Applied Catalysis B: Environmental 285 (2021) 119817

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Applied Catalysis B: Environmental

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

In-situ photovoltage transients assisted catalytic study on H2O2

photoproduction over organic molecules modified carbon
nitride photocatalyst
Jingjing Cao , Qingyao Wu , Yajie Zhao , Kaiqiang Wei , Yi Li , Xiao Wang , Fan Liao , Hui Huang ,
Mingwang Shao *, Yang Liu *, Zhenhui Kang *
Institute of Functional Nano & Soft Materials (FUNSOM), Jiangsu Key Laboratory for Carbon Based Functional Materials & Devices, Soochow University, 199 Ren’ai
Road, Suzhou, 215123, Jiangsu, PR China

A R T I C L E I N F O A B S T R A C T

Keywords: Artificial photocatalysis holds great promise for the production of cheap and clean H2O2. Therefore, it is
H2O2 photoproduction emerging interest to develop metal-free photocatalysts due to their adjustable band gap, wide spectral response
Carbon nitride range and cheap. Here, we demonstrated the high efficient H2O2 photoproduction of 833 μmol g− 1 h− 1 (18.41
Double channels photocatalyst
μmol m-2 h− 1) with terephthalic acid modified carbon nitride (PTA0.6/CN) hybrids as catalysts, which was 13.6
In-situ photovoltage transients analysis
times (20.92 times) higher than that of pristine carbon nitride. The apparent quantum efficiency (QE) is up to
0.67 % (at λ =420 nm). Notably, with the assistance of in-situ transient photovoltage (TPV) analysis, the catalytic
mechanism, catalytic kinetics and optimized reaction conditions were determined in this alluring approach.
These in-situ TPV tests and analysis offered a thermodynamic-kinetic model, which showed the great capability to
directly extract the half reaction rate, electron transfer number and catalytic activities without carrying out
complex parallel, contrast and optimal experiments. This study not only provides a new model system for
exploring photoelectric interface, thermodynamic and kinetic properties of catalysts, but also opens up oppor­
tunities for the design of next-generation high-performance photocatalysts.

1. Introduction
Hydrogen peroxide (H2O2) is a potential energy carriers and eco-
friendly oxidant for one-compartment fuel cells, pollutant degrada­
tion, and chemical synthesis [1–6]. At present, the industrial production
of H2O2 is based on the anthraquinone method. However, this tradi­
tional process has some serious issues, such as the H2O2 purification,
high cost, severe safety issue, and slow regeneration of anthraquinone to
anthrahydroquinone [7–11]. Solar-driven photoproduction of H2O2 is
considered as an ideal alternative to the traditional anthraquinone
method. Then, the direct conversion of water and oxygen to H2O2
involving semiconductor photocatalyst is a tremendously promising
research topic. Thus, an efficient and inexpensive photocatalyst is
necessary for the production of H2O2. The previous reports have shown
that some photocatalysts are capable for oxidizing H2O to H2O2 (1.78
eV) by the photogenerated holes and reducing O2 to H2O2 (0.68 eV) by
the photogenerated electrons [12–17].
Up to date, much attention has been paid on carbon nitride (CN) for
the H2O2 production due to its appropriate band, physical stability and
low-cost [18–21]. However, the ineffective visible light absorption ca­
pacity and the serious charge recombination restrict the photocatalytic
activity of pristine carbon nitride. Carbon nitride based catalysts can be
optimized through element doping, compounding with semiconductors,
and modifying with small organic molecules [22–25]. For example,
g-C3N4 nanosheets are modified with various organic species, such as
perylene imides, biphenyl diimide, pyromellitic diimide (PDI), has
exhibited efficient two-channel photocatalytic ability for the production
of H2O2 under sunlight irradiation [26–29].
Herein, we reported that terephthalic acid modified carbon nitride
nanosheets (PTA0.6/CN) can promote H2O2 generation through a two-
channel pathway,including oxygen reduction reaction and water
oxidation, and thus significantly improve H2O2 generation. In order to
more accurately determine the advantages of photocatalysts, both the
reaction rate per unit mass and the rate on the surface area of the
catalyst were both proposed in this work. The H2O2 production rate of
PTA0.6/CN was up to 833 μmol g− 1 h-1 (18.41 μmol m-2 h− 1), which was

* Corresponding authors.
E-mail addresses: mwshao@suda.edu.cn (M. Shao), yangl@suda.edu.cn (Y. Liu), zhkang@suda.edu.cn (Z. Kang).

https://doi.org/10.1016/j.apcatb.2020.119817
Received 24 September 2020; Received in revised form 8 November 2020; Accepted 30 November 2020
Available online 22 December 2020
0926-3373/© 2020 Elsevier B.V. All rights reserved.
J. Cao et al.
Fig. 1. Morphology and structure of PTA0.6/CN. (a) TEM image of PTA0.6/CN. (b) HAADF-STEM image of PTA0.6/CN. The elemental mapping images for (c) C (d) N
and (e) O elements of PTA0.6/CN. High-resolution XPS spectra of PTA0.6/CN for (f) C 1s and (g) N 1s.
13.6 times (20.92 times) than that of pristine CN. The PTA0.6/CN hy­
brids effectively produced H2O2 with 0.07 % SCC (solar energy con­
version chemical energy) efficiency.
As an important part of catalytic design, photocatalytic activity is
urgently needed to carry out in-depth research on the kinetics and
mechanism corresponding to the experiments [30]. Specifically,
compared to the current measurements, in-situ transient photovoltage
(TPV) analysis provided an opportunity to study the catalytic mecha­
nism, catalytic kinetics and optimized reaction conditions in a conve­
nient strategy [31]. Based on the in-situ TPV tests, it could be found that
CN was the active component of the reaction while PTA accelerated the
transport of carriers, and thus improving the photocatalytic activity of
catalysts. A series of in-situ TPV tests further suggested that the oxygen
reduction reaction rate was faster than water oxidation reaction rate,
indicating the water oxidation reaction was the rate-determining step.
We also established a thermodynamic-kinetic model to efficiently
extract the half reaction rate, electron transfer number and catalytic
activities through the in-situ photovoltage transients, which simplified
complex parallel, contrast and optimization experiments. Our work
provided a new and promising research strategy for optimizing
photocatalysts.
2. Experimental section
2.1. Synthesis of pure carbon nitride (CN)
Added 10 g of urea into a porcelain crucible and sealed it with
2
Applied Catalysis B: Environmental 285 (2021) 119817
sealant. The heating rate was 10 ℃ min− 1 and it is calcined in a muffle at
550℃ for 3 h. The sample will be naturally cooled to normal room-
temperature status to acquire a yellow powder.
2.2. Synthesis of PTAx/CN catalysts
The organic acid modified CN was prepared by adding the different
weights of terephthalic acid (PTA) to 0.5 g as-prepared CN. Specifically,
different weights of terephthalic acid (0.1, 0.2, 0.4, 0.6, 0.8, 1.0 and 2.0
g) and 0.5 g CN were dispersed in 10 mL anhydrous ethanol and 50 mL
ultrapure water. The obtained mixtures were ultrasonically dispersed for
30 min. After that, the mixtures were transferred to 100 mL Teflon re­
actors for solvothermal treatment at 150 ℃ for 8 h. When naturally
cooled to room temperature, the obtained samples were washed with
anhydrous ethanol and ultrapure water, respectively. The as-prepared
samples were named PTAx/CN (x represents the weight ratio of added
terephthalic acid and CN, x = 0.1, 0.2, 0.4, 0.6, 0.8, 1.0 and 2.0).
3. Results and discussion
3.1. Characterization and photoelectrical properties
The as-prepared PTA0.6/CN displayed the hierarchical morphology
assembled with irregular 2D nanosheets was shown in Fig. 1a. And the
further observation of element distribution from Fig. 1b-1e suggested
that the C, N and O elements were distributed uniformly on the PTA0.6/
CN nanostructure. Besides, the SEM and TEM images of CN (Fig. S1a,b)
J. Cao et al.
Fig. 2. Band structure of PTA0.6/CN. (a) UV–vis absorption spectra of CN (black line), PTA (blue line) and PTA0.6/CN (red line). Insert: Determination of band gap of
PTA0.6/CN composition based on Kubelka–Munk function. (b) The VBXPS spectrum (xps valence band) of PTA0.6/CN as photocatalyst. (c) The CV curve and (d)
Energy diagram of PTA0.6/CN. (For interpretation of the references to colour in this figure legend, the reader is referred to the web version of this article).
also shown the hierarchical morphology similar to PTA0.6/CN. These
results confirmed that the embedding of PTA did not change the original
structure of CN. To further confirm the component structure, the XPS
spectra of PTA0.6/CN were acquired. The C 1s spectrum in Fig. 1f shows
five deconvoluted peaks at 293.0, 288.4, 287.5, 285.8 and 284.4 eV. The
peak at 288.4 eV is arranged as N–C＝N, and the weaker one at 284.4 eV
arranged to graphitic carbon. These two peaks usually can be found in
the XPS spectrum of CN (Fig. S1c). The peaks with binding energies of
293.0 and 285.8 eV can be identified to the characteristic peaks of PTA,
which correspond to − COOH and –C6H4 in PTA. It could be seen from
Fig. 1f, a new appeared peak at 287.5 eV compares to CN, which can be
ascribed to the O–– C–N bond, confirms the existence of amide bonds in
the PTA0.6/CN nanocomposites, indicating that CN and PTA have been
compounded through the amide bonds. As shown in Fig. 1g, N 1s
spectrum, the peak at 398.5 eV corresponds to C– – N–C while the peak
at 399.7 eV is assigned to the N–(C)3. In addition, the weaker peak with
high binding energy at 404.5 eV is attributed to the π excitations. Noting
that the new peaks at 400.6 eV in the N 1s spectrum of PTA0.6/CN can be
distinguished to N-C=O. Moreover, the N 1s peaks of CN was shown in
Fig. S1d. The weaker peak with a high binding energy at 401.1 eV is
attributed to quaternary N bonded to three carbon atoms in the aromatic
cycles. Above all illustrated the component structure of PTA0.6/CN
assembled by amide bonds, and PTA did not change the hierarchical
morphology of CN [32–35]. Fig. S2a described the nitrogen
adsorption-desorption isotherms and Fig. S2b showed the pore-size
distribution of samples,respectively. The specific surface area of
PTA0.6/CN (45.24 m2 g− 1) is smaller than that of CN (65.11 m2 g− 1),
contributing to the covered pores with addition of PTA, which is
consistent with the reduced pores around 35 nm.
The FT-IR spectra of the as-prepared CN, PTA and PTA0.6/CN were
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Applied Catalysis B: Environmental 285 (2021) 119817
shown in Fig. S3a. The spectrum of CN displays several characteristic
bands between 1200 and 1650 cm− 1, representing the stretching modes
of CN heterocycles. The typical breathing mode at 806.5 cm− 1 corre­
sponds to tri-s-triazine units of CN. In addition, the stretching vibration
mode of N–H at 3156 cm− 1 is observed in the FT-IR spectrum of CN.
The FTIR spectrum of PTA shows that the peak around 3500 cm− 1 is
corresponded to the stretching vibration of OH bond. The absorption
bands at 1545 and 1476 cm− 1 are assigned to typical aromatic carbon
heterocycles. The band at 1700 cm− 1 is arised from the stretching vi­
bration of C–
– O bond. For PTA0.6/CN, the characteristic bands of CN and
PTA are all observed in the FTIR pattern. The peaks around 3400 and
1600 cm− 1 are corresponded to the stretching vibrations of amide
bonds, however, the peaks of amide bonds can’t be observed indepen­
dently due to the overlap of bonds [36]. Fig. S3b displayed the XRD
patterns of CN, PTA and PTA0.6/CN, showing that the characteristic
peaks of PTA and CN also existed in the PTA0.6/CN. These results pro­
vided solid evidence for the successful synthesis of PTA0.6/CN composite
through amide bonds [37–41].
The optical properties of CN (black line), PTA (blue line) and PTA0.6/
CN (red line) were examined by UV–vis diffuse reflectance spectroscopy.
As shown in Fig. 2a, PTA0.6/CN showed better light absorption perfor­
mance than CN, which was favorable for harvesting sunlight energy and
generating carries pairs. According to the Kubelka-Munk function, the
bandgap energy of PTA0.6/CN was calculated to be 2.77 eV. From the
VBXPS spectrum presented in Fig. 2b, the valence band (VB) of PTA0.6/
CN was determined to be 2.16 eV, thus the conduction band (CB) of
PTA0.6/CN could be calcuated to be -0.61 eV. The cycle voltammetry
(CV) curve of PTA0.6/CN composite shown in Fig. 2c was used to
investigate the lowest unoccupied (LUMO) and the highest occupied
(HOMO) molecular orbital. The HOMO and LUMO levels were derived
J. Cao et al.
Fig. 3. Mechanism researches of PTA0.6/CN. (a) Koutecky–Levich plot of PTA0.6/CN derived from RDE measurements in O2-saturated ultrapure water with visible
light irradiation of λ > 420 nm (scan rate: 50 mV s− 1). (b) RRDE i-t curves of PTA0.6/CN under dark and light circumstance (λ > 420 nm) in N2-saturated Na2SO4
solution (0.1 M, scan rate: 50 mV s− 1). (c) Transient photovoltage (TPV) patterns of CN and PTA0.6/CN. (d) TPV patterns of PTA and PTA0.6/CN.
from the following equations:
( )
ox
EHOMO = − Eonset ox
− Eferrocene + 4.8 eV
( )
ELUMO = − red
Eonset red
− Eferrocene + 4.8 eV
where Eox red
onset , Eonset and Eferrocene were the onset of oxidation potential,
the onset of reduction potential and the redox potential of ferrocene,
respectively. The resulting HOMO/LUMO energy levels for PTA0.6/CN
composite were -6.30 eV and -3.88 eV, which was consistent with the
results from the VBXPS spectrum and UV–vis diffuse reflectance spec­
troscopy. The band structure of PTA0.6/CN, the theoretical redox po­
tentials (vs. RHE) of O2/H2O2 and H2O/H2O2 were shown in Fig. 2d. It
was proved that PTA0.6/CN with appropriate energy level positions
could realize the production of H2O2 by a two-channel pathway
theoretically.
The electron transfer number (n) of the O2 reduction reaction was
analyzed through the electrochemical rotating disk electrode (RDE)
method. Fig. S4 showed the LSV curves of PTA0.6/CN measured on RDE
in the O2-saturated ultrapure water solution at 0.05 V vs. RHE with
different rotating speeds. As shown in Fig. 3a, the Koutecky-Levich plots
derived from LSV curves, n value for the PTA0.6/CN is 1.99, indicating
the O2 reduction reaction was a two-electron transfer process [42]. The
n of water oxidation reaction was calculated by a collection experiment
with rotating ring disk electrode (RRDE), which was determined to be
1.78 according to the result shown in Fig. 3b, indicating that the water
oxidized process to generate H2O2 was a two-electron pathway [43]. The
⋅O−2 and ⋅OH, as intermediates in reducing oxygen and oxidazing water
to produce H2O2, were carried out under dark and light conditions by
the EPR experiments. As shown in Fig. S5a and b, the characteristic
Applied Catalysis B: Environmental 285 (2021) 119817
peaks of DMPO-⋅O2-and DMPO-⋅OH can be observed in PTA0.6/CN
sample under irradiation (λ > 420 nm). However, no EPR signal is
(1) observed in dark, indicating that the radicals are producted in the
presence of light. Fig. 3c and 3d showed the TPV diagrams of CN, PTA
(2) and PTA0.6/CN powders. It can be clearly observed from Fig. 3c that the
photovoltage intensity of PTA0.6/CN is higher than CN. Also, as shown in
Fig. 3d, the photogenic carriers of PTA0.6/CN are much higher than that
of pristine PTA. These results suggestted that PTA may accelerate car­
riers transmission and inhibit charges recombination, so as to be more
favorable for the H2O2 photoproducion.
3.2. Photocatalytic mechanism research based on in-situ TPV analysis
Fig. 4a showed the in-situ TPV diagrams of CN under different re­
action conditions to further demonstrate the role of PTA in the catalytic
reactions. Obviously, the photovoltage intensity of CN in 0.5 vol%
water/MeCN (v/v) solution is higher than that of N2-saturated MeCN
solution, which can be attributed to that the water was oxidized by
holes. When the O2-saturated MeCN was introduced to the test system,
the intensity of the photovoltage was much lower than N2-saturated
MeCN solution, which may be due to the electrons consumption during
the oxygen reduction reaction, leading to the decrease of the photo­
voltage (Fig. 4b). Similarly, in-situ TPV tests were carried out under
different gas atmosphere conditions for PTA (Fig. 4c and 4d). The weak
photovoltage signal of PTA proves that PTA only plays the role of
electron transfer, while CN is the active component for the catalyst.
Photoresponse curves of the samples with intermittently visible light in
Fig. S6a, indicating that the analysis of photocurrent is concordant with
the catalysts activity. The photocurrent of PTA0.6/CN with the highest
intensity ideally, corresponding to the most excellent photoresponse
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J. Cao et al. Applied Catalysis B: Environmental 285 (2021) 119817

Fig. 4. The in-situ TPV patterns of CN, PTA and PTA0.6/CN under N2-saturated MeCN solution versus N2-saturated 0.5 vol% water/MeCN (v/v) or O2 -saturated
MeCN solution for (a-b) CN (c-d) PTA (e-f) PTA0.6/CN with the integral diagram (resistance = 1 MΩ).

ability, meaning the most excellent carriers separation efficiency ability.
In the same way, EIS patterns were conducted to appraise the carriers
transmission capacity of the photocatalysts. Due to a smaller semicircle
shows a faster interfacial electron transfer rate in the EIS Nyquist plot, as
shown in Fig. S6b, PTA0.6/CN with the fastest electron transfer ability,
consequently clarify the most excellent photocatalytic activity. Fig. S7
gives the photoluminescence (PL) spectra of CN and PTA0.6/CN powder.
The PL intensity of PTA0.6/CN is obviously weaker than that in pristine
CN, indicating an enhanced charge extraction and suppressed carrier
recombination. All these can be explained that PTA modified carbon
nitride has better carriers mobility, which is favorable for photocatalytic
H2O2 generation.
3.3. The photocatalytic performance evaluation based on
thermodynamic-kinetic model and experiments
To optimize the reaction conditions, we offered a thermodynamic-
kinetic model based on in-situ TPV technology. Firstly, it was assumed
that the I (ionic strength) and pH of KOH solution would not affect
electrons and holes, and then the OER and ORR tests were carried out in
1 M KOH solution with a scanning rate of 10 mV s− 1 at different tem­
peratures, these results were displayed in Fig. S8 [44–48]. As shown in
Fig. S9, the optimal reaction conditions were obtained through simu­
lation calculation. However, I and pH affected the electrons and holes, so
we further performed OER and ORR tests in 0.1 M Na2SO4 solution. The
optimal reaction conditions were obtained with simulation combining
in-situ TPV analysis technique and electrochemical classical tests. As

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J. Cao et al. Applied Catalysis B: Environmental 285 (2021) 119817

shown in Fig. 4e and f, in oxygen atmosphere system, the oxygen

reduction reaction happened to consume electrons, leading to the peak
intensity sharply decreased compared with the nitrogen atmosphere. At
the same time, when the system under N2-saturated 0.5 vol% water/­
MeCN (v/v) solution, the peak intensity increased, that is the water
oxidation reaction has taken place in this system, and the intensity of the
oxygen reduction process decreases more obviously than that of the
water oxidation process for PTA0.6/CN, which demonstrated that the
rate of oxygen reduction is faster than the water oxidation reaction at
atmospheric pressure. By integrating the TPV curves (here, resistance =
1 MΩ), the amount of charges consumed during the reaction can be
calculated. (1) In the atmosphere of N2-saturated MeCN solution, the
charges generated by photoexcitation of the catalyst and finally
consumed by the whole circuit were defined as Q0. (2) In the case of
N2-saturated 0.5 vol% water/MeCN (v/v) solution, water as the reactant
consumed the charges, and the residual charges was consumed by the
entire circuit, were defined as Q1. (3) In the O2-saturated MeCN solution, Fig. 5. 3D map of the rate based on the thermodynamic-kinetic model for
the oxygen as the reactant consumes part of the charges, and the PTA0.6/CN in different partial oxygen pressure (Po2) and rotating speed (ω ＞0).
remaining charges were consumed by the whole circuit, which were
defined as Q2. Therefore, the absolute value of (Q1 – Q0) and (Q0 - Q2)
E2 /RT − αF(U2 − U20 ) /RT) E2 /RT − αF(U2 − U20 ) /RT)
were the number of charges required for the system to undergo water jf = n2 Fk20 e− e C2m = k20 ’e− e Pom2
oxidation reaction and oxygen reduction reaction. The ratio of (Q1 – Q0) 7 − 12981.76 − 0.5×96500×(0.66− 0.68)
1.136 × 10− = k20 ’×e8.314×298 ×e × 0.21
and (Q0 - Q2) were defined as the ratio of the rate of water oxidation
8.314×298

reaction to the oxygen reduction reaction. ’

k20 = 6.93 × 10 − 5

Q1 − Q0 5202.41 − 4653.94 (4)

λ= = = 0.31
Q0 − Q2 4653.94 − 2857.68 The rate of water oxidation (r1), rate of oxygen reduction (r2), and
Electrochemical measurement techniques were used to provide the rate of oxygen diffusion (r3) in solution were taken into account in the
activation energy of the reaction. According to the essential properties of mathematical modeling process. The separate parts of the
the formulas involved in the simulation calculation, it is not necessary to thermodynamic-kinetic model [5–7], were as follows (Here, U’1 is the
solve the activation energy and rate constants, but these constants are valence band of the catalyst, and U’2 is the conduction band of the
still solved that to verify the accuracy of the simulation process. As catalyst):
shown in Fig. S10a, OER curves of PTA0.6/CN were measured in 0.1 M E1 /RT αF(U1’ − U10 )/RT
Na2SO4 solution, with a temperature range changed from 298 K to 338 r1 = λ k10 ’e− e C1m
K. The corresponding Tafel curves (Fig. S10b) could be obtained from − 18419.55 0.5×96500×(2.16− 1.78)
= 0.31 × 5.16 × 104 × e8.314×298 × e 8.314×298 × 10− 7
= 1.55 × 10− 3
the LSV curves of OER [49–51]. Log j0 (exchange current density) could
(5)
be calculated from the Tafel curves, and the Arrhenius curves (Fig. S10c)
could be acquired by linear fitting between Log j0 and 1/T (according to ( ω )0.5
(
− αF U ’ − U20 )
Arrhenius equation Log j0 = Log (FKC) − ΔG0 /2.303RT, R = 8.314 J
E2 2
’ −
r2 = k20 e RT e RT Pom2 ×
mol− 1k− 1, ΔG0 is apparent activation energy, F = 96,500 C mol− 1), thus,
1600 (6)
the ΔG0 of water oxidation reaction value was calculated to be 18419.55 = 6.93 × 10 − 5
×e
− 12981.76
8.314×298 ×e
− 0.5×96500(− 0.61− 0.68)
8.314×298 × Po2 × (ω/1600) 0.5

J mol− 1 for PTA0.6/CN [52]. According to the jf =

nFke− E /RT eαF(U− U0 ) /RT) Cm (n is the electron transfer number, k is reaction r3 = jmax (60 rpm) × (ω/60)0.8 × Po2
(7)
rate constant, E = ΔG0 as reaction activation energy, m = 1, (jf, U) as the = 2.99 × 104 × Po2 × (ω/1600)0.5 (ω＞0)
any point data of tafel curve region, U10 = 1.78 V, U20 = 0.68 V) to
calculate the k value. The k10 ’ value was calculated from the following where jmax (60 rpm) = jmax (1600 rpm) × (60/1600)0.8 = 8.503 ×
formula [3]: 10− 5
× (60/1600) 0.8
= 6.15 × 10 A − 6

− E1 /RT (αF(U1 − U10 )/RT ) ’ − E1 /RT (αF(U1 − U10 )/RT ) m

jf = n1 Fk10 e e C1m = k10 e e C1 r3 =6.15×10− 6 ×(ω/60)0.8 ×Po2 (ω＞0)
r=min(r1 ,r2 ,r3 )
(3)
− 18419.55 0.5 ×96500 ×(1.79− 1.78)
6 7
3.705 × 10− = k10 ’ × e8.314×298 ×e 8.314×298 × 10− =min(1.55×10− 3 ,2.99×104 ×Po2 ×(ω/1600)0.5 ,6.15×10− 6 ×(ω/60)0.8 ×Po2 )
’
k10 = 5.16 × 104 (8)
According to the calculation based on the proposed thermodynamic-
Similarly, as shown in Fig. S10d, the ORR curves of PTA0.6/CN were
kinetic model, a three-dimensional (3D) diagram for the present pho­
also measured in 0.1 M Na2SO4 solution at different temperatures
tocatalytic reaction rate was obtained in Fig. 5, the corresponding rate
ranging from 283 K to 328 K with a sweep rate of 10 mV s− 1. Then the
on the surface area of the catalyst was given in Fig. S11, proving that the
corresponding ORR Tafel curves (Fig. S10e) could be obtained from the
reaction rate is proportional to of PO2 and ω (ω＞0). However, the
ORR curves. Arrhenius curves (Fig. S10f) were derived from Tafel curves
increment of the reaction rate will gradually stabilizes with the increase
to calculated the ΔG0 value of oxygen reduction reaction for photo­
of the the rotating speed, indicating that the influence of the O2 diffusion
catalyst PTA0.6/CN, which was 12981.76 J mol-1. Not surprisingly, ox­
rate will also gradually slow down on the reaction rate. In other words,
ygen reduction reaction activation energy was less than the activation
an optimal reaction rate can be obtained by altering the rotational speed
energy of water oxidation reaction, that also proved temperature
and partial pressure of O2. Then, the minimum reaction rate (or optimal
increasing was more conducive to oxygen reduction reaction. The k20 ’
reaction rate) could be determined by a simple simulation calculation
value was calculated to be 6.93 × 10-5 from the formula [4]:
based on formula [8]. Specifically, the theoretical minimum rate of
PTA0.6/CN was 954.71 μmol g− 1 h− 1 (21.10 μmol m-2 h− 1) through the

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J. Cao et al. Applied Catalysis B: Environmental 285 (2021) 119817

Fig. 6. Theoretical and experimental photoproduction of H2O2. The relationship between the H2O2 production rate and the (a) rotation speed, ω and (b) Po2. (c)
Time-dependent change in H2O2 evolution during photoreaction with PTA0.6/CN, PTA and CN as catalysts respectively. (d) The cyclic stability of PTA0.6/CN as
catalyst for H2O2 evolution. (e) Comparisons of H2O2 evolution in 12 h over PTA0.6/CN with diff ;erent PTA contents. (f) The quantum efficiency of PTA0.6/CN at
different wavelengths. (g) Comparison of H2O2 evolutions with PTA0.6/CN as catalyst under different gas atmosphere conditions (h) and different scavenger con­
ditions (MeOH + O2 and AgNO3 + N2 for h+ and e− , respectively). Photocatalytic condition: 10 mg catalyst was added to 15 mL pure water (420 nm ≤ λ ≤ 700 nm)
and normal pressure.

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J. Cao et al. Applied Catalysis B: Environmental 285 (2021) 119817

erent PTA content was displayed in Fig. 6e, indicating that the catalyst
had excellent H2O2 production activity (833 μmol g− 1 h− 1) (18.41 μmol
m-2 h− 1) with 0.6 wt% (PTA:CN), while the content of PTA over 0.6 wt%,
the H2O2 production was inhibited due to excessive PTA could override
the reactive sites. According to the absorbed photo flux and the rate of
photocatalytic H2O2 production, the quantum yield was calculated to be
0.67 % at 420 nm wavelength in Fig. 6f. Fig. 6g provided the amount of
H2O2 production by PTA0.6/CN in different gas contions. The production
of H2O2 decreases in N2-saturated water, showing that water can
oxidized by catalyst to H2O2. In the case of the O2-saturation of water,
the content of H2O2 increases, which testifying that the production of
H2O2 is consistent to the content of O2. Moreover, it can be reagared as
these two processes are mutually sacrificing, thus effectively increasing
the generation of H2O2 without any sacrificial agent.
Next, the rate of the half reactions was further studied. As shown in
Fig. 6h, the O2-saturated methanol solution (hole sacrificial agent) was
added in the system to explore the oxygen reduction reaction rate, which
was 1307.4 μmol g− 1 h-1 (28.90 μmol m-2 h− 1). Meanwhile, the N2-
saturated AgNO3 solution (electron sacrifice agent) could be used to
estimate the rate of water oxidation reaction, which was 309.2 μmol g− 1
h-1 (6.83 μmol m-2 h− 1). Moreever, the ratio rate of the experimental half
reactions is 0.35, which is similar to the in-situ TPV analysis result of
0.31. As shown in Fig. S16, the reaction mechanism schematic of
PTA0.6/CN as photocatalyst was proposed with visible-light-driven
water splitting and oxygen (oxygen in the air) reduction through the
two channel reaction. As displayed in Fig. 7, the catalytic data and
analysis result from in-situ TPV test were integrated into the flowchart of
new research strategy based on the proposed thermodynamic-kinetic
model. After the fabrication of the PTAx/CN through a simple hydro­
Fig. 7. Flowchart of the research results by a thermodynamic-kinetic model
with corresponding in-situ TPV test data.
thermal process, the basic structure characterizations of these catalysts
were performed through the TEM, XPS, FTIR, XRD and UV–vis-DRS, etc.
Then, the tests based on the in-situ photovoltage transients showed that
thermodynamic-kinetic model, and the simulation condition was under
PTA0.6/CN possessed the most excellent photocatalytic activity, CN was
normal pressure at a rotating speed of 150 rpm, which is the same as the
the active component of catalyst, and PTA played the role of accelerating
actual experimental conditions
carriers transfer. The rate ratio of the water oxidation reaction and the
Next, the theoretical calculation rate and the catalytic experiment
oxygen reduction reaction derived from the thermodynamic-kinetic
rate were fitted and displayed in Fig. 6a and 6b, simultaneously, the
mode was 0.31, showing that the water oxidation reaction was the
corresponding rate on the surface area of PTA0.6/CN was also given in
rate-determining step of the reaction. These in-situ TPV analysis can
Fig. S12. With increasing ω and PO2, the yield of H2O2 increased to a
extract the half reaction rate, electron transfer number and catalytic
maximum value around the certain range, in which, the experimental
activities without carrying out complex parallel, contrast and optimal
H2O2 production rate was slightly lower than that of the theoretical
experiments. Based on the above TPV measurements and analysis, once
calculation. It could be attributed to H2O2 degradation was not taken
a satisfactory photocatalyst is obtained or the optimal reaction condi­
into account in the theoretical calculations. The time-dependent change
tions are determined, just simple catalytic experiments are needed to
for H2O2 generation rate on the surface area with different photo­
verify the catalytic activity. Compared with the traditional photocatalyst
catalysts were given in Fig. S13. As displsyed in Fig. 6c, the amount of
research route, this new process not only avoids the complicated and
H2O2 generated on PTA0.6/CN was 833 μmol g− 1 h− 1 (18.41 μmol m-2
large amount of repeated labor, but also reduces complex and time-
h− 1) under visible-light irradiation, which was 13.6 times (20.92 times)
consuming comparative experiments and parallel experiments,
higher than the pristine CN (61.25 μmol g− 1 h− 1) (0.88 μmol m-2 h− 1, the
providing a promising vision for the optimization of the photocatalysts.
detailed experimental conditions can be seen in the photocatalytic ac­
tivity tests of the experimental section). These results clarify that the
4. Conclusion
hybridization of PTA with CN really enhances the photoproduction rates
of H2O2. Fig. S14a showed the time-dependent change in H2O2 gener­
We have developed a CN based metal-free photocatalyst (PTA0.6/
ation with PTA0.6/CN as catalyst. Continuous H2O2 generation rate with
CN), which produces H2O2 via the synergistic effect of water oxidation
no significant decline was observed within 12 h. Fig. S14b demonstrated
and oxygen reduction with dual-electron process. This PTA0.6/CN pho­
the dependence of H2O2 concentration on catalyst dosage for PTA0.6/CN
tocatalyst exhibits high H2O2 production activity (833 μmol g− 1 h− 1)
catalyst, 10 mg catalyst with 15 mL H2O was the best choice. Fig. 6d
(18.41 μmol m-2 h− 1) under visible light (normal pressure and temper­
indicated that the photocatalytic activity of PTA0.6/CN decreased
ature) without any sacrificial agent, which is 13.6 times (20.92 times)
slightly after four cycles, suggesting that PTA0.6/CN has good stability
than that of pristine CN. Significantly, we have established a
and anti-hydrogen peroxide corrosion ability. The stability of PTA0.6/CN
thermodynamic-kinetic model based on in-situ TPV tests and analysis,
was also verified by XPS high-resolution N 1s spectra after four cycles. In
which offers new research Fig. 7. Flowchart of the research results by a
Fig. S15a, a slight decrease for the content of the amide bond at 400.6 eV
thermodynamic-kinetic model with corresponding in-situ TPV test data.
can be observed, which can be attributed to the damaged amide bond
strategy to optimize catalysts without complex parallel, contrast and
due to the generated H2O2. No obvious decline can be observed in the
optimal experiments. The proposed in-situ TPV analysis proved that the
FT-IR spectra of PTA0.6/CN after photocatalytic H2O2 production reac­
activity of PTA0.6/CN is much higher than that of CN, and the active site
tion (Fig. S15b). It also proves the PTA0.6/CN exhibits good stability.
is located on CN. PTA accelerates the carriers migration, and water
The photocatalytic performance measurement of PTA/CN with diff ;
oxidation rate is the rate-determining step in this reaction system. The

8
J. Cao et al.
related experiments experiments were carried out to further verify the
catalytic results from in-situ TPV analysis. This work provides a prom­
ising approach for developing CN based photocatalysts, and also offers a
new, facile and practical method to explore the catalytic reaction,
especially for the revealing of catalytic mechanism, catalytic kinetics
and optimal reaction conditions.
CRediT authorship contribution statement
Jingjing Cao: Data curation, Visualization. Qingyao Wu: Formal
analysis. Yajie Zhao: Investigation. Kaiqiang Wei: Software. Yi Li:
Software. Xiao Wang: Investigation. Fan Liao: Investigation. Hui
Huang: Project administration, Writing - original draft, Writing - review
& editing, Supervision. Mingwang Shao: Writing - review & editing,
Supervision. Yang Liu: Resources, Writing - review & editing, Super­
vision. Zhenhui Kang: Conceptualization, Funding acquisition, Writing
- review & editing, Supervision.
Declaration of Competing Interest
The authors report no declarations of interest.
Acknowledgements
This work is supported by National MCF Energy R&D Program
(2018YFE0306105), National Key Research and Development Project of
China (2020YFA0406104), Innovative Research Group Project of the
National Natural Science Foundation of China (51821002), National
Natural Science Foundation of China (51725204, 21771132, 51972216,
52041202), Natural Science Foundation of Jiangsu Province
(BK20190041), Collaborative Innovation Center of Suzhou Nano Sci­
ence & Technology, the Priority Academic Program Development of
Jiangsu Higher Education Institutions (PAPD), and the 111 Project.
Appendix A. Supplementary data
Supplementary material related to this article can be found, in the
online version, at doi:https://doi.org/10.1016/j.apcatb.2020.119817.
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