Surfaces and Interfaces 23 (2021) 101006

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Surfaces and Interfaces

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Thermal coupled photocatalysis to enhance CO2 reduction activities on Ag

loaded g-C3N4 catalysts
Xiaojing Han a, b, Mengwei Li a, Yongning Ma c, *, Yingxuan Li a, *, Hongrui Ma a, Chuanyi Wang a
a
School of Environmental Science and Engineering, Shaanxi University of Science & Technology, Xi’an 710021, China
b
Department of Chemistry and Chemical Engineering, Lvliang University, Lvliang 033000, China
c
College of Chemistry and Chemical Engineering, Shaanxi University of Science & Technology, Xi’an 710021, China

A B S T R A C T

The contribution of heat input in traditional photocatalytic processes is rarely studied. Herein, a series of the Ag nanoparticles deposited g-C3N4 (Ag-CN) was
prepared by photochemical method and used for photocatalytic CO2 reduction with the assistance of thermal energy. The photocatalytic properties were investigated
under light-emitting diode light (420 nm, on the order of solar intensity) irradiation at temperatures up to 200 ºC, confirming that the CO evolution rate was strongly
dependent on the reaction temperature. The CO production reached to a maximum value of 179.6 μmol•g− 1•h− 1 (about 4.2 times higher than that of CN) on the 20%
Ag loaded CN at 190 ◦ C although negligible photocatalytic activity was observed under light illumination at ambient temperature. The enhancement of the tem­
perature could not only improve the transfer rate and energy of the excited electrons, but also increase the population of the activated molecules, which might
contribute to the enhancement on the CO production. Our finding provides an alternative way for integrating infrared light (accounting for ~50% of the solar light)
in photocatalysis considering the thermal effect of the infrared light.

1. Introduction their excellent conductivity and/or light absorption properties [20–22].

Furthermore, it is well known that noble metals have been widely
Fossil fuel combustion causes a significant increase in carbon dioxide adopted for CO2 reduction by thermal catalysis, which was usually
(CO2) emissions, which has triggered a series of environmental issues carried out at the temperatures between 550 and 750 ºC [23]. Therefore,
such as the greenhouse effect [1–3]. Therefore, CO2 conversion is highly the noble metal composited photocatalysts can be potentially used for
attractive because of the simultaneous carbon emission reduction and CO2 reduction by coupling thermal and light energies.
high-value chemical production [4,5]. For achieving this goal, Compared with thermal catalysis, photocatalysis has an advantage
numerous technologies based on photocatalysis [6,7], thermocatalysis that can be carried out at room temperature. However, the efficiency for
[8] and electrocatalysis [9], or the synergistic effect of the above method solar CO2 conversion over semiconductor photocatalysts can be poten­
[10,11] have been developed. Among these processes, photocatalysis tially affected by the inevitable temperature rise under solar irradiation
based on semiconductors was regarded as a feasible approach for con­ (mainly from infrared light) [24]. Therefore, the synergistic photo­
verting CO2 because clean solar energy can be used as the driving force. chemical and thermal effect on the catalytic activities of semiconductor
At present, different photocatalysts, such as graphene oxide [12], photocatalysts is important in practical applications. To our knowledge,
graphite carbon nitride [13], single atom catalysts [14], metal sulfides this effect was rarely studied in previous reports [25]. In the present
[15], organic perovskite nanocrystals [16,17], et al., were employed for study, the Ag nanoparticles were deposited on the surface of CN by
converting CO2. Among these catalysts, graphite carbon nitride (g-C3N4, in-situ photoreduction method and the thermal coupled photocatalytic
simplified to CN), as a metal-free photocatalyst, has received extensive CO2-to-CO conversion on the obtained samples was investigated, indi­
attentions for CO2 reduction because of the unique energy band struc­ cating that the catalytic activities were highly dependent on the reaction
ture, good thermal and chemical stability [18]. However, the practical temperatures. Maximum photocatalytic CO2 conversion rate was ach­
application of the bare CN photocatalyst is still hindered by the high ieved at 190 ◦ C, which was 4.2 times higher than that of pristine CN.
recombination rate of photogenerated e− /h+ pairs [19]. As an effective This study will open an approach for developing novel high-temperature
approach, deposition of noble metals, such as Pt, Au and Ru, was photocatalysts for CO2 reduction.
generally used to improve the photocatalytic performance of CN due to

* Corresponding authors.
E-mail addresses: [email protected] (Y. Ma), [email protected] (Y. Li).

https://doi.org/10.1016/j.surfin.2021.101006
Received 8 January 2021; Received in revised form 31 January 2021; Accepted 3 February 2021
Available online 7 February 2021
2468-0230/© 2021 Elsevier B.V. All rights reserved.
X. Han et al. Surfaces and Interfaces 23 (2021) 101006

Fig. 1. (a) XRD patterns and (b) FTIR spectra of CN and Ag-CN.

Fig. 2. TEM images of (a) CN and (b) 20Ag-CN. The two illustrations in (b) are
the HRTEM image of 20Ag-CN (the lower part) and the size distribution of the
2. Experimental Ag nanoparticles (the upper part), respectively.

2.1. Synthesis of CN and Ag-CN

2.2. Characterization
All regents were analytical grade without further purification and
used as raw materials directly. The CN powder was obtained via thermal
The X-ray diffraction (XRD) patterns were performed on D8 Advance
treatment of urea to 550◦ C for 3 h in tube furnace as reported previously
Bruker diffractometer with Cu Kα radiation. The measurements were
[19].
conducted in a 2θ range of 10-70◦ with a scan rate of 0.02◦ steps•s− 1.
The Ag-CN (Ag nanoparticles deposited g-C3N4) composite catalysts
The transmission electron microscopy (TEM) images were obtained
were synthesized via in-situ photoreduction method using the obtained
using a FEI Tecnai G2 20 at 200kV. The percentage of silver was
CN as the precursor. Typically, 0.2 g of CN was dispersed in 60 mL of
measured by inductively coupled plasma-optical emission spectroscopy
deionized water by sonication for 10 min. Then, a certain quantity of
(ICP-OES, Aglient 5110). X-ray photoelectron spectroscopy (XPS) mea­
AgNO3 solution (0.5 g•L− 1) was added in the above solution and the
surements were carried out on a Kratos AXIS UL trabld spectrometer
mixture was irradiated by 420 nm light-emitting diode (LED) light for
equipped with monochromatic Al Kα radiation as the exciting source,
30 min with constant stirring. The resulting product was separated by
using C1s peak (284.6 eV) as the calibration reference. The ultraviolet-
centrifugation and washed with ethanol and deionized water in turns,
visible (UV-Vis) absorption spectra were measured on a Shimadu UV-
and dried overnight in a vacuum oven at 60◦ C. The nominal mass per­
2600 spectrometer with BaSO4 as the reference. The Fourier transform
centage ratios of Ag-to-CN in Ag-CN samples were 5%, 10%, 20%, and
infrared (FTIR) spectra were collected on a Bruker VERTEX 70v FTIR
30%, which were denoted as 5Ag-CN, 10Ag-CN, 20Ag-CN and 30Ag-CN,
spectrophotometer. The Hitachi F-4500 fluorescence spectrophotometer
respectively.
was employed to record the photoluminescence (PL) spectra of the

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X. Han et al. Surfaces and Interfaces 23 (2021) 101006

samples. Photoelectrochemical measurements were carried out on an chromatography-mass spectrometry (GC-MS).

electrochemical workstation (CHI660E, Chenhua, Shanghai) using a The apparent quantum efficiency (AQE) for CO evolution was
standard three-electrode system with Ag-CN as working electrode, measured under the same reaction conditions by using LED lamps with
platinum wire as the counter electrode, and saturated Ag/AgCl electrode different wavelengths (365, 420, 450, 520 and 590 nm). The light in­
as reference electrode. The transient photocurrent intensity was evalu­ tensity was detected by a PL-MW200 photoradiometer (Perfect Light,
ated at the bias potential of 0.5 V in Na2SO4 aqueous solution (0.1 mol Beijing, China). The AQE was calculated by the following formula:
•L− 1) under a 420 nm LED light irradiation.
2 × number of evolved CO molecules
AQE = × 100%
the number of incident photos
2.3. Gas-phase CO2 reduction test
3. Results and discussion
The CO2 reduction reaction was performed in a 300 mL closed system
equipped with a quartz window and a temperature control device. A 420 Ag-CN photocatalysts were synthesized via photoreduction method
nm LED light was used as the light source. The catalyst (30 mg) was using the as-prepared CN as the precursor. XRD was used to identify the
evenly distributed on the glass which was put under the quartz window phase structure of as-prepared samples. As shown in Fig. 1, XRD pattern
of the reactor. Prior to the irradiation, the reactor was sealed and blown of CN displays two distinct diffraction peaks at 13.1o and 27.3o, which
with pure Ar for at least 15 min to completely eliminate the air. Then, correspond to the (100) and (002) planes of CN, respectively [26]. For
0.1 mL deionized water and 50 mL CO2 were added into the reactor. the Ag-CN composites, the peaks belonging to the CN can also be
After a certain reaction time, the gas products were analyzed by an observed, which proves that the phase structure of CN was not changed
Agilent 7890B gas chromatograph with a TCD detector. The products in by the deposited Ag nanoparticles. Meanwhile, a new peak located at
isotopic experiments were determined using a HP 5973 gas about 38o was detected in the XRD patterns of Ag-CN composites

Fig. 3. Fitted XPS spectra of (a) C 1s spectrum, (b) N 1s spectrum, (c) O 1s spectrum and (d) Ag 3d spectrum of 20Ag-CN.

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X. Han et al. Surfaces and Interfaces 23 (2021) 101006

Fig. 5. (a) CO evolution rates using 20Ag-CN as photocatalyst at different

temperatures; (b) Stability of 20Ag-CN during five photocatalytic cycles for CO2
reduction at 190 ◦ C.

Fig. 4. (a) CO evolution rates on the CN samples loaded with different amounts
of Ag at 190 ◦ C; (b) TEM image of 30Ag-CN. The inset in (b) is the size dis­
tribution of the Ag nanoparticles. highest catalytic activity was achieved on it. As shown in Fig. 2a, the
TEM image of CN displays that the CN is layered structure with irregular
shape, which is similarly to the reported morphology of CN [30]. The
TEM image of 20Ag-CN (Fig. 2b) indicates that the Ag nanoparticles are
(Fig. 1a), which can be ascribed to the (111) plane of Ag nanoparticles
uniformly deposited on the surface of CN. The size distribution histo­
[21,27]. Based on the above analysis, it can be inferred that the Ag
gram of the Ag nanoparticles (inset of Fig. 2b in the upper part) de­
nanoparticles were successfully deposited on the surface of CN.
termines that the diameters of the Ag nanoparticles are mainly in the
Fig. 1b shows the FTIR spectra of the as-prepared CN and Ag-CN
range of 4-6 nm. Furthermore, the high-resolution TEM (HRTEM) image
composites. For pristine CN, the peaks between 1200 cm− 1 and 1600
of a single Ag nanoparticle on 20Ag-CN is also shown in the inset of
cm− 1 can be attributed to the C-N stretching vibration mode [22,27] and
Fig. 2b (lower part). The lattice fringe with d spacing of 0.236 that
the peak around 1632 cm− 1 is the characteristic stretching vibration
corresponds to the (111) plane of Ag is observed [19], which is consis­
mode of C-N heterocycle [28]. The absorption peaks at 3000-3400 cm− 1
tent with the XRD analysis in Fig. 1a. The Ag content in 20Ag-CN
can be assigned to the -NH and -OH stretching vibration modes, which
determined to be 14.6 wt% by ICP.
may be due to the residual amino group and adsorbed water, respec­
The chemical states of 20Ag-CN were investigated by XPS spectra
tively [29]. As shown in Fig. 1b, all the typical peaks corresponding to
and the results are shown in Fig. 3. As shown in Fig. 3a, the high-
the pristine CN can be found in the Ag-CN composites, which further
resolution C1s spectrum could be fitted into two peaks at 284.6 and
confirms that the main structure of CN was still maintained after the
288.0 eV, which can be assigned to the C-N linkages and the sp2 C-C
deposition of Ag nanoparticles.
bonds, respectively [31]. The N1s spectrum (Fig. 3b) can be deconvo­
Next, the distribution state and microstructure of the loaded Ag were
luted into four peaks at 398.5, 399.7, 400.9 and 404.3 eV, which
investigated by TEM. The typical TEM observation and the following
correspond to the sp2-hybridized nitrogen (C-N=C), three-coordinated
XPS analysis were performed on the 20Ag-CN sample because the
nitrogen atoms (N-(C)3), N-H bonding, and π-excitation in the CN,

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X. Han et al. Surfaces and Interfaces 23 (2021) 101006

respectively [22,32]. In the O 1s spectrum (Fig. 3c), the peak at 532.4 eV

can be attributed to the presence of -OH that chemisorbed on the surface
of CN [33]. As shown in Fig. 3d, two peaks with binding energies at
368.3 and 374.5 eV were observed due to the presence of metallic Ag
species [19,34], which is in agreement with the results of XRD analysis
(Fig. 1a) and HRTEM observation (Fig. 2b).
The photochemical-thermal CO2 reduction activities of the samples
were evaluated in stainless steel reactor equipped with a quartz window
and a device for controlling the reaction temperature. Firstly, the effect
of the Ag contents on the photochemical-thermal CO2 reduction per­
formance of CN was investigated at 190 ◦ C. As shown in Fig. 4a, without
any modification, blank CN shows a very low CO evolution rate of 34.72
μmol•g− 1•h− 1. After loading of the Ag nanoparticles, the Ag-CN samples
show significantly enhanced activities for CO2 reduction, which in­
creases to a maximum value of 179.6 μmol•g− 1•h− 1 for 20Ag-CN. It is
worth noting that the activity of 20Ag-CN is 4.2 times higher than that of
CN. However, further increasing the amount of the deposited Ag on Ag-
CN to 30% leads to a decreased CO production (162.6 μmol•g− 1•h− 1),
which might be caused by the increased size of the Ag nanoparticles as
certified by the TEM image in Fig. 4b. From the inset of Fig. 4b, the size
distribution of the Ag nanoparticles on the 30Ag-CN sample is mainly in
the range of 10-20 nm, which is much higher than that of 20Ag-CN (4-6
nm).
Fig. 5a shows the reaction-temperature dependent CO production
activity on 20Ag-CN under 420 nm LED light irradiation with an in­
tensity of 34.5 mW•cm− 2. As shown in Fig 5a, CO production activities
with near 100% selectivity were obtained. Interestingly, with the reac­
tion temperature increasing from 90 ◦ C to 190 ◦ C, the CO evolution rates
increased from 14.63 μmol•g− 1•h− 1 to 179.6 μmol•g− 1•h− 1. This result
indicates that the elevated temperature is benefit for the reduction of
CO2 to CO. The reasons for the enhanced performance of Ag deposited
samples will be discussed in the following. When the reaction temper­
ature was further increased to 200 ◦ C, the CO evolution rate is reduced
to 116.4 μmol•g− 1•h− 1, which might be caused by the reduced
adsorption capacity of the reactants on 20Ag-CN with the increased
temperature.
For comparison, the photocatalytic activities of the recently reported
g-C3N4 based samples for CO2 reduction are listed in Table 1. In com­
parison with most previous reports, the present 20Ag-CN shows a higher
catalytic activity for CO2-to-CO conversion, which confirms that the

Table 1 Fig. 6. (a) XRD pattern and (b) fitted XPS curve of Ag 3d spectrum of 20Ag-CN
Comparison with other similar photocatalysts on the photoreduction of CO2 after photocatalytic reaction.
Catalyst Product CO Yied Experimental Ref.
(μmol•g− 1•h− 1) conditions

BIF-20@g- CO and 1.7 Xe lamp (Visible [35] thermal coupled photocatalysis is an effective approach for enhancing
C3N4 CH4 light) CO2 reduction properties of CN.
Pt@45CeO2/ CO and 4.69 UV light [36] In order to study the stability of catalyst, photocatalytic reduction of
3DCN CH4
− 2 CO2 on 20Ag-CN through five test cycles was carried out. As shown in
CN-PA12 CO and 5.42 (100 mW•cm ) [37]
CH4 Fig. 5b, the as-prepared 20Ag-CN sample exhibits stable CO evolution
LaPO4/g- CO 14.4 300W Xe lamp [13] within at least 5 cycles (30 h reaction), indicating that the stability of the
C3N4 prepared catalyst is good. Furthermore, in order to further prove the
NiO/g-C3N4 CO 4.17 300W Xe lamp [38] stability of 20Ag-CN, the XRD pattern and XPS spectrum of 20Ag-CN
g-C3N4@CeO2 CO, CH4 16.8 300W Xe lamp [39]
and (λ>420 nm)
after photocatalytic reaction was measured and the results are shown
CH3OH in Fig. 6. Compared with the results in Figs. 1a and 3d, no obvious
CsPbX3/g- CO 28.5 Visible-light [40] changes are observed on the used 20Ag-CN, confirming the high dura­
C3N4 (λ>420 nm) bility of the photocatalyst.
K-CN-7 CO 8.7 Visible-light [41]
To identify the effects of the reaction conditions for CO2 reduction,
(λ>420 nm)
g-C3N4/ CO 45.6 300W Xe lamp [42] the control experiments in the absence of light or heat were carried out
Bi4O5I2 (λ>400 nm) by monitoring the production of CO. As shown in Fig. 7a, no CO evo­
Cu/C3N4-6 CO 9.9 350W Xe lamp [43] lution was detected, indicating that CO2-to-CO conversion was initiated
3D g-C3N4/C- CO and 32.7 500W Xe lamp (110 [44] by the synergetic effect of light and thermal energies. Furthermore,
NS CH4 KPa)
nearly no CO was observed without adding CO2 in the reaction system
20Ag-CN CO 179.6 420 nm LED (34.5 This
mW•cm− 2,190 ◦ C) work (Fig. 7a), determining that the CO production was due to the reduction

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X. Han et al. Surfaces and Interfaces 23 (2021) 101006

of CO2 on 20Ag-CN. To further confirm the produced CO is from CO2, influenced by the Ag deposition.
isotopic labeling experiment with 13CO2 as reactant was performed on To further confirm the effect of SPR absorption of Ag nanoparticles
20Ag-CN. As shown in Fig. 7b, the peak at m/z = 29 that is relative to on the catalytic CO2 reduction reaction, the wavelength-dependent
13
CO was detected, which directly demonstrates that the produced CO apparent quantum efficiency (AQE) for CO production on 20Ag-CN
was indeed from CO2 reduction rather than from other carbon con­ was examined. As shown in Fig. 8b, the AQE value clearly deviate
taining compounds. In this isotopic labeling experiment, H18
2 O was used from the absorption pattern at 520 nm. In contrast, the AQE value of
as proton source, the peak at m/z = 36 (18O2) can be observed in Fig. 7b, 20Ag-CN matches well with the absorption spectrum of CN rather than
confirming that the H2O was oxidized into O2 by 20Ag-CN in the that of 20Ag-CN. These observations demonstrate that the extended
photochemical-thermal reaction conditions. absorption of 20Ag-CN show inactivity toward CO2 reduction at 520 nm
To obtain an insight into the improved CO2 reduction efficiency of although a strong SPR absorption was achieved by Ag loading. There­
the Ag-CN nanocomposites, optical characterizations were carried out. fore, it is reasonable to speculate that Ag nanoparticles mainly played as
The UV-Vis absorption spectra were used to study the effect of Ag co-catalyst for enhancing the efficiency of the photogenerated charge
deposition on the absorption properties of the as-prepared samples. As separation.
shown in Fig. 8a, the absorption edge for the pristine CN is located at To compare the separation rates of the photoinduced charge carriers
about 460 nm (2.70 eV), which is in agreement with the previous reports of the obtained samples, the transient photocurrent intensity measures
[19,29]. In contrast, the Ag-CN nanocomposites show an absorption in were carried out. As shown in Fig. 9a, the 20Ag-CN catalyst shows the
the range of 450-600 nm, which is a characteristic of the surface plas­ highest photocurrent in the investigated samples. This means that the
mon resonance (SPR) effect of Ag nanoparticles [38]. In addition, the highest charge separation efficiency was achieved on 20Ag-CN, which is
absorption intensity in the range between 450 and 800 nm is gradually coincided well with the photocatalytic activities of the samples.
enhanced with the increasing content of Ag in the samples, indicating Furthermore, the transport efficiency of charge carriers in dark was
that the light absorption properties of the samples were greatly analyzed by electrochemical impedance spectroscopy (EIS). As shown in
Fig. 9b, a smallest radius of EIS curve is found for 20Ag-CN, indicating
that the 20Ag-CN is the best catalyst for the transport of charge carriers
[42,45]. These electrochemical tests revealed that 20Ag-CN is the most
suitable catalyst for charge carrier generation and transport, which is

Fig. 7. (a) Symbolical description of CO evolution under different experimental Fig. 8. (a) UV-Vis spectra of the prepared Ag-CN samples; (b) Wavelength-
conditions; (b) Mass spectra of the products using 13CO2 and H18
2 O as reactants. dependent AQEs of CO production on 20Ag-CN catalyst.

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X. Han et al. Surfaces and Interfaces 23 (2021) 101006

Fig. 10. PL spectra of CN and Ag-CN samples.

CO production on 20Ag-CN, which has rarely been studied in previous

literatures [19]. With temperature raising, two positive effect can be
achieved on the metal catalysts. Firstly, the more adsorbed molecules on
the surface of Ag nanoparticles would be activated, which means the
excited electrons will be reacted with the active CO2 more easily [46].
Secondly, the excited electrons will transport faster and obtain more
energy with the enhancement of the temperature [46]. As a result of the
two positive effects, the CO production activity was increased with the
increasing of the reaction temperature in the range of 90-190 ◦ C. Ac­
cording to the above studies, a possible mechanism for
thermo-photocatalytic CO2 reduction on 20Ag-CN is depicted in Fig. 11.
Under 420 nm LED light irradiation, the photoinduced electrons in the
valance band (VB) of g-C3N4 are excited into the conduction band (CB),
and then migrate to the surface of Ag nanoparticles (Step 1). With the
help of thermal energy, the energy levels for the photoinduced electrons
Fig. 9. (a) Transient photocurrent intensity and (b) EIS spectra of CN and Ag- on Ag nanoparticles can be enhanced (Step 2), which further facilitates
CN samples. the photocatalytic CO2-to-CO reduction [47]. Meanwhile, the holes in
the CB of g-C3N4 migrate to the surface of the catalyst for H2O oxidation.

consistent with the CO2 reduction performances of the catalysts. 4. Conclusions

Additionally, in order to explore the separation properties of the
photogenerated electron-hole pairs, PL measurements were carried out In summary, novel high-temperature Ag-CN photocatalysts were
on the catalysts. As shown in Fig. 10, after the introduction of Ag designed and prepared via an in-suit photoreduction method. The Ag
nanoparticles, the intensities of PL curves decrease gradually, implying nanoparticles with a diameter of 4-6 nm uniformly distributed onto the
that the Ag-CN nanocomposites can effectively reduce the recombina­ entire surface of 20Ag-CN, which showed the highest activities for the
tion of charges carriers, which is helpful for improving the photo­ thermal coupled photocatalytic CO2-to-CO conversion. The Ag-
catalytic CO2 reduction activities [19]. Among the obtained samples, nanoparticle loading was benefit for the migration of the photo­
20Ag-CN shows the lowest PL intensity, which indicates that the loading produced charge carriers and played an important role for improving the
amount of Ag can optimize the recombination efficiency of photoin­ photocatalytic performance of the CN sample. It was also found that the
duced charges. All the observations confirm that Ag loading can indeed CO2 reduction rates on the 20Ag-CN photocatalyst increased quickly
enhance the separation of photogenerated electrons and holes on CN, with the increasing of the reaction temperature, which reached to a
which is consistent with the CO production efficiencies of the catalysts maximum value of 179.6 μmol•g− 1•h− 1 at 190 ◦ C that is about 4.2 times
as shown in Fig. 4a. higher than that of CN; higher reaction temperatures resulted in a
As shown in Figs. 9 and 10, the increasing charge transfer and sep­ decreased reduction rate. This high temperature activity was highly
aration after Ag loading is beneficial for the enhanced photocatalytic contrasted with the ambient temperature photoactivity that showed
performance of the samples. Moreover, the result in Fig. 5a clearly negligible CO production. The thermal coupled photocatalysis could
shows that the heat input is also critical to the catalytic performance for provide a promising approach for enhancing photocatalytic CO2

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X. Han et al. Surfaces and Interfaces 23 (2021) 101006

Fig. 11. Schematic illustration of the charge transfer and separation in the Ag-CN photocatalyst.

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[20] Y.S. Fu, T. Huang, B.Q. Jia, J.W. Zhu, X. Wang, Reduction of nitrophenols to
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