbon-based material
obtained from hydrothermal treatment of biomass (glucose,
cellulose, weed, rice, cow dung, sunflower, etc.) (Figure
1a).29−31 This material can be prepared in a large scale
Figure 1. Schematic diagrams. (a) Scheme showing the preparation of
HTCC from biomass. (b) Proposed photocatalytic method for H2O2
synthesis with HTCC.
considering the low-cost raw material of biomass and the facile
preparation process. The semiconductive property of HTCC
has been recently found, which can be used for photocatalytic
applications.31−33 It has been demonstrated that this semi-
conductive property can be attributed to the conjugated
structure of sp2-hybridized polyfuran within HTCC. The
polyfuran units could be a favorable structure for oxygen
reduction to generate H2O2 (Figure 1b). For each furan
monomer, there are six electrons in the conjugated orbital
plane, which could contribute to electron-rich surfaces of
HTCC. Therefore, the HTCC could exhibit high affinity for
electrophilic O2, and the electron-transfer process could be
favorable too. However, it remains unknown whether this
emerging photocatalyst could be used for H2O2 synthesis.
Herein, on the basis of the abovementioned opinion, we first
discovered that various biomass (glucose, sucrose, starch,
cellulose, and paperboard) can be used to prepare high-
efficiency photocatalysts for efficient H2O2 synthesis in pure
water using visible or even near-infrared light. The HTCC can
adsorb and activate O2 with the penta-cycles as active sites.
According to theoretical calculation, the energy for O2
adsorption on HTCC is −0.69 eV, and the adsorbed O2
owns a greatly lengthened OO bond (from 1.209 to 1.291
Å). Besides, the electron transfer from HTCC to O2 is also
favorable, and the O2 activation process in the HTCC system
is found to be an energy-favorable process. With the favorable
structure for ORR, HTCC can be used for high-efficiency
H2O2 synthesis with a ΦAQY of 18.2% (at 420 nm) and a rate
up to 1.16 mmol gcat−1 h−1. Interestingly, the waste of
paperboard can be also used to prepare HTCC for photo-
catalytic H2O2 synthesis. This work demonstrates the
activation process of O2 on the emerging HTCC photocatalyst
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and highlights the promising application for H2O2 synthesis in
pure water.
■ RESULTS AND DISCUSSION
Characterization of Catalysts. Five kinds of HTCC were
prepared by hydrothermal treatment of various biomass
(glucose, sucrose, starch, cellulose, and paperboard). Notably,
to convert cellulose-based raw materials (cellulose and
paperboard) to HTCC, dilute sulfuric acid was used as a
solvent, while pure water was used for the others. The
paperboard is cellulose-rich biomass waste which is widely
used in the packaging industry. g-C3N4 was prepared as a
reference photocatalyst by a traditional method, and its X-ray
diffraction (XRD) pattern is shown in Figure S1. As shown in
Figure S2, the precursors were successfully converted to yellow
to dark particles after hydrothermal treatment. Furthermore,
the HTCC synthesized from cellulose/paperboard exhibits a
brown color, unlike the black color of HTCC prepared from
glucose, sucrose, and starch (Figure S2). The morphology of
HTCC prepared with cellulose is irregular micron particles
(Figure S3). The HTCC exhibits a broad peak in the XRD
pattern, suggesting an amorphous structure (Figure S1).
The Fourier transform infrared (FT-IR) spectrum was
recorded to determine the chemical structure of HTCC.
Typical IR peaks associated to polyfuran are observed (Figure
S4a). The characteristic CC stretching vibration of
polyfuran is observed at 1517 and 1614 cm−1, while the C−
O−C stretching vibration is located at 1010 cm−1.31,34 The C−
H in-plane deformation together with the C−C stretching
vibration in polyfuran is observed at around 1440 cm−1, while
the C−H out-of-plane deformation is at 870 and 645
cm−1.35,36 Moreover, a distinct band at 800 cm−1 induced by
the α-substitution in polyfuran is observed, suggesting the
linkage by α-position to form the carbon backbone of
polyfuran.35 These observations strongly demonstrate the
presence of α-substituted five-membered heterocyclic structure
of polyfuran. Additionally, the bands of aliphatic CO (1705
cm−1), C−O (1190 and 960 cm−1), and C−H (2936 cm−1)
stretching are also observed.31 The wide peak at 3410 cm−1 is
derived from O−H stretching, indicating the adsorption of
water molecules on the material.
In the 13C solid-state cross-polarization magic angle spinning
nuclear magnetic resonance (CP-MAS NMR) spectrum
(Figure S4b), the observed signals are mainly in the range
from 100 to 160 ppm, which represent the characteristic of the
sp2 hybrid C in CC double bonds of furan units.37,38
Specifically, the strongest signal at 152 ppm is assigned to O−
CC (C1 and C4) in the terminal furan rings, while the peaks
between 115 and 125 ppm represent the CC−C (C2 and
C3). An obvious signal at 128 ppm is related to the condensed
arene group induced by the linkage of adjacent furan rings with
the carbon atom at C2 or C3.39 Extra signals are also observed
in 0−100 ppm, which represent the characteristic of sp3 carbon
atoms, including aliphatic C−H groups and C−OH group
(centered at 40 ppm).31 The signals at 175 and 205 ppm are
assigned to −COOH and −CO groups, respectively. The
Raman spectrum of HTCC is also in consistent with the
abovementioned observations. The bands at 1580 cm−1
represents CC stretching in furan, while the broad band at
1352 cm−1 represents the C−C stretching (Figure S5).40
Furthermore, the weak bands at 1030 and 950 cm−1 can be
assigned to C−H wagging and ring deformation, respectively.
The abovementioned analysis clearly demonstrates the
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Figure 2. Comparing the band structure of HTCC with g-C3N4. (a) UV−vis−NIR diffuse-reflectance spectra. (b) Mott−Schottky plots. (c) VB
XPS spectra. (d) Summary of the band structure of HTCC and g-C3N4 (vs NHE at pH 7).

Figure 3. Photocatalytic performance of HTCC on synthesis of H2O2. (a) Photocatalytic H2O2 production on HTCC derived from varying
biomass under visible-light irradiation. (b) Calculated H2O2 synthesis rates for HTCC and g-C3N4. (c) Dependence of the H2O2 synthesis rate on
the wavelength of incident light with HTCC (cellulose) as a catalyst. (d) Production of H2O2 in a longer duration time and the corresponding
production rate in each hour.

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Table 1. Activity Comparison between HTCC and Other Reported Photocatalysts for H2O2 Synthesis in Pure Water
Photocatalysts concentration of catalyst (g L−1)
g-C3N4/PDIx 1.7
g-C3N4/PDI/rGO 1.7
g-C3N4 aerogels 1.7
TiO2−Pt 0.05
graphene oxide 0.32
g-C3N4/PDI-BN-RGO 1.7
resorcinol-formaldehyde resins 1.7
HTCC (cellulose) 0.2
chemical nature of HTCC, which is composed of polyfuran
units dominantly together with some functional groups (e.g.,
−CO, −COOH, aliphatic C−H, and C−OH).
In the high-resolution C 1s spectrum, three peaks
representing the binding of C−C, CO, and C−O are
observed. The areas of these peaks follow the order of CO <
C−O < C−C. In the O 1s spectrum, O−C also exhibits higher
peak area than that of OC. These observations are in
consistent with the reported spectra of pure polyfuran (Figure
S6),36 as well as the spectra in Figure S4. The elemental
composition of HTCC (64.5% C, 4.1% H, and 30.3% O) is
also close to that of furan (70.6, 5.9, and 23.5%). These results
further confirm the preponderant polyfuran structure in
HTCC.
The band structure of HTCC prepared with cellulose and g-
C3N4 was estimated. From the UV−vis−NIR diffuse-
reflectance spectra (Figure 2a), it can be found that HTCC
exhibits strong absorbance to light between 420 and 800 nm,
while g-C3N4 shows a dramatic decrease for absorbance of light
with wavelength >475 nm. This suggests a higher solar energy
utilization efficiency of HTCC compared with the well-studied
g-C3N4. The photosensitive units of HTCC can be assigned to
the preponderant polyfuran structure, which has been proved
to be a semiconductive polymer due to the sp2-conjugated
hybrid structure.31 The other groups, such as aliphatic C−H
and C−OH, are less likely to absorb visible light. There are six
electrons derived from C and O atoms in the conjugated plane
of the furan monomer to form a large π bond,41 which could
absorb light with sufficient energy, thus, getting excited. The
valence band (VB) of polyfuran should be constituted of the C
2p orbit, while it is C 2p/O 2p orbits for the conduction band
(CB) according to calculation of density of states (DOS).31
The band structure was further estimated with additional
measurements. As shown in Figure 2b, the estimated Fermi
level of HTCC is −0.51 eV, close to that of g-C3N4 (−0.57
eV), indicating a possibly comparable reducing ability of these
two photocatalysts. Notably, as the CB edge is above the Fermi
level, the O2 reduction to •O2− (−0.33 V vs NHE) is favorable
thermodynamically for HTCC, which is the first step for H2O2
production. As presented in Figure 2c, the VB maximum (EVB)
for HTCC and g-C3N4 is 1.69 and 1.97 eV below their
corresponding Femi level, respectively. Then, EVB of HTCC
and g-C3N4 should be 1.18 and 1.4 eV, respectively. The band
diagram of HTCC and g-C3N4 is summarized in Figure 2d. It
is found that the EVB of HTCC is 0.22 eV more negative than
that of g-C3N4, thus giving rise to a weaker oxidation power of
HTCC thermodynamically. This could relieve the oxidative
decomposition of H2O2 during the photocatalytic reaction.
Therefore, the HTCC is possibly a good candidate for
photocatalytic H2O2 synthesis in terms of the favorable band
structure.
Research Article
irradiation H2O2 synthesis rate (μmol g−1 h−1) ΦAQY refs.
λ > 420 nm 0.6 2.5% at 420 nm 21
λ > 420 nm 11.2 6.1% at 420 nm 22
λ > 420 nm 0.8 NA 23
full spectrum 101.9 NA 24
λ > 420 nm 0.7 NA 25
λ > 420 nm 0.8 7.3% at 420 nm 26
λ > 420 nm 2.4 7.5% at 450 nm 27
λ > 420 nm 1160 18.2% at 420 nm this work
Photocatalytic Performance on H2O2 Synthesis. Figure
3a shows the time courses of H2O2 concentration under
irradiation of visible light in 60 min. The corresponding H2O2
synthesis rates are shown in Figure 3b. All the HTCC materials
show considerable activity on H2O2 production, and the rates
are in the order of HTCC (cellulose) > HTCC (starch) >
HTCC (sucrose) > HTCC (paperboard) > HTCC (glucose),
ranging from 0.42 to 1.16 mmol gcat−1 h−1. It is found that the
synthesis rate of H2O2 for HTCC (cellulose) is twice of
HTCC (glucose). This can be attributed to the more negative
ECB of HTCC (cellulose) compared with HTCC (glu-
cose). 31,33 Notably, compared with g-C3 N 4 , the H 2 O 2
production rates for HTCC is greatly higher (17−49 times),
indicating the outstanding activity of HTCC. The paperboard,
a kind of biomass waste which is widely used in the packaging
industry, can be also used to prepare HTCC with considerable
activity on H2O2 synthesis. This finding offers a promising
approach to turn biomass waste into valuable material with
significant applications.
The H2O2 synthesis rate in pure water for HTCC (cellulose)
(1.16 mmol gcat−1 h−1) exceeds all the previous reports by
dozens to thousands of times (Table 1). Moreover, the ΦAQY
of HTCC was calculated (Text S1), which is 18.2% at 420 nm.
This value exceeds the benchmark by twofold (resorcinol-
formaldehyde resins, Table 1). These results suggest that the
HTCC is a high-efficiency photocatalyst and owns a high solar
energy utilization efficiency. Given the features of low cost and
easy to prepare, the HTCC is potentially an advanced
photocatalyst for sustainable and green H2O2 synthesis in a
large scale using the free solar energy and abundant water and
O2 on earth.
The synthesis rate of H2O2 regarding the surface area of
material was determined to show the geometric effects. The
measured Brunauer−Emmett−Teller specific surface areas of
g-C3N4 and HTCC are 31.31 and 15.08 cm2 g−1, respectively.
Accordingly, the H2O2 synthesis rates were calculated to be
0.73 and 77.19 μmol cm−2 h−1. In terms of this rate, the
activity of HTCC is 105 times of g-C3N4, twice of the
enhancement (49 times) determined by mass of the catalyst
(Table S1). This result suggests that HTCC owns more
favorable surfaces for H2O2 synthesis.
The turnover frequency (TOF) was determined to associate
the activity to the number of active sites of catalysts. Here, the
TOF was calculated using the following equation42
mol of product
TOF =
mol of catalyst × time (1)
with calculation, the TOF of g-C3N4 and HTCC is 2.2 × 10−6
and 7.9 × 10−5 h−1, respectively (Table S1). The TOF of
HTCC outperforms g-C3N4 by 35 times, indicating the
superior activity of HTCC.
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Figure 4. Comparing the photoelectric properties of HTCC and g-C3N4. (a) Transient photocurrent responses of HTCC and g-C3N4 under
visible-light irradiation. (b) Photoluminescence spectra of HTCC and g-C3N4.

Figure 5. Mechanism for production of H2O2 on HTCC. (a) H2O2 synthesis rate under different atmosphere/solution conditions. (b) EPR spectra
of HTCC suspension using DMPO as a trapping agent under visible-light irradiation. (c) Diagram showing the pathway of H2O2 production on
HTCC.

The H2O2 production under irradiation of various single-
wavelength lights was also evaluated. As indicated in Figure 3c,
the H2O2 synthesis rates closely match the absorption
spectrum of HTCC, which were determined to be 0.28,
0.26, 0.16, and 0.09 mmol gcat−1 h−1 at 420, 500, 600, and 700
nm, respectively. This indicates that HTCC can use even near-
infrared light for H2O2 synthesis. This is the first time that
H2O2 has been produced using the near-infrared light in the
solar spectrum. Hence, the HTCC could be considered an
advanced material in terms of efficient conversion of solar
energy to chemical energy via synthesis of H2O2.
Production of H2O2 in a longer duration time was also
tested to evaluate the H2O2 accumulation property in the
photocatalytic system of HTCC. It has been found that the
produced H2O2 would further suffer from the oxidative
decomposition induced by photogenerated holes.14 The
decomposition of H 2 O 2 on g-C 3 N 4 and HTCC was
investigated in a N2-saturated atmosphere. After 1 h
14484
irradiation, the concentration of H2O2 decreased by 17% for
g-C3N4, while no obvious decrease was observed for HTCC
(Figure S7). This probably results from the more negative EVB
of HTCC compared with g-C3N4. Hence, the H2O2 tends to
remain stable in the photocatalytic system of HTCC, thus
avoiding the undesirable loss and guaranteeing the continuous
accumulation in water. As shown in Figure 3d, H2O2 keeps a
steady accumulation in aqueous solution even in 4 h, and the
final H2O2 concentration can reach up to 1.6 mmol L−1 under
visible-light irradiation. These results suggest that HTCC has
the potential for synthesis of H2O2 in a higher concentration,
thus fulfilling the requirement for practical applications.
The cyclic test was conducted to evaluate the catalyst’s
reusability and stability. The H2O2 synthesis rate did not
exhibit significant decrease (<8%) even in the fifth cycle
(Figure S8), suggesting that the HTCC is stable and reusable.
Furthermore, the 13C solid-state CP-MAS NMR and FT-IR
spectra before and after photoreaction was also compared, and
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Figure 6. Density functional calculations for activation of O2 on HTCC. (a) Process for activation of the O2 molecule on HTCC. (b) Charge
difference map of the O2-HTCC system. (c) Structure change. (d) Energy change for the O2 activation in the NEB calculations on the HTCC
system.
no visible difference could be observed (Figure S9). In the
NMR spectra, the peaks (152 and 115−128 ppm) associated
to polyfuran remained after photoreaction (Figure S9a). The
IR peaks attributed to the polyfuran structure (1614, 1517,
1440, and 1010 cm−1) are also retained (Figure S9b). Hence,
the polyfuran units of HTCC should be stable during
photocatalysis.
To get insights into the efficient H2O2 production over
HTCC, the well-studied g-C3N4 was selected as a comparison
to show the photoelectric properties of HTCC. It has been
widely accepted that the catalysts’ photocatalytic activity is
highly restrained by the separation/recombination of photo-
induced charge carriers. For example, the poor activity of g-
C3N4 on H2O2 production is related to its inferior separation
and fast recombination of photoinduced electrons and holes.43
Here, the electron transfer and recombination process were
evaluated by measurements. Compared with g-C3N4, the
photocurrent density for HTCC is significantly higher (Figure
4a), indicating an efficient separation of electrons and holes of
HTCC. Moreover, HTCC exhibits extremely weak fluores-
cence intensity, which is much lower than that of g-C3N4
(Figure 4b), suggesting the much slower recombination of
charge carriers of HTCC. In this case, compared with g-C3N4,
the photoexcited HTCC can offer far more electrons and holes
for further redox reactions. Besides, HTCC exhibits a Nyquist
circle with a smaller diameter compared with g-C3N4 (Figure
S10). It indicates that the resistance value for HTCC is lower,
representing a higher transfer rate for the interfacial charges.
These results demonstrate the superior photoelectric proper-
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ties of HTCC compared with g-C3N4, which could contribute
to efficient photocatalytic H2O2 production over HTCC.
Mechanism for Production of H2O2. The H2O2 can be
generated in the process of oxygen reduction and/or water
oxidation. 11,44,45 To distinguish the pathway for H2O 2
production, the photocatalytic H2O2 production experiments
were conducted under varying atmosphere conditions. It can
be found that the H2O2 synthesis rate is promoted under an
O2-saturated condition and greatly inhibited when O2 is
removed by N2 (Figure 5a). Therefore, ORR should be the
dominating process for H2O2 production.
There are also two pathways for H2O2 production in terms
of ORR, a multistep (O2 to •O2− to H2O2) and a one-step (O2
to H2O2) O2 reduction process.11,46 To identify the pathway
for ORR, the effect of scavenger of •O2− was investigated. It is
obvious that the H2O2 production is greatly inhibited by
adding p-benzoquinone (p-BQ), suggesting the important role
of •O2− (Figure 5a).
Electron paramagnetic resonance (EPR) spectra were
measured to confirm the formation of •O2− by using spin
trap of 5,5-dimethyl-1-pyrrolineN-oxide (DMPO). As shown
in Figure 5b, no visible peak occurred in the dark (0 min).
After irradiation, however, a four-line 1:1:1:1 signal can be
observed. These peaks correspond well to a standard signal of
the DMPO-•O2− adduct, indicating the occurrence of •O2−.47
Furthermore, the intensity for these peaks keeps increase with
further irradiation to 6 min. This result further proves that
•O2− is the key intermediate in H2O2 production, which is
generated through the O2 reduction on HTCC. Therefore, the
pathway for H2O2 synthesis over HTCC should be the
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multistep ORR (Figure 5c). Moreover, it is found that there is
production of a trace amount of small organic acids (formic
acid and acetic acid) in the solution after photoirradiation
(Figure S11), indicating the hole-induced oxidation of some
groups within HTCC, such as −C−OH and −CH3 (Figure
S12, Table S2). However, the oxidation of terminal groups of
HTCC would not inhibit the activity on H2O2 production as
proved by the long-duration time test and cyclic test (Figures
3d and S8).
Activation of O2 Molecules on HTCC. The activation of
O2 molecules on HTCC was further investigated by density
functional calculations. As HTCC is dominantly composed of
polyfuran units, we constructed a slab consisting polyfuran and
O2 molecule.
The energy for O2 adsorption (Ead) on HTCC was
calculated using eq 2
Ead = Etot − Esubstrate − EO2
(2)
where Etot, Esubstrate, and EO2 are energy of the whole of O2 and
substrate, substrate, and adsorbed O2, respectively.
The calculated adsorption energy is about −0.69 eV. The
value is negative, indicating that the O2 adsorption on HTCC
is thermodynamically favorable.
Importantly, the O2 can be activated once adsorbed on the
HTCC. The initial bonding of OO bond is 1.209 Å (Figure
6a). After relaxation and activation, the bonding greatly
increases to 1.291 Å, indicating the activation of O2 molecules.
Under this circumstance, the OO is just on the top of the
penta-cycles of HTCC. Its location is limited around the
penta-cycles of HTCC, which suggests that the penta-cycles of
HTCC could be the active site for O2 activation.
The activation and electron transfer can be also reflected in
the charge difference map. The charge difference map was
acquired via using the O2 and HTCC charge density map to
subtract that of O2-HTCC. As shown in Figure 6b, the red
region and green region are electron-rich and electron-poor,
respectively. Obviously, the two carbon atoms in the penta-
cycle of HTCC loss some electrons, while the O2 molecule on
the top gains electrons. This result indicates the electron
transfer from HTCC to O2 molecule, which is in good
agreement with the fact that O2 gains electron to form •O2−.
Then, the method of nudged elastic band (NEB) was applied
to study the O2 activation process on the HTCC system.48
First, full relaxation was involved to acquire optimized
reactant/product adsorbates. Then, eight intermediate states
are investigated. There are totally nine states in our calculation
(Figure 6c). The energy-change diagram is shown in Figure 6d.
It can be found that the energy just keeps dropping in all the
states and finally reach a steady state. Therefore, it can be
concluded that the activation process of O2 on the HTCC
system is an energy-favorable process, suggesting that HTCC is
a superior catalyst for O2 activation and H2O2 production.
■ CONCLUSIONS
The HTCC photocatalyst with superior activity on H2O2
synthesis was successfully prepared using various biomass
(glucose, sucrose, starch, cellulose, and paperboard), and
cellulose is found to be the most suitable raw material. The
H2O2 synthesis rate in pure water can reach as high as 1.16
mmol gcat−1 h−1 on HTCC with visible-light irradiation, and a
record-high ΦAQY of 18.2% (at 420 nm) was achieved. By
boosting H2O2 synthesis up to 700 nm, the HTCC is
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potentially a good candidate for solar-to-chemical energy
conversion. It is also demonstrated that the production of
H2O2 on HTCC is mainly via oxygen reduction. The
underlying mechanism for efficient H2O2 production can be
attributed to the favorable adsorption and activation of O2
molecules on the HTCC surfaces composed of polyfuran units.
As a cheap and easy-to-prepare material, the HTCC could be a
promising catalyst for photocatalytic synthesis of the
demanding H2O2 in pure water.
■ EXPERIMENTAL SECTION
Preparation of Materials. The HTCC was prepared
according to previous work.31 Briefly, the precursor (0.8 g) was
added into ultrapure water (20 mL), followed by ultrasound
for 30 min. Additional concentrated sulfuric acid (0.22 mL)
was added to the solution when using cellulose-based raw
materials (cellulose and paperboard). Then, the homogeneous
solution/suspension was transferred into a 25 ml hydrothermal
reactor, which was sealed and maintained at 200 °C for 12 h.
The obtained solid product was filtered and washed using
ultrapure water/ethanol for four times. The material was finally
dried with a temperature of 60 °C for 12 h. For comparison,
the g-C3N4 photocatalyst was prepared by heating melamine
(550 °C, 4 h) in a ceramic crucible.
Photoreaction. In all photocatalytic experiments, 10 mg of
catalyst was added into ultrapure water (50 mL) with
ultrasound for 15 min. For the H2O2 accumulation experiment,
the dosage of the catalyst is 50 mg. The suspension was then
transferred to a jacketed beaker, followed by 0.5 h O2 bubbling
and continuous stirring prior to photoirradiation. A water-
circulating system was used to keep the temperature of the
reaction solution at 20 ± 0.1 °C. The light source was a xenon
lamp (300 W), and the UV light was cut using a filter (420
nm). The concentration of H2O2 was analyzed by a classic I3−
method.49 Specifically, the supernatant was mixed with
phthalic acid (0.1 M) and potassium iodide (0.4 M) in a
volume ratio of 1:1:1. The absorbance at 355 nm was analyzed
using a UV−vis spectrophotometer after complete color
development (30 min). The calibration curve is shown in
Figure S13, and a good linear relation (R2 = 0.999) is observed
between absorbance and the H2O2 concentration.
Apparent Quantum Efficiency Analysis. The photo-
reaction was performed using an HTCC suspension (1.5 g L−1,
80 mL) in a borosilicate glass bottle. The suspension was
ultrasonicated and bubbled with O2, followed by irradiation for
an hour. A band-pass glass filter (420 nm) was equipped to the
xenon lamp.
Photoelectrochemical Measurements. An electrochem-
ical workstation (CHI 660D) was used. All the measurements
were carried out using a three-electrode system, including a
working electrode, a reference electrode of saturated-KCl/
AgCl, and a counter electrode of platinum foil. For fabrication
of the working electrode, HTCC was first dispersed in ethanol
with 0.05% nafion and then coasted on a 1.0 × 1.0 cm−2 FTO
glass. Na2SO4 solution (0.1 mol L−1) was used as an
electrolyte.
Theoretical Calculations. All calculations used the Vienna
Ab initio Simulation Package (VASP).50 The projector-
augmented-wave method with the Perdew−Burke−Ernzerhof
GGA functional was used.51−53 We set the electronic
convergence limit at 1 × 10−4 eV.54 We took optimization of
atomic coordinates as converged so long as the Hellmann−
Feynman force below 2 × 10−2 eV Å−1. Moreover, the slab
https://doi.org/10.1021/acscatal.1c03690
ACS Catal. 2021, 11, 14480−14488
ACS Catalysis pubs.acs.org/acscatalysis
consisted of polyfuran and an O2 molecule was built with the
vacuum region at a height of about 10 Å.
■
ASSOCIATED CONTENT
* Supporting Information
sı
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acscatal.1c03690.
XRD patterns; appearences of raw materials and HTCC;
SEM and TEM images; FT-IR and 13C solid-state CP-
MAS NMR spectra; Raman spectrum; C 1s and O 1s
XPS spectra; calculation of apparent quantum efficiency;
photocatalytic performance; decomposition of H2O2;
cycling test; 13C solid-state CP-MAS NMR and FT-IR
spectra; Nyquist plots; 1H NMR spectra; C 1s XPS
spectra; atomic ratios; and calibration curve (PDF)
■ AUTHOR INFORMATION
Corresponding Authors
Zhuofeng Hu − School of Environmental Science and
Engineering, Guangdong Provincial Key Laboratory of
Environmental Pollution Control and Remediation
Technology, Sun Yat-sen University, Guangzhou 510275,
China; orcid.org/0000-0002-7879-6446;
Email: huzhf8@mail.sysu.edu.cn
Jimmy C. Yu − Department of Chemistry, The Chinese
University of Hong Kong, Hong Kong 999077, China;
orcid.org/0000-0001-9886-3725; Email: jimyu@
cuhk.edu.hk
Authors
Liangpang Xu − Department of Chemistry, The Chinese
University of Hong Kong, Hong Kong 999077, China
Yang Liu − Department of Chemistry, The Chinese University
of Hong Kong, Hong Kong 999077, China
Lejing Li − Department of Chemistry, The Chinese University
of Hong Kong, Hong Kong 999077, China
Complete contact information is available at:
https://pubs.acs.org/10.1021/acscatal.1c03690
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
This work is supported by the National Natural Science
Foundation of China (grant no. 51902357), the Guangdong
Basic and Applied Basic Research Foundation
(2019B1515120058), the Natural Science Foundation of
Guangdong Province, China (2019A1515012143), the Start-
up Funds for High-Level Talents of Sun Yat-sen University
(38000-18841209), and the Fundamental Research Funds for
the Central Universities (19lgpy153). The theoretical calcu-
lation is supported by National Supercomputer Center in
Guangzhou and National Supercomputing Center in Shenzhen
(Shenzhen Cloud Computing Center).
■
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