Journal of Alloys and Compounds 903 (2022) 163806

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Journal of Alloys and Compounds

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

Tubular g-C3N4 coupled with lanthanide oxides Yb2O3 as a novel

bifunctional photocatalyst：Enhanced photocatalytic NO removal and H2 ]]
]]]]]]
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evolution, dual regulation and reaction pathway

⁎ ⁎
Youzhou He , Mingzuo Chen, Yao Jiang , Lei Tang, Jianning Yu, Ya Chen, Min Fu, Xuemei Tan,
⁎
Jiajia Jing, Guizhi Zhang, Xingyan Liu
Chongqing Key Laboratory of Catalysis and New Environmental Materials, College of Environment and Resources, Chongqing Technology and Business University,
Chongqing 400067, China

a r t i cl e i nfo a bstr ac t

Article history: The modification of graphite carbonitride (g-C3N4) is beneficial to increase its specific surface area and high
Received 29 November 2021 quantum efficiency, thus improving its activity. Herein, the Yb2O3/g-C3N4 composites were adjusted through
Received in revised form 12 January 2022 dual regulation synergistically (nanostructure design of g-C3N4 and addition of lanthanide oxides Yb2O3) to
Accepted 13 January 2022
improve the photocatalytic performance of hydrogen production and NO removal simultaneously. The as-
Available online 21 January 2022
prepared 1% Yb2O3/tubular g-C3N4 could efficiently promote the photocatalytic hydrogen evolution (4071.763
μmol·g−1·h−1) and NO removal performance (54.20%), which was approximately 8.85 times and 32.01% higher
Keywords:
Dual regulation respectively than that of bulk g-C3N4 prepared by melamine (g-C3N4-M). The formation process of·O2- and·OH
H2 production radicals and the oxidation process of NO had been systematically studied through ESR and in-situ DRIFTS,
NO removal which proved that the coupling of tubular g-C3N4 with Yb2O3 had a positive effect. This work provided a novel
Tubular g-C3N4 strategy for dual regulation (adjust morphology and metal oxide introduction) synergistically design of
Photocatalytic bifunctional photocatalysts to enhance H2 production and NO removal simultaneously.
© 2022 Elsevier B.V. All rights reserved.

1. Introduction photocatalysis is a novel purification technology with the ad­

vantages of low energy consumption and fine removal effects [4].
The continuous consumption of nonrenewable resources has Thus, it is a very key issue to find a fine photocatalyst for both
caused more and more serious energy crisis and environmental hydrogen evolution and NO removal.
pollution, which leads to severe challenges in human survival and Graphitic carbon nitride (g-C3N4) is a typical polymer semi­
development [1,2]. To seek clean energy instead of fossil fuels has conductor with appropriate electronic band structure and high
become a universal direction, but it will take a long time to com­ physicochemical stability [5,6], which has been used as an important
pletely replace fossil fuels, during which time the pollutants will still material in the field of photocatalysis [7,8]. Nevertheless, there are
be generated. Therefore, a more effective solution for above problem still some disadvantages, for instance, the high electron-hole re­
is to simultaneously find clean energy (such as hydrogen energy) combination rate, inferior electrical conductivity, and insufficient
from "source control" method and deal with pollutants (such as NO) visible-light (λ > 420 nm) absorption, which hinder the photo­
from "end-of-pipe treatment" approach. Hydrogen, a clean energy catalytic effect of bulk g-C3N4 [9,10]. One of the effective problem-
source with high energy density that is about three times of same solving strategies is to design unique nanostructure of g-C3N4 (such
gasoline, could be obtained through water splitting, among which as constructing tubular and porous structures), which is beneficial to
photocatalytic production of hydrogen from water is a clean and obtain a bigger specific surface area to reveal further active sites and
simple process with high-purity hydrogen and low energy con­ regulate the electron-hole diffusion distance, further enhancing the
sumption [3]. Treatment of terminal pollutants (such as NO) by photocatalytic activity [11]. The hydrogen production rate of com­
posite material photocatalyst is as high as 1575 µmol·g−1·h−1
(λ > 420 nm), which is approximately five times higher than that of
⁎
Correspondence to: Chongqing Technology and Business University, Xuefu bulk g-C3N4. The investigation shows that the tube-like structure is
Avenue, Nan'an District, Chongqing 400067, China. conducive to the longitudinal transfer of electrons, which tre­
E-mail addresses: [email protected] (Y. He), [email protected] (Y. Jiang),
[email protected] (X. Liu).
mendously reduces the probability of electron hole recombination

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0925-8388/© 2022 Elsevier B.V. All rights reserved.
Y. He, M. Chen, Y. Jiang et al. Journal of Alloys and Compounds 903 (2022) 163806

Scheme1. Synthesis of Yb2O3/g-C3N4-CA·M.

[12]. The porous graphene like g-C3N4 nanosheets were obtained by (adamas-beta, 99.95%, ≥47% Pt), Triethanolamine (Adamas, 98%). All
changing the microstructure of g-C3N4, which could increase the chemicals were bought from commercial channels and used without
active sites and improve the photocatalytic removal rate of NO and further processing.
NO2 [13]. In addition to increasing more active sites via regulating
the structure of bulk g-C3N4, it is also possible to adjust the band gap 2.2. Synthesis procedure
by coupling with other materials to enhance the photocatalytic
activity [14]. 2.2.1. Preparation of g-C3N4
An extremely available strategy has been adopted to improve the g-C3N4 synthesized by calcining urea (g-C3N4-U). Urea (10 g,
photocatalytic effect of g-C3N4 through supporting with metals or 166.5 mmol) was heated at 5 °C/min to 500 °C for 3 h in air to get the
metal oxides. A series of materials such as metals (Pt [15], Ag [16], K product.
[17], Ni-Cu [18]) and metal oxides (Cu2O [19], TiO2 [20], WO3 [21]) g-C3N4 prepared by calcining melamine (g-C3N4-M). Melamine
have been widely compounded with the g-C3N4 to facilitate ad­ (10 g, 79.3 mmol) was heated at 5 °C/min to 500 °C for 3 h in air to
justment of the electronic structure and promote the efficiency of get the sample.
carrier separation, which could improve the photocatalytic activity. Tubular g-C3N4 (g-C3N4-CA·M). Melamine (630.6 mg, 5 mmol)
To our knowledge, the lanthanide elements, the major rare earth and cyanuric acid (645.4 mg, 5 mmol) were dissolved in 150 mL H2O
elements with special physical and chemical properties, have an and stirred for 4 h. Next, the suspension liquid that was poured into
unsaturated 4f5d electronic configuration with a large radius that a 200 mL autoclave containing polytetrafluoroethylene material was
could be easily polarized by adjacent atoms, which could adjust the kept in an oven at 180 °C for 6 h and cooled to room temperature.
energy band structure as much as possible [22,23], and also could The white liquid was filtered to obtain crystals, and then it was dried
form various sub-levels in the energy band via Vis-to-UV or NIR-to- at 45 °C for 12 h. Eventually, the crystals were calcined at 2.3 °C/min
UV up-conversion effect to expand the utilization of light energy to 550 °C under N2 for 4 h to gain the product.
[24,25], further improving the photocatalytic efficiency. Therefore, it
is great potential to introduce the lanthanide elements as an active
2.2.2. Synthesis of Yb2O3/g-C3N4
ingredient in the g-C3N4 to enhance the catalytic activity [26,27].
Yb2O3/g-C3N4. Yb(NO3)3.5 H2O (based on g-C3N4, the mass frac­
However, there are few examples that g-C3N4 improve the photo­
tion of Yb was 0.2%, 0.5%, 1%, 3%, 5%) was dissolved in a 30 mL H2O
catalytic performance of NO removal and hydrogen production
beaker which was added 400 mg g-C3N4, then sealed the beaker with
simultaneously through dual regulation (nanostructure design and
plastic wrap, after stirring in water bath kettle at 70 °C for 6 h, re­
lanthanide element introduction).
moved the plastic wrap and continued heating until the water in the
Yb, a kind of lanthanide element with excellent spectral char­
beaker was boiled dry. Finally, the obtained crystals under the cal­
acteristics, has been widely used in optical fiber amplifying materials
cination temperature of 550 °C for 4 h with rate of 5 °C/min in N2.
for optical communications to improve the efficiency of light am­
plification [28,29]. In this work, the Yb2O3/g-C3N4 composites were
adjusted through synergistic effects between the nanostructure of g-
C3N4 and the addition of metal oxides to simultaneously enhance
hydrogen evaluation and NO elimination under the visible light ir­
radiation. In contrast to pristine bulk g-C3N4, the loaded-Yb2O3
tubular g-C3N4 could greatly improve H2 evolution and the NO re­
moval rate, suggesting the fabricating lanthanide elements with
tubular g-C3N4 could be a feasible way to enhance the photocatalytic
effect, which provided a new tactic for the straightforward design of
g-C3N4-based bifunctional catalysts. This work provided a novel
strategy for dual regulation (adjust morphology and metal oxide
introduction) synergistically design of bifunctional photocatalysts to
improve the photocatalytic performance of hydrogen production and
NO removal simultaneously, which could realize “source control”
and “end treatment”. Scheme1.

2. Experimental section

2.1. Materials

Urea (General-reagent, 99%), Melamine (Adamas, 99%), Cyanuric Fig. 1. XRD patterns of Yb2O3, simulate Yb2O3, g-C3N4-CA·M and Yb2O3/g-C3N4-CA·M
acid (Adamas, 98%), Yb (NO3)3.5 H2O (Aladdin, 99.9%), H2PtCl6 (Yb2O3 content is 0.2%, 0.5%, 1%, 3%, 5%).

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Y. He, M. Chen, Y. Jiang et al. Journal of Alloys and Compounds 903 (2022) 163806

Fig. 2. The SEM of (a) g-C3N4-M (b) g-C3N4-CA·M and (c) 1% Yb2O3/g-C3N4-CA·M；(d) TEM and (e) HRTEM of 1% Yb2O3/g-C3N4-CA·M.

(0.2% Yb2O3/g-C3N4-CA·M, 0.5% Yb2O3/g-C3N4-CA·M, 1% Yb2O3/ composite Yb2O3 is very low and difficult to detect. We also could
g-C3N4-CA·M, 3% Yb2O3/g-C3N4-CA·M, 5% Yb2O3/g-C3N4-CA·M, 1% see that the diffraction peak of g-C3N4-U and g-C3N4-M decreased
Yb2O3/g-C3N4-U and 1% Yb2O3/g-C3N4-M, respectively). with the addition of Yb2O3 from Fig. S1. Therefore, the crystalline
phase of g-C3N4 would reduce along with the addition of Yb2O3, but
3. Results and discussion the overall phase of g-C3N4 could maintain.
To understand the morphologies of the composite catalysts, the
3.1. Morphology and structure SEM and TEM images of g-C3N4-M, g-C3N4-CA·M and 1% Yb2O3/
g-C3N4-CA·M were shown in Fig. 2. It was clearly found from SEM
The XRD diffraction patterns of pristine g-C3N4 and Yb2O3/g-C3N4 that g-C3N4-M had a bulk morphology and g-C3N4-CA·M had a
composites were shown in Fig. 1 and Fig. S1. The prepared original tubular morphology (Figs. 2a and 2b). After adding Yb2O3, the tub­
g-C3N4-CA·M, g-C3N4-U and g-C3N4-M catalysts all showed two ular morphology could maintain, but the surface became rougher
characteristic peaks (13.1° and 27.5°), which were corresponded to (Fig. 2c). The TEM image (Fig. 2d) of 1% Yb2O3/g-C3N4-CA·M showed
the (100) and (002) lattice plane of g-C3N4 [30,31]. It was completely the tubular structure was porous tube. From the corresponding en­
consistent with the standard spectrum of g-C3N4, confirming that g- larged high resolution TEM image of 1% Yb2O3/g-C3N4-CA·M (Fig. 2e),
C3N4 was successfully obtained. In addition, it could be seen from the lattice fringe spacing of 0.17 nm, 0.23 nm, 0.26 nm and 0.30 nm
Fig. 1 that the peak strength of the Yb2O3/g-C3N4-CA·M composite could be observed, which was attributed to (600), (420), (400) and
material became weaker than that of original g-C3N4-CA·M, and the (222) crystalline structure of exposed Yb2O3 in the photocatalytic
higher the amount of Yb2O3, the weaker the peak. This could be as material (PDF No.41–1106), further confirmed that Yb2O3 was suc­
the Yb2O3 was added in g-C3N4 and they combined closely and cessfully fabricated on g-C3N4-CA·M [32]. Moreover, the SEM-EDX
covered each other, which reduced the intensity of diffraction peaks. spectrum and mapping of 1% Yb2O3/g-C3N4-CA·M showed that C, N,
The simulate XRD peak of Yb2O3 was also added in Fig. 1, from the O and Yb elements were evenly distributed (Fig. S2), which could
data display, the diffraction peak of Yb2O3 is not observed in other further confirm that the synthesis of 1% Yb2O3/g-C3N4-CA·M was
materials loaded with Yb2O3, which might be because the content of successful.

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Y. He, M. Chen, Y. Jiang et al. Journal of Alloys and Compounds 903 (2022) 163806

Fig. 3. XPS profiles of (a) C 1 s, (b) N 1 s and (c) O 1 s of g-C3N4-CA·M and 1% Yb2O3/g-C3N4-CA·M, (d) Yb 4d of 1% Yb2O3/g-C3N4-CA·M.

The surface chemical composition of as-prepared g-C3N4-CA·M Table1

and 1% Yb2O3/g-C3N4-CA·M materials were studied by XPS Comparison of BET surface area, pore volume for g-C3N4 series and 1% Yb2O3/g-C3N4
(Fig. 3a~d). The scan XPS spectra (Fig. S3) of g-C3N4-CA·M and 1% series.
Yb2O3/g-C3N4-CA·M showed that both of them contain C, N and O Sample name Total pore volume (cm3g−1) SBET m2g−1
elements, while the Yb element only does existed in 1% Yb2O3/g-
g-C3N4-M 0.06 1.0
C3N4-CA·M. There were two obvious peaks at 288.3 and 284.8 eV in g-C3N4-U 0.16 48.6
the C1s spectra of the two samples (Fig. 3a), which belonged to C-N g-C3N4-CA·M 0.34 56.5
coordination and C-C bonding in graphite carbon. In Fig. 3b, we 1% Yb2O3/g-C3N4-M 0.04 5.7
could observe three peaks, the peaks at 398.9 eV, 400.6 eV and 1% Yb2O3/g-C3N4-U 0.22 57.0
1% Yb2O3/g-C3N4-CA·M 0.37 59.4
401.6 eV, which were corresponded to C-N]C, C-(N)3 and C-N-H
groups respectively [12]. In Fig. 3c, g-C3N4-CA·M and 1% Yb2O3/g-
C3N4-CA·M had the same peak at 532.2 eV, which was attributed to showed that these samples were alike and all of them were type IV
the O-H species adsorbed on the sample surface. We found that 1% isotherms with a H3-type hysteresis loop (classified by IUPAC), de­
Yb2O3/g-C3N4-CA·M has a weak peak at 534.6 eV, which belongs to monstrating the existence of slit like mesopores [34,35]. As shown in
the O2- of Yb2O3, and its ratio to O-H is approximately 26.56%:73.44% Fig. 4b, the Yb2O3/g-C3N4-U series show a sharp peak at 4 nm and a
[32]. In Fig. 3d, a peak observed at 184.9 eV was attributed to Yb3+, broad peak ranging from 10 to 60 nm; the Yb2O3/g-C3N4-CA·M series
which could further confirm the existence of Yb again [33]. show a sharp peak at and 5 nm and a broad peak ranging from 10 to
It was displayed the nitrogen adsorption−desorption isotherms at 100 nm [41].
77 K and the obtained pore size distributions by Barret-Joyner- The specific surface area (SBET) and pore volume were declared in
Halenda (BJH) method for g-C3N4 and Yb2O3/g-C3N4 in Fig. 4. Fig. 4a Table 1. The 1% Yb2O3/g-C3N4-CA·M had a higher specific surface

Fig. 4. (a) N2 adsorption-desorption isotherms and (b) Pore size distribution curves for g-C3N4 series and 1% Yb2O3/g-C3N4 series.

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Y. He, M. Chen, Y. Jiang et al. Journal of Alloys and Compounds 903 (2022) 163806

Fig. 5. Photocatalytic hydrogen evolution diagram of (a) g-C3N4-CA·M and Yb2O3/g-C3N4-CA·M (Yb2O3 content is 0.2%, 0.5%, 1%, 3%, 5%); (b) Stability test of photocatalytic
hydrogen evolution of 1% Yb2O3/g-C3N4-CA·M under visible light irradiation.

area (59.4 m2g−1) and correspondingly larger pore volume improve the removal effect of NO. Fig. 6b showed good stability of 1%
(0.37 cm3g−1) than the other samples. The increased surface area Yb2O3/g-C3N4-CA·M, and further illustrated that 1% Yb2O3/g-C3N4-
could be beneficial for obtaining more active sites for photocatalysis CA·M could act as good catalytic materials for NO elimination.
application.
3.4. Optical features of the photocatalysts
3.2. Photocatalytic H2 production activity
The UV-Vis absorption and the band gap energy of g-C3N4-CA·M
Fig. 5a showed the photocatalytic hydrogen evolution rate (HER) and different contents of Yb2O3/g-C3N4-CA·M composites were de­
of original g-C3N4-CA·M and Yb2O3/g-C3N4-CA·M composites. The scribed in Fig. 7. Obviously, the absorption range slightly shifted to
HER of original g-C3N4-CA·M was extremely low, however the hy­ the longer visible region, and the absorption peak of Yb2O3/g-C3N4-
drogen evolution amount of all Yb2O3/g-C3N4-CA·M were better than CA·M was higher than that of g-C3N4-CA·M (Fig. 7a), which indicated
that of pristine g-C3N4-CA·M. At first the hydrogen production in­ the Yb2O3 could promote the light absorption ability of g-C3N4-CA·M,
creased with the increased loading amount of Yb2O3. The 1% Yb2O3/ further improving the efficiency of photocatalytic hydrogen pro­
g-C3N4-CA·M composite had the superior photocatalytic perfor­ duction. To adopt the Kubelka-Munk function transformation, the
mance (4071.763 μmol·g−1·h−1), which was almost 2.1 times than band gap of g-C3N4-CA·M (Fig. 7b) was determined to be approxi­
pure g-C3N4-CA·M. The apparent quantum efficiency (AQE) for hy­ mately 2.74 eV, while the band gap of 1% Yb2O3/g-C3N4-CA·M was
drogen generation at 420 nm was calculated to be 7.0%. However, the about 2.67 eV, which showed Yb2O3 could help reduce the band gap,
hydrogen evolution rate decreased when the loading content of thereby enhancing the photocatalytic performance.
Yb2O3 (3%, 5%) further gradually increased, which might be inferred As shown in Fig. S5, we could see clearly that the g-C3N4-U and g-
that the excessive Yb2O3 could hinder the active sites on the catalyst C3N4-M had a strong fluorescence emission around 465 nm, while
surface. It could be seen from Fig. 5b that 1% Yb2O3/g-C3N4-CA·M along with the addition of Yb2O3, the 1% Yb2O3/g-C3N4-U and 1%
maintained good photocatalytic stability performance. Fig. S4a and Yb2O3/g-C3N4-M showed a remarkably decreased fluorescence
Fig. S4b indicated the HER of g-C3N4-U and g-C3N4-M would also be emission intensity. In addition, as revealed in Fig. 8, the sample of 1%
improved after Yb2O3 was added, which were 4 times (3137.43 Yb2O3/g-C3N4-CA·M exhibited the lowest PL than any other g-C3N4-
μmol·g−1·h−1) and 2.2 times (1020.26 μmol·g−1·h−1) than original CA·M with different contents of Yb2O3, which indicated that the 1%
g-C3N4 respectively. Yb2O3/g-C3N4-CA·M could more efficiently reduce the recombination
of electrons and holes. The quenched fluorescence revealed a rapid
3.3. Photocatalytic NO removal injection of photoexcited electrons from g-C3N4 into Yb2O3.

It was illustrated the NO removal rate of g-C3N4-M, g-C3N4-CA·M 3.4.1. The electrochemical characterization test
and 1% Yb2O3/g-C3N4-CA·M composites in Fig. 6. As described in To further determine the electron transport characteristics, the
Fig. 6a, the elimination rate of original g-C3N4-M had reached 22.19%, photoelectrochemical properties were measured. From Fig. 9a,
while the removal rate of 1% Yb2O3/g-C3N4-CA·M reached 54.20%, the photocurrent-time curve revealed that the photocurrent
which suggested the addition of Yb2O3 in g-C3N4-CA·M could response intensity of 1% Yb2O3/g-C3N4-CA·M was the highest. The

Fig. 6. (a) NO elimination graph of g-C3N4-M, g-C3N4-CA·M and 1%Yb2O3/g-C3N4-CA·M; (b) NO elimination stability test graph of 1%Yb2O3/g-C3N4-CA·M under visible light
irradiation.

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Y. He, M. Chen, Y. Jiang et al. Journal of Alloys and Compounds 903 (2022) 163806

Fig. 7. (a) UV-Vis diffuse reflectance spectra and (b) the plots of (αhν)2 versus energy (hν) for the band gap energy of g-C3N4-CA·M and 1%Yb2O3/g-C3N4-CA·M.

photogenerated electron lifetime, which was consistent with the

photocurrent result [5].

1
r =
2 fpeak

3.5. Possible photocatalytic mechanism over Yb2O3/g-C3N4

To further shed light on the NO adsorption and removal process

by the photocatalyst, the in-situ DRIFTS measurements of g-C3N4-
CA·M and 1%Yb2O3/g-C3N4-CA·M were studied as a function of time
(Fig. 10). As shown in NO adsorption process on g-C3N4-CA·M
(Fig. 10a), the adsorption intensity was raised at absorption bands of
871 cm−1, 1035 cm−1and 1089 cm−1, which illustrated the accumu­
lation of adsorption species (the stretching vibration of mono­
dentate nitrite, cis-N2O2 and NO-) [36]. For 1% Yb2O3/g-C3N4-CA·M
photocatalyst (Fig. 10b), the formation of the adsorption bands of
819 cm−1 (N2O), 893 cm−1 (N2O3), 1001 cm−1 (the stretching vibration
of monodentate nitrites) and 1118 cm−1 (NO3-) were attributed to the
Fig. 8. Fluorescence diagrams of g-C3N4-CA·M and Yb2O3/g-C3N4-CA·M (Yb2O3 con­ adsorption of NO [37]. Compared with g-C3N4-CA·M, 1% Yb2O3/
tent is 0.2%, 0.5%, 1%, 3%, 5%). g-C3N4-CA·M had new absorption bands, indicating that the oxida­
tion ability of 1% Yb2O3/g-C3N4-CA·M was stronger than g-C3N4-
CA·M [38].
results showed that the electron transfer rate at the interfacial After reaching the adsorption equilibrium, the infrared spectra of
boundary of 1% Yb2O3/g-C3N4-CA·M was the best, which could be g-C3N4-CA·M and 1% Yb2O3/g-C3N4-CA·M were monitored over time.
adjusted by the addition of Yb2O3. Therefore, a certain content of As described in Fig. 10c, the intensity of these bands at 871 cm−1 and
Yb2O3 could promote electron migration and suppress the re­ 1035 cm−1 had increased, but only a new absorption band appeared
combination of electron and hole, which could improve the photo­ at 814 cm−1, which indicated an inferior NO removal ability of
catalytic hydrogen evolution efficiency. Fig. S6a and Fig. S6b also g-C3N4-CA·M [39]. In the IR spectra of 1% Yb2O3/g-C3N4-CA·M
indicated that the photocurrent intensity of g-C3N4-M and g-C3N4-U (Fig. 10d), the intensity of the bands at 819 cm−1 and 893 cm−1 in­
with Yb2O3 addition was stronger than pristine g-C3N4, which con­ creased with the illumination time. At the same time, some new
firmed again that a certain amount of Yb2O3 could improve the se­ absorption bands appeared at 995 cm−1 (N2O3), 1015 cm−1 (bidentate
paration efficiency of charge carriers and further enhance NO3-) and 1084 cm−1 (bidentate NO2-) and 1139 cm−1 (NO-), which
photocatalytic ability. further confirmed that the loaded-Yb2O3 benefited the significant
EIS was also measured for further prove the relevant conclusions enhancement of photocatalytic NO removal [40].
above. The radius of the curve reflected the ability of the charge The spin-trapping electron spin resonance (ESR) spectra were
transfer resistance. As shown in Fig. 9b, the radius of 1% Yb2O3/g- detected to fully confirm the active species produced during the
C3N4-CA·M was the smallest, indicating that the charge transfer was photocatalytic reaction, like the superoxide radicals and the hy­
faster, which matched with photocatalytic performance. In addition, droxyl radicals (∙O2- and ∙OH). As shown in Fig. 11a, ESR showed
Fig. S7a and Fig. S7b also exhibited that the radius of g-C3N4-M and typical peaks of DMPO-·O2- with about signal intensity ratio of
g-C3N4-U become smaller along with the Yb2O3 added, which in­ 1:1:1:1. 1% Yb2O3/g-C3N4-CA·M displayed a stronger signal of DMPO-
creased the rate of charge transfer to enhance the photocatalytic ·O2- in comparison with g-C3N4-CA·M. With the increase of light
effect. time, the signal of DMPO-·O2- also became much stronger, which
Fig. 9 showed the Bode phase plot of g-C3N4-CA·M and 1% Yb2O3/ suggested the O2 molecules gained more electrons to enhance ac­
g-C3N4-CA·M, which could compare the electron lifetime of the tivation. Besides, Fig. 11b revealed the signal peaks which was the
sample, in which the electron lifetime (τr) can be calculated from peak intensity ratio of 1:2:2:1 belonged to DMPO-·OH. Among which
formula (1). From the diagram, it could be seen that 1% Yb2O3/g- the 1% Yb2O3/g-C3N4-CA·M also had a stronger signal intensity. It
C3N4-CA·M had a lower peak frequency, indicated that compared was demonstrated that loaded-Yb2O3 could promote the formation
with g-C3N4-CA·M, 1% Yb2O3/g-C3N4-CA·M had a higher of both the ·O2-and ·OH.

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Y. He, M. Chen, Y. Jiang et al. Journal of Alloys and Compounds 903 (2022) 163806

Fig. 9. (a) Photocurrent diagram and (b) Impedance graphs of g-C3N4-CA·M and Yb2O3/g-C3N4-CA·M (Yb2O3 content is 0.2%, 0.5%, 1%, 3%, 5%), (c) Bode plots of the g-C3N4-CA·M
and 1% Yb2O3/g-C3N4-CA·M.

The Mott-Schottky plots were used to evaluate the flat-band the flat band potential (EFB) of g-C3N4-CA·M and 1% Yb2O3/g-C3N4-
potential (EFB) of g-C3N4-CA·M and 1% Yb2O3/g-C3N4-CA·M in 0.2 M CA·M were estimated to be − 1.42 V and − 0.90 V. For n-type semi­
Na2SO4 electrolyte with a frequency of 1.0 kHz. As shown in Fig. 12, conductors, the conduction band potential (ECB) was more negative
g-C3N4-CA·M and 1% Yb2O3/g-C3N4-CA·M had a positive slope, which (−0.1 or −0.2 V) than its flat-band potential. Therefore, relative to
were typical n-type semiconductor behavior [41]. Relative to SCE, SCE, the conduction bands (ECB) of g-C3N4-CA·M and 1% Yb2O3/g-

Fig. 10. In situ DRIFTS spectra of photocatalytic NO oxidation on g-C3N4-CA·M and 1% Yb2O3/g-C3N4-CA·M under visible light illumination and an oxygen atmosphere under visible
light irradiation.

7
Y. He, M. Chen, Y. Jiang et al. Journal of Alloys and Compounds 903 (2022) 163806

Fig. 11. ESR spectra in dark and under visible-light (λ ≥ 420 nm) for 10 min in (a) methanol dispersion for ·O2− and (b) deionized water dispersion for ·OH.

Fig. 12. Mott-Schottky plots of (a) g-C3N4-CA·M and (b) 1% Yb2O3/g-C3N4-CA·M.

C3N4-CA·M were roughly calculated to be − 1.62 V and − 1.10 V, and (EVB, XPS) measured by VB-XPS plots. As shown in Fig. S8, the cor­
further estimated to be − 1.38 and − 0.86 V relative to the normal responding EVB, XPS of g-C3N4-CA·M and 1% Yb2O3/g-C3N4-CA·M is
hydrogen electrode (NHE) (ENHE = ESCE + 0.241 V). According to the measured to be 1.64 and 2.15 eV, respectively. Then, the EVB of the
test results of Mott-Schottky experiments, the band structure of g- corresponding standard hydrogen electrode (EVB, NHE) can be calcu­
C3N4-CA·M and 1% Yb2O3/g-C3N4-CA·M could be further analyzed. As lated according to the following formula: EVB, NHE = φ + EVB, XPS− 4.44,
described in Fig. 7b, the band gap energies of g-C3N4-CA·M and 1% where φ is the work function of the instrument (4.2 eV). Thus, the
Yb2O3/g-C3N4-CA·M could be found out through the Kubelka-Munk EVB, NHE of g-C3N4-CA·M and 1% Yb2O3/g-C3N4-CA·M is calculated to
function transformation, which were 2.74 eV and 2.67 eV, respec­ be 1.40 and 1.91 eV, respectively [42].
tively. The valence bands of g-C3N4-CA·M and 1% Yb2O3/g-C3N4-CA·M A possible mechanism for the purification of NO by Yb2O3/g-
could be obtained through the formula of EVB = ECB + Eg, whose va­ C3N4-CA·M under visible light was explained (Fig. 13a). The electrons
lues were 1.36 eV and 1.81 eV, respectively. In order to further con­ in VB of g-C3N4-CA·M were excited to transfer to CB along with
firm the accuracy of the band structure, we also consider directly leaving holes in VB, which formed electron-hole pairs under the
using the VB-XPS method to measure the valence band potential light. The CB potential of Yb2O3 was more positive than that of

Fig. 13. A possible photocatalytic mechanism for (a) treatment of NO and (b) efficient hydrogen production via Yb2O3/g-C3N4-CA·M under visible light.

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Y. He, M. Chen, Y. Jiang et al. Journal of Alloys and Compounds 903 (2022) 163806

g-C3N4-CA·M, and the electrons in CB of g-C3N4-CA·M were easily 1952019), National College Students' Innovation and Entrepreneurship
transferred to the CB of Yb2O3, resulting in effective charge separa­ Training Program of China (202111799003), Student Science and
tion and transfer. These electrons will migrate to the surface of the Technology Innovation Fund Project of Chongqing Technology and
Yb2O3 and react with water and oxygen to generate ·O2- and ·OH, Business University（20318）, the Chongqing College Students’
further changing NO into NO3- and NO2-. What is more, Fig. 13b Innovation and Entrepreneurship Training Program (S202011799027,
showed the H2 production mechanism of the Yb2O3/g-C3N4-CA·M S202111799028), the Chongqing Key Laboratory of Catalysis and New
composites. The CB energy level of g-C3N4-CA·M was more negative Environmental Materials (CQCM-2016-04), the Innovation Group of
than that of Yb2O3 under visible light, so the electrons on g-C3N4- New Technologies for Industrial Pollution Control of Chongqing
CA·M could be easily transferred to first the surface of Yb2O3 and Education Commission (CXQT19023), Graduate Innovation Program of
further to Pt nanoparticles to catalyze the reduction of H+ to H2. At Chongqing Technology and Business University (yjscxx2021-112-46).
the same time, electron sacrificial agent (TEOA) in the reaction so­
lution consumed the holes in the g-C3N4-CA·M valence band (VB) to Supplementary material
promote the charge transfer. In short, loading with Yb2O3 could
reduce electron-hole recombination of nanotube g-C3N4-CA·M to Important information is provided in the support information.
further improve photocatalytic effect [43].
Appendix A. Supporting information
4. Conclusion
Supplementary data associated with this article can be found in
In summary, a train of loaded-Yb2O3 tubular g-C3N4 bifunctional the online version at doi:10.1016/j.jallcom.2022.163806.
catalysts had been synthesized via dual regulation synergistically
method, which could simultaneously enhance the photocatalytic References
hydrogen evolution effect and improve the NO removal rate. Based
[1] D. Rodríguez Padrón, A. Puente Santiago, A.M. Balu, M. Muñoz Batista, R. Luque,
on the experimental results, the as-prepared 1% Yb2O3/g-C3N4-CA·M Environmental catalysis: present and future, ChemCatChem 11 (2019) 18–38,
composite has the highest photocatalytic effect in photocatalytic https://doi.org/10.1002/cctc.201801248
hydrogen evolution (4071.763 μmol·g−1·h−1), which was approxi­ [2] P. Wang, T. Wu, Y. Ao, C. Wang, Fabrication of noble-metal-free CdS nanorods-
carbon layer-cobalt phosphide multiple heterojunctions for efficient and robust
mately 8.85 times higher than the bulk g-C3N4-M. Meanwhile, the photocatalyst hydrogen evolution under visible light irradiation, Renew. Energy
NO removal rate of 1% Yb2O3/g-C3N4-CA·M also could increase by 131 (2019) 180–186, https://doi.org/10.1016/j.renene.2018.07.028
32.01% compared with the original g-C3N4-M. The obvious im­ [3] T.X. Liu, K.C. Yang, H.M. Gong, Z.L. Jin, Visible-light driven S-scheme Mn0.2Cd0.8S/
CoTiO3 heterojunction for photocatalytic hydrogen evolution, Renew, Energy 173
provement of photocatalytic ability could be mainly attributed to the (2021) 398–400, https://doi.org/10.1016/j.renene.2021.03.146
high specific surface area and the wide light energy utilization, [4] K. Skalska, J.S. Miller, S. Ledakowicz, Trends in NOx abatement: a review, Sci.
which could provide some meaningful lead for the dual regulation Total. Environ. 408 (2010) 3976–3989, https://doi.org/10.1016/j.scitotenv.2010.
06.001
design of bifunctional catalyst, further simultaneously improving the
[5] A.M. Saray, N. Zare-Dehnavi, F. Jamali-Sheini, R. Yousefi, Type-II p(SnSe)-n(g-
photocatalytic activity. C3N4) heterostructure as a fast visible-light photocatalytic material: Boosted by
an efficient interfacial charge transfer of p-n heterojunction, J. Alloy. Compd. 829
(2020) 154436, https://doi.org/10.1016/j.jallcom.2020.154436
CRediT authorship contribution statement [6] L. Yang, J. Liu, L. Yang, M. Zhang, H. Zhu, F. Wang, J. Yin, Co3O4 imbedded g-C3N4
heterojunction photocatalysts for visible-light-driven hydrogen evolution,
Youzhou He: Writing – original draft, Project administration, Renew. Energy 145 (2020) 691–698, https://doi.org/10.1016/j.renene.2019.06.
072
Supervision. Mingzuo Chen: Conceptualization, Methodology, [7] S. Fang, Y. Xia, K. Lv, Q. Li, J. Sun, M. Li, Effect of carbon-dots modification on the
Investigation, Validation, Formal analysis, Writing – original draft. structure and photocatalytic activity of g-C3N4, Appl. Catal. B Environ. 185 (2016)
Yao Jiang: Investigation, Validation, Visualization. Lei Tang: 225–232, https://doi.org/10.1016/j.apcatb.2015.12.025
[8] N.D. Martins, I.C.H. Gomes, G. da Silva, J.A. Torres, W. Avansi, C. Ribeiro,
Investigation, Validation, Visualization. Jianning Yu: Investigation, A.R. Malagutti, H. Mourao, Facile preparation of ZnO:g-C3N4 heterostructures
Validation, Visualization. Ya Chen: Investigation, Formal analysis. and their application in amiloride photodegradation and CO2 photoreduction, J.
Min Fu: Investigation, Formal analysis. Xuemei Tan: Investigation, Alloy. Compd. 856 (2021) 156798, https://doi.org/10.1016/j.jallcom.2020.156798
[9] M. Hojamberdiev, M.M. Khan, Z. Kadirova, K. Kawashima, K. Yubuta, K. Teshima,
Formal analysis. Jiajia Jing: Formal analysis. Guizhi Zhang: Formal R. Riedel, M. Hasegawa, Synergistic effect of g-C3N4, Ni(OH)2 and halloysite in
analysis. Xingyan Liu: Supervision, Writing – original draft, nanocomposite photocatalyst on efficient photocatalytic hydrogen generation,
Investigation, Conceptualization. Renew, Energy 138 (2019) 434–444, https://doi.org/10.1016/j.renene.2019.01.103
[10] R. Jiang, G. Lu, J. Liu, D. Wu, Z. Yan, Y. Wang, Incorporation of π-conjugated
molecules as electron donors in g-C3N4 enhances photocatalytic H2-production,
Declaration of Competing Interest Renew, Energy 164 (2021) 531–540, https://doi.org/10.1016/j.renene.2020.09.
040
[11] S. Guo, Y. Tang, Y. Xie, C. Tian, Q. Feng, W. Zhou, B. Jiang, Sulfur-mediated
The authors declare that they have no known competing fi­ synthesis of carbon nitride: band-gap engineering and improved functions for
nancial interests or personal relationships that could have appeared photocatalysis, Appl. Catal. B. 218 (2017) 664–671, https://doi.org/10.1039/
to influence the work reported in this paper. C0EE00418A
[12] Z. Tong, D. Yang, Y. Sun, Y. Nan, Z. Jiang, Tubular g-C3N4 Isotype Heterojunction:
enhanced Visible-Light Photocatalytic Activity through Cooperative
Acknowledgements Manipulation of Oriented Electron and Hole Transfer, Small 12 (2016)
4093–4101, https://doi.org/10.1002/smll.201601660
[13] Y. Li, Y. Sun, W. Ho, Y. Zhang, H. Huang, Q. Cai, F. Dong, Highly enhanced visible-
This work was supported by the National Natural Science light photocatalytic NOx purification and conversion pathway on self-structu­
Foundation of China (21502012，22001026), the Chongqing Science rally modified g-C3N4 nanosheets, Sci. Bull. 63 (2018) 609–620, https://doi.org/
10.1016/j.scib.2018.04.009
and Technology Commission (cstc2018jcyjAX0531, cstc2017jcyjAX0404, [14] Y. Zhang, Z. Jin, Boosting photocatalytic hydrogen evolution achieved by NiSx
cstc2017jcyjAX0116，cstc2020jcyj-msxmX0335), the Science and coupled with g-C3N4@ZIF-67 heterojunction, Phys. Chem. C. 123 (2019)
Technology Research Program of Chongqing Municipal Education 18248–18263, https://doi.org/10.1021/acs. jpcc.9b04695
[15] a) X. Wang, K. Maeda, A. Thomas, K. Takanabe, G. Xin, J.M. Carlsson, K. Domen,
Commission (KJQN201900838, KJQN201800836, KJQN202100843),
M. Antonietti, A metal-free polymeric photocatalyst for hydrogen production
Funding Project for Scientific Research of Chongqing Technology and from water under visible light, Nat. Mater. 8 (2009) 76–80, https://doi.org/10.
Business University (1756002, 1752015, 2015-56-11, 1952004， 1038/NMAT2317;

9
Y. He, M. Chen, Y. Jiang et al. Journal of Alloys and Compounds 903 (2022) 163806

b) B. Chai, T. Peng, J. Mao, K. Lia, L. Zan, Graphitic carbon nitride (g-C3N4)–Pt- [30] J. Zhang, X. Chen, K. Takanabe, K. Maeda, K. Domen, J.D. Epping, X. Fu,
TiO2 nanocomposite as an efficient photocatalyst for hydrogen production under M. Antonietti, X. Wang, Synthesis of a carbon nitride structure for visible-light
visible light irradiation, Phys. Chem. Chem. Phys. 14 (2012) 16745–16752 catalysis by copolymerization, Angew. Chem. Int. Ed. 49 (2010) 441–444, https://
[16] L. Ge, C. Han, J. Liu, Y. Li, Enhanced visible light photocatalytic activity of novel doi.org/10.1002/anie.200903886
polymeric g-C3N4 loaded with Ag nanoparticles, Appl. Catal. A: Gen. 409–410 [31] J. Xu, T.J.K. Brenner, Z. Chen, D. Neher, M. Antonietti, M. Shalom, Upconversion-
(2011) 215–222, https://doi.org/10.1016/j.apcata.2011.10.006 agent induced improvement of g-C3N4 photocatalyst under visible light, ACS
[17] Y. Wang, S. Zhao, Y. Zhang, J. Fang, Y. Zhou, S. Yuan, C. Zhang, W. Chen, One-pot Appl. Mater. Interfaces 6 (2014) 16481–16486, https://doi.org/10.1021/
synthesis of K-doped g-C3N4 nanosheets with enhanced photocatalytic hydrogen am5051263
production under visible-light irradiation, Appl. Surf. Sci. 440 (2018) 258–265, [32] Y. Sohn, Yb2O3 nanowires, nanorods and nano-square plates, Ceram. Int. 44
https://doi.org/10.1016/j.apsusc.2018.01.091 (2018) 3341–3347, https://doi.org/10.1016/j.ceramint.2017.11.11
[18] Z. Jin, L. Zhang, Performance of Ni-Cu bimetallic co-catalyst g-C3N4 nanosheets [33] Y. Ohno, XPS studies of the intermediate valence state of Yb in (YbS)1.25CrS2, J.
for improving hydrogen evolution, J. Mater. Sci. Technol. 49 (2020) 144–156, Electron Spectros Relat. Phenom. 165 (2008) 1–4, https://doi.org/10.1016/j.
https://doi.org/10.1016/j.jmst.2020.02.025 elspec.2008.05.009
[19] C. Jia, S. Yin, S. Sun, S. Yang, An in situ mediator-free route to fabricate Cu2O/g- [34] D. Ren, W. Zhang, Y. Ding, R. Shen, Z. Jiang, X. Lu, X. Li, In situ fabrication of
C3N4 type-II heterojunctions for enhanced visible-light photocatalytic H2 gen­ robust cocatalyst-free CdS/g-C3N4 2D–2D step-scheme heterojunctions for
eration, Appl. Surf. Sci. 434 (2018) 1224–1231, https://doi.org/10.1016/j.apsusc. highly active H2 evolution, Sol. Rrl. 4 (2019) 1900423, https://doi.org/10.1002/
2017.11.233 solr.201900423
[20] J. Pan, Z. Dong, B. Wang, Z. Jiang, C. Zhao, J. Wang, C. Song, Y. Zheng, C. Li, The [35] H. Che, C. Liu, G. Che, G. Liao, H. Dong, C. Li, N. Song, C. Li, Facile construction of
enhancement of photocatalytic hydrogen production via Ti3+ self-doping black porous intramolecular g-C3N4-based donor-acceptor conjugated copolymers as
TiO2/g-C3N4 hollow core-shell nano-heterojunction, Appl. Catal. B. 242 (2019) highly efficient photocatalysts for superior H2 evolution, Nano Energy 67 (2020)
92–99, https://doi.org/10.1016/j.apcatb.2018.09.079 104273, https://doi.org/10.1016/j.nanoen.2019.104273
[21] J. Singh, A. Arora, S. Basu, Synthesis of coral like WO3/g-C3N4 nanocomposites for [36] C. Wang, M. Fu, J. Cao, X. Wu, X. Hu, F. Dong, BaWO4/g-C3N4 heterostructure with
the removal of hazardous dyes under visible light (Article), J. Alloy. Compd. 808 excellent bifunctional photocatalytic Performance, Chem. Eng. J. 385 (2020)
(2019) 151734, https://doi.org/10.1016/j.jallcom.2019.151734 123833, https://doi.org/10.1016/j.cej.2019.123833
[22] J. Robertson, K. Xiong, Electronic structure and band offsets of lanthanide oxides, [37] K. Hadjiivanov, Identification of neutral and charged NxOy surface species by IR
Rare Earth Oxide Thin Films 106 (2007) 313–329, https://doi.org/10.1007/ spectroscopy, Catal. Rev. Sci. Eng. 42 (2000) 71–144, https://doi.org/10.1081/CR-
11499893_18 100100260
[23] R. Gillen, S.J. Clark, J. Robertson, Nature of the electronic band gap in lanthanide [38] H. Wang, W. He, X. Dong, G. Jiang, Y. Zhang, Y. Sun, F. Dong, In situ DRIFT in­
oxides, Phys. Rev. B. 87 (2013) 12–15, https://doi.org/10.1103/PhysRevB.87.125116 vestigation on the photocatalytic NO oxidation mechanism with thermally ex­
[24] P. Sing, P.K. Shahi, S.K. Singh, A.K. Singh, M.K. Singh, R. Prakashc, S.B. Rai, foliated porous g-C3N4 nanosheets, RSC Adv. 7 (2017) 19280, https://doi.org/10.
Lanthanide doped ultrafine hybrid nanostructures: multicolour luminescence, 1039/c7ra00879a
upconversion based energy transfer and luminescent solar collector applica­ [39] G. Jiang, J. Cao, M. Chen, X. Zhang, F. Dong, Photocatalytic NO oxidation on N-
tions, Nanoscale 9 (2017) 696–705, https://doi.org/10.1039/c6nr07250j doped TiO2/g-C3N4 heterojunction: Enhanced efficiency, mechanism and reac­
[25] X. Ge, J. Liu, L. Sun, Controlled optical characteristic of lanthanide doped up­ tion pathway, Appl. Surf. Sci. 458 (2018) 77–85, https://doi.org/10.1016/j.apsusc.
conversion nanoparticles for emerging applications, Dalton Trans. 46 (2017) 2018.07.087
16729–16737, https://doi.org/10.1039/C7DT03049E [40] B. Lin, S. Chen, F. Dong, G. Yang, A. Ball-in-Ball, g-C3N4@SiO2 nano-photoreactor
[26] J. Tang, W. Zhou, R. Guo, C. Huang, W. Pan, P. Liu, An exploration on in-situ for highly efficient H2 generation and NO removal, Nanoscale 9 (2017)
synthesis of europium doped g-C3N4 for photocatalytic water splitting, Energy 5273–5279, https://doi.org/10.1039/C7NR00501F
Procedia 158 (2019) 1553–1558, https://doi.org/10.1016/j.egypro.2019.01.365 [41] S. Yi, J. Yan, B. Wulan, S. Li, K. Liu, Q. Jiang, Noble-metal-free cobalt phosphide
[27] W. Zou, B. Deng, X. Hu, Y. Zhou, Y. Pu, S. Yu, K. Ma, J. Sun, H. Wan, L. Dong, modified carbon nitride: an efficient photocatalyst for hydrogen generation,
Crystal-plane-dependent metal oxide-support interaction in CeO2/g-C3N4 for Appl. Catal. B 200 (2017) 477–483, https://doi.org/10.1016/j.apcatb.2016.07.046
photocatalytic hydrogen evolution, Appl. Catal. B. 238 (2018) 111–118, https:// [42] L. Zhang, X. Hao, Q. Jian, Z. Jin, Ferrous oxalate dehydrate over CdS as Z-scheme
doi.org/10.1016/j.apcatb.2018.07.022 photocatalytic hydrogen evolution, J. Solid. State Chem. 274 (2019) 286–294,
[28] S. Jetschke, M. Leich, S. Unger, U. Röpke, Combined effect of Yb inversion and pump https://doi.org/10.1016/j.jssc.2019.03.040
photons on photodarkening in Yb laser fibers: experiments and model considera­ [43] X.B. Li, B.B. Kang, F. Dong, Z.Q. Zhang, X.D. Luo, L. Han, J.T. Huang, Z.J. Feng,
tions, JOSA B 36 (2019) 2438–2444, https://doi.org/10.1364/JOSAB.36.002438 Z. Chen, J.L. Xu, B.L. Peng, Z.L. Wan, Enhanced photocatalytic degradation and H2/
[29] G. Liu, X. Jiang, A. Wang, G. Chang, F. Kaertner, Z. Zhang, Robust 700 MHz mode- H2O2 production performance of S-p CN/WO2.72 S-scheme heterojunction with
locked Yb: fiber laser with a biased nonlinear amplifying loop mirror, Opt. appropriate surface oxygen vacancies, Nano Energy 81 (2021) 105671, https://
Express 26 (2018) 26003–26008, https://doi.org/10.1364/OE.26.026003 doi.org/10.1016/j.nanoen.2020.105671

10