Chemical Engineering Journal 396 (2020) 125263

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Chemical Engineering Journal

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

A readily synthesis of oxygen vacancy-induced In(OH)3/carbon nitride 0D/ T

2D heterojunction for enhanced visible-light-driven nitrogen fixation
⁎ ⁎
Junyu Fana, Meimei Zuoa, Zhaoxia Dinga, Zhiwei Zhaob, Jie Liua, , Bo Sunc,
a
Department of Military Facilities, Army Logistics University, Chongqing 401311, China
b
Key laboratory of the Three Gorges Reservoir Region's Eco-Environment, State Ministry of Education, Chongqing University, Chongqing 400045, China
c
College of Life and Environmental Science, Wenzhou University, Zhejiang 325035, China

H I GH L IG H T S G R A P H I C A L A B S T R A C T

• heterojunction
OV-induced In(OH) /carbon nitride
3
was firstly synthesized.
• The heterojunction was prepared by a
facile and readily method at moderate
condition.
• The heterojunction showed excellent
NH generation rate to be 3.81 mM /h
3
per 1 g.
• The “trap effect” of OVs on In(OH)3
accounts for enhancement of photo-
catalytic activity.

A R T I C LE I N FO A B S T R A C T

Keywords: A promising and practicable catalyst is the key challenge for industrial perspective to promote photocatalytic
0D /2D composite nitrogen fixation. In this study, a new 0D /2D heterojunction, oxygen vacancy-induced In(OH)3 /carbon nitride
C3N4 (OV-In(OH)3/CN), was synthesized by generating In(OH)3 nanoparticles on g-C3N4 nanosheets in the presence of
In(OH)3 glyoxal through a facile and readily precipitation growth method at 60℃and under atmospheric pressure. The
Oxygen vacancy
existence of oxygen vacancies, structure, morphology and optical-electronic properties of the composite were
Photocatalytic nitrogen fixation
characterized by HRTEM, XPS and EPR analysis and other measurements. The OV-In(OH)3 /CN heterojunction
exhibited excellent photocatalytic activity for nitrogen fixation with a good chemical stability. The OV-In/CN-3
sample reached the maximum NH3 generation rate to be 3.81 mM*h−1*g−1, which was about 10 times as that of
pure g-C3N4 and was also higher than that of other catalysts reported. Though the In(OH)3 in heterojunction was
demonstrated incapable of producing photogenerated electrons under vis-light irradiation, its oxygen vacancy
was found to “receive” and “trap” some excited electrons from g-C3N4, promoting electron-hole pairs separation
efficiency and prolonging the lifetime of carriers. And it also can introduce many chemisorption sites for N2.
Those are the two key reasons for its high photocatalytic activity.

1. Introduction the air and its main synthesis method is Haber-Bosch process [1,2].
However, this synthesis process under high pressure and temperature
Ammonia is a widely used raw material of chemical industry. consumes a lot of energy and would release large amounts of carbon
Industrial production of ammonia relies on the nitrogen fixation from dioxide into the atmosphere [3]. Recently, many alternatives of

⁎
Corresponding authors.
E-mail addresses: liujiely@hotmail.com (J. Liu), sunbohit@126.com (B. Sun).

https://doi.org/10.1016/j.cej.2020.125263
Received 2 January 2020; Received in revised form 9 April 2020; Accepted 27 April 2020
Available online 29 April 2020
1385-8947/ © 2020 Elsevier B.V. All rights reserved.
J. Fan, et al.
Fig. 1. Schematic diagram of preparation process for oxygen vacancy-induced In(OH)3 /carbon nitride composites.
traditional techniques have been developed, and photocatalytic ni-
trogen fixation under mild reaction conditions is an attractive one due
to its lower energy consumption [4]. Therefore, efficient, stable and
sustainable photocatalysts of nitrogen fixation are earnestly desired [5].
Graphitic carbon nitride (g-C3N4), a versatile metal-free n-type
semiconductor with facile synthesis, reliable physico-chemical stability,
medium band gap and “renewability from organic”, has shown a great
potential in many aspects especially for photocatalytic nitrogen fixation
[6–8]. Nevertheless, the fast recombination rate of charge carriers is
always an inherent deficiency for pure g-C3N4, which inevitably limit
its practical applications [9]. However, modification of g-C3N4 with
semiconductor to construct heterojunction is one of the controllable
and effective way to improve its photocatalytic activity [1,10]. Hadi
et al. [11] reported that using carbon dots and CdS nanoparticles to
decorate g-C3N4 can increase the mobility of electrons during the cat-
alytic reaction. The obtained CDs/CdS/g-C3N4 exhibited excellent N2
fixation performance. Xiao et al. [12] proposed the bridged SiW12 could
improve the adsorption and activation of nitrogen, which greatly up-
shift the reduction of nitrogen to ammonia on g-C3N4. Mou et al. [9]
compared five different g-C3N4/metal oxide composites prepared by
deep eutectic solvents method and confirmed that the efficient inter-
facial interaction between the g-C3N4 nanosheets and metal oxide na-
noparticles can promote the transfer efficiency of charge carriers, which
resulted in promotion for ammonia generation.
In(OH)3 is also an emerging n-type semiconductor and has been
extensively studied in many fields of photochemistry. Owning to its
wide bandgap (~5.2 eV), In(OH)3 is also usually used to fabricate
heterostructured photocatalysts with other semiconductors for photo-
activity amelioration, including AgPO4 [13], In2O3 [14], ZnIn2S4 [15]
and Bi2MoO6 [16], but In(OH)3 /g-C3N4 heterojunction has not been
reported yet. Moreover, hydroxides or oxides with high valence metal
ions, like In(OH)3, are easy to be created vacancies with reductants
during chemical precipitation synthesis [17,18]. And the existence of
vacancies would notably result into a superior photocatalytic activity
by preventing the recombination of photogenerated charge carriers
[19,20]. But to the best of our knowledge, use of vacancy-induced In
(OH)3 as one of the component to composite of other semiconductors
for improvement has rarely been reported either.
In this work, we reported a readily synthesis of oxygen vacancy-
induced In(OH)3 /carbon nitride heterojunction (OV-In(OH)3/CN) at
60℃and under atmospheric pressure. The In(OH)3 nanoparticles gen-
erated on the surfaces of g-C3N4 via a facile in-situ growth process, and
the oxygen vacancy was simultaneously etched by introducing glyoxal
as the reductant. The morphologies, structure and optical properties of
the OV-In(OH)3/CN were characterized by XRD, BET, FT-IR, TGA,
2
Chemical Engineering Journal 396 (2020) 125263
HRTEM, XPS, EPR, UV–vis DRS, PL spectra and electrochemical de-
tections. The photocatalytic activity of as-synthesized catalysts was
evaluated by N2 photofixation under ambient conditions and the pos-
sible mechanism was also discussed.
2. Experimental section
2.1. Materials and chemicals
Urea (≥99.5%), ethanol (≥99.8%), Indium chloride(InCl3,
≥99.9%) and Triethanolamine(≥99.5%) were purchased from
Shanghai Macklin Biochemical Technology Co., Ltd. Nafion® 117 so-
lution (5 wt%) were purchased from Shanghai Aladdin Industrial Co.,
Ltd. Other materials were purchased from Sinopharm Chemical Reagent
Co., Ltd and all reagents were used as received without further pur-
ifications.
2.2. Synthesis of OV-In(OH)3/CN photocatalysts samples
Pure g-C3N4 was prepared by reported thermal polymerization
method from urea[21]. The designed of OV-In(OH)3/CN composites
were then prepared as following steps. Firstly, 0.097 g InCl3 and 0.6 g
PVP were dissolved into 100 mL of deionized water under vigorous
stirring and 0.5 g as prepared g-C3N4 sample was subsequently dis-
persed in above mixed solution. Then, dilute NH3 solution was added
drop-wise to it at room temperature until pH reached to 8.5. Subse-
quently, 2 mL of 40% glyoxal aqueous solution was injected into the
mixture. After stirring for 4 h at 60℃, the final resulting sample was
obtained after centrifugation, alternately several times washing with
deionized water and ethanol and drying at 60℃.The weight ratio of
indium to g-C3N4 in obtained above sample was 1%, so it was denoted
as OV-In/CN-1. Three more samples, OV-In/CN-3, OV-In/CN-5 and OV-
In/CN-0 containing 3 wt%, 5 wt% and without indium, were also
prepared as the same process. For comparison, In(OH)3 / g-C3N4
composites, containing 3 wt% indium but without oxygen vacancy on
In(OH)3, was also synthesized in the absence of glyoxal, denoted as In/
CN-3. Schematic diagram of preparation process was shown in Fig. 1.
2.3. Characterization
The crystalline structures and phase compositions of the samples
were investigated by a Shimadzu 6100 X-ray diffractometer (XRD) with
a Cu Kα radiation flux (λ = 0.15418 nm, 35 kV, 200 mA) at a scanning
rate of 6° min −1 in the 2θ range of 10-80°. The micro-morphologies of
the samples were determined by means of the JEOL-2100F TEM
J. Fan, et al.
(120 kV). The components amount of all samples were determined by
TG analysis on a Mettler-Toledo STAR TG instrument at a heating rate
of 10 °C min –1 in oxygen with a 100 mL/min flow rate. The BET surface
area and pore sizes measurements were performed by using a
Quantachrome ASAP2020 BET instrument at 77 K. The composition
and surface properties were investigated using an ESCALAB 250Xi X-
ray photoelectron spectroscopy (XPS) measurement with Al Kα X-ray
(hν = 1486.6 eV) radiation. The existence of oxygen vacancies and
reactive species were analysed by an Albutran AXM-09 Electron spin
resonance (ESR) spectroscopy. For characteristics of semiconductor, the
UV–vis diffuse reflectance spectra (DRS) were performed on a Hitachi
3010 spectrophotometer at wavelengths of 200–800 nm with BaSO4 as
the reflectance standard. The steady-state photoluminescence (PL)
spectra were collected on a Hitachi F-4600 fluorescence spectro-
photometer under excitation at 370 nm and the time-resolved fluores-
cence emission decay spectra was detected using an Edinburgh
Analytical FLS1000 time-domain fluorescence spectrophotometer.
Photoelectrochemical measurements were measured using 0.1 M
Na2SO4 as an electrolyte solution on a CHI 660 electrochemical work-
station with a three-electrode cell system. The Pt wire and Ag/AgCl was
used as the counter and the reference electrode, respectively. The
working electrode was an FTO coating some samples on, the prepara-
tion and testing methods of it were same as those of Zhang et al[10].
2.4. Nitrogen photofixation testing
All nitrogen photofixation experiments were conducted in a double-
walled quartz reactor under the irradiation of a 300 W Xe lamp with a
420 nm cutoff filter (light density 100 mW /cm−2). The temperature of
reactor was maintained at 25℃ by water circulation in the outer jacket.
Typically, 0.1 g of photocatalyst was dispersed into 100 mL deionized
water in the reactor assisted by ultrasound. And 5 mL of triethanola-
mine was added to the suspension, as a hole scavenger. High-purity N2
was bubbled through the suspension at a flow rate of 100 mL /min.
After 1 h of dark bubbling, the visible light irradiation was turned on
and 3 mL of suspension was gathered as the sample at 1 h time inter-
vals. It was monitored by Nessler's reagent method to determine the
concentration of NH4+ after filtered through a 0.22 μm membrane
filter.
3. Results and discussion
3.1. Structure and morphology
The XRD analysis was used to investigate the crystalline structure of
the as-prepared catalysts (Fig. 2a). All patterns of the synthesized
composites displayed two clear diffraction peaks at 13.1° and 27.7°,
which are accordance with the (1 0 0) and (0 0 2) planes of g-C3N4
(JCPDS 87–1526) [22]. The results revealed that the original frame-
work of g-C3N4 would not be destroyed during the synthesis process.
However, almost no obvious peak of In(OH)3 (JCPDS No 76–1464) can
be observed because of its low contents, small particle size or low
crystallinity [23,24]. Meanwhile, the chemical functional groups of the
solids were further confirmed by FTIR spectra. As it can be seen in
Fig. 2b, all composites showed the similar characteristic absorption
peaks like g-C3N4, including a board peaks between 3000 and
3400 cm−1 (indicating N–H band), several peaks located in the range of
1240–1650 cm−1 (typical stretching modes of C-N heterocycles) and a
sharp peak at 810 cm−1 (vibration of triazine rings) [25,26]. Other-
wise, there are little absorption features of In(OH)3 displayed among
them, demonstrating no change of the layer structure of g-C3N4 by
combination with low amount of In(OH)3 [27,28], which corresponded
well to the XRD analysis.
The composition and In(OH)3 contents in the prepared composites
were determined by the thermogravimetric analysis (TGA). As can be
seen in Fig. 3, the TGA curves of all samples showed an obvious weight
3
Chemical Engineering Journal 396 (2020) 125263
loss between 480 and 680 °C because of the decomposition of the g-
C3N4 nanosheets [29]. The remaining mass of pure g-C3N4 sample al-
most equal to zero and remaining mass percentage for In/CN-3, OV-In/
CN-1, OV-In/CN-3 and OV-In/CN-5 was 3.13%, 1.29%, 3.21% and
5.39%, which was the weight of the residual In2O3. The conversion to
In2O3 from In(OH)3 can be reflected on the curve of OV-In/CN-3 and
OV-In/CN-5, just like an increase of weight loss rate between 285 and
312 °C [24,30]. Finally, the calculated accurate weight percentages (wt
%) of In(OH)3 in all samples were 3.74% for In/CN-3, 1.54% for OV-In/
CN-1, 3.83% for OV-In/CN-3 and 6.44% for OV-In/CN-5. Furthermore,
the mass loss of the composites occurred at lower temperature than that
of pure g-C3N4, which was attributed to catalytic oxidation by metal
oxides at high temperatures [31,32].
N2 adsorption–desorption isotherms were measured to investigate
the textural properties of the prepared photocatalysts, and the results
were shown in Table 1 and Fig. S1. All isotherms showed type IV, in-
dicating the presence of mesopores [33]. The BET specific surface areas
(SBET) of pure g-C3N4, In/CN-3, OV-In/CN-1, OV-In/CN-3 and OV-In/
CN-5 was 26.37, 51.64, 48.27, 57.19 and 63.08 m2/g, while their total
pore volume was 0.114, 0.237, 0.202, 0.253 and 0.287 cm3/g, re-
spectively. It can be seen that the SBET and pore volume of all com-
posite samples does not increased proportionally with the In(OH)3
content, which could be attributed to the aggregates of In(OH)3 parti-
cles on g-C3N4 [34].
The morphology and microstructure of In/CN-3 and OV-In/CN-3
samples were surveyed by TEM and HRTEM. As shown in Fig. 4a, the
image of g-C3N4 displayed an irregular stacked layer plates. The TEM
images of In/CN-3 and OV-In/CN-3 were shown in Fig. 4b and Fig. 4d.
It can be seen that In(OH)3 particles were uniformly distributed on the
surface of g-C3N4 sheet with a little aggregates. The average size of In
(OH)3 particle both in In/CN-3 and OV-In/CN-3 was similar, estimated
to be 5 ~ 25 nm, which was attributed to short crystal ripening time
and may confirm that the size would not be affected by the addition of
glyoxal [35]. As can be seen from HRTEM images (Fig. 4c, e and f),
lattice fringes with spacing values of 0.282 nm can be observed, cor-
responding to (2 2 0) crystal plane of cubic In(OH)3. And there was a
clear phase interface between g-C3N4 and In(OH)3, which was favorable
for heterojunction construction [16,36]. It was worth noticing that
some lattice fringes of In(OH)3 in OV-In/CN-3 image (Fig. 4e and f)
were damaged or distorted, which was the evidence of the existence of
oxygen vacancy on In(OH)3. Besides, the elemental mapping images
(Fig. 4g ~ k) ascertained the coexistence of C, N, O and In in the
composites and revealed their distribution furtherly.
XPS analysis was performed to identify the element composition and
surface chemical state of pure g-C3N4, In/CN-3 and OV-In/CN-3 sam-
ples. The survey XPS spectra revealed that C, N, O and In elements were
constituent elements of the composites (Fig. S2). The high resolution
spectra of C 1 s, N 1 s, O 1 s and In 3d were shown in Fig. 5. As can be
seen in Fig. 5a, the C 1 s spectra for pure g-C3N4 and OV-In/CN-3 both
showed two peaks located at 284.8 and 288.3 eV, corresponding to C–C
bonds of surface absorbed carbon and the sp2 hybridized nitrogen (N-
C = N) in the framework of g-C3N4, respectively[37]. Meanwhile, the N
1 s spectrum of pure g-C3N4 (Fig. 5b) can be deconvoluted into three
main peaks at 398.7 (N1), 399.1 (N2) and 400.7 eV (N3), which were
respectively ascribed to N-sp2C, N–H, and N-(C)3 bond in layered
structure. Compared with pure g-C3N4, the N2 and N3 peaks of OV-In/
CN-3 shifted towards higher binding energy to 400.0 and 401.1 eV due
to the interactions between g-C3N4 and In(OH)3 to form the hetero-
junction [38,39]. In the O 1 s spectrum of In/CN-3 (Fig. 5c), two peaks
at 531.4 and 533.2 eV corresponded to the lattice oxygen of In(OH)3
and absorbed hydroxyl groups on the surface of g-C3N4 and In
(OH)3[24,40]. While in that of OV-In/CN-3, another new peak ap-
peared at 531.8 eV, which may be attributed to the surface oxygen from
oxygen vacancies of In(OH)3 [38,41]. Moreover, compared with that of
In/CN-3, the In 3d high resolution spectra of OV-In/CN-3 sample
(Fig. 5d) exhibited that both of the two characteristic peaks moved to
J. Fan, et al. Chemical Engineering Journal 396 (2020) 125263

a 22.3 31.7 35.5 39.1 45.4 51.2 56.5

(220) (013)(222) (400) (420) (422)
66.2 70.8 75.3 b In(OH)3 1161
In-OH bonds

(200) (440)(442)(620)
OV-In/CN-5 505
In(OH)3 (JCPDS 76-1464) 1644 1416 1246

Transmittance (a.u.)
OV-In/CN-5 OV-In/CN-3 1560 1320
Intensity (a.u.)

OV-In/CN-1
OV-In/CN-3
In/CN-3

OV-In/CN-1
pure g-C3N4
In/CN-3
810
3200
hydrogen
pure g-C3N4 bonds heterocyclic
triazine
13.1 27.3 rings
(100) (002) JCPDS 87-1526 C-N bonds

10 20 30 40 50 60 70 80 4000 3100 2200 1300 400

2ș (Gegree) Wavenumber (cm-1)
Fig. 2. a) XRD patterns and b) FT-IR spectra of all synthesized photocatalyst samples.

vacancy in composites were originated from In(OH)3 rather than g-

95 pure g-C3N4 C3N4.

In/CN-3
75 In(OH)3 In2O3 3.2. Optical and electronic properties
OV-In/CN-1
In0.01
Weight %

OV-In/CN-3
In0.03 The light absorption property of pure g-C3N4, In(OH)3 and other
55 composite samples were determined by UV–vis DRS. As shown in
OV-In/CN-5
In0.05
Fig. 7a, In(OH)3 only presented a weak light absorption in ultraviolet
region and the g-C3N4 exhibited a typically valid absorption in the re-
35 gion from 250 nm to 450 nm. For other hybrids, although the absorp-
tion intensity in UV region decreased with the increase of coupled In
15 (OH)3, the photoabsorption ability for vis-light was similar with that of
pure g-C3N4, which may be due to the no absorbance of visible light of
In(OH)3 [16,43]. On the other hands, the absorption band edges of
-5 composites were hardly to be altered in the presence of In(OH)3.
0 200 400 600 800 The generation, separation, migration, and recombination efficiency
Temperature ( ) of photo-induced electron-hole pairs were monitored by photo-
luminescence (PL) and electrochemical analyses. The PL spectra of pure
Fig. 3. The TGA curves of all synthesized samples. g-C3N4 and other hybrid photocatalyst with 370 nm excitation lumi-
nescence was shown in Fig. 7b. The g-C3N4 sample displayed the
Table 1 highest emission intensity at 440 nm, which revealed its fastest re-
The textural structure parameters of all synthesized photocatalyst samples. combination rate of electrons and holes. For the In(OH)3 based com-
posites, their obviously decreased PL intensity suggested that hetero-
Surface Area (m2/ Pore Volume (cm3/ Average Pore Size
junction structure could enhance separation efficiency of photo-induced
g) g) (nm)
carriers [44]. Moreover, the PL peaks of all OV-In/CN samples is lower
pure g-C3N4 26.37 0.114 12.18 than that of In/CN-3 sample, demonstrating that oxygen vacancy would
In/CN-3 51.64 0.237 16.56 furtherly restrict the recombination of carriers and may enhance the
OV-In/CN-1 48.27 0.202 14.68
photocatalytic activity [45]. Meanwhile, the same results were also
OV-In/CN-3 57.19 0.253 15.57
OV-In/CN-5 63.08 0.287 18.10 obtained in electrochemical impedance spectra (EIS). In Fig. 7c, it can
be observed that OV-In/CN samples exhibited smaller radius than that
of In/CN-3 and pure g-C3N4. Namely, the smaller radius in EIS means
the direction of low energy, which revealed the appearance of In with lower recombination rate of photogenerated charge carriers [46]. In
low chemical valence, furtherly indicating the existence of oxygen va- addition, OV-In/CN-3 showed the lowest PL emission and smallest ra-
cancies [17,42]. dius among all prepared samples, implying the highest photocatalytic
Meanwhile, the oxygen vacancies in composite were confirmed by activity of OV-In/CN-3.
the EPR spectra as shown in Fig. 6, also. A remarkable signal at Photocurrent response is the direct evidence to figure charge carrier
g = 2.001 could be observed only for OV-In/CN-3 sample, which re- separation efficiency [47]. The photocurrent-time (I-t) curves were
vealed the electrons trapped on oxygen vacancies and confirmed the shown in Fig. 7d. All five samples displayed a sharp and stable response
existence of oxygen vacancies on composites. The absence of this signal to the light either on or off, and the photocurrent density for pure g-
in pure g-C3N4 and In/CN-3 samples implied their very low con- C3N4 and In/CN-3 was 0.35 and 1.4 μA/cm2 respectively. Compara-
centration of oxygen vacancies. Besides, no typical signal in the EPR tively, the response value of OV-In/CN-1, OV-In/CN-3 and OV-In/CN-5
spectra of OV-In/CN-0 sample (Fig. S3) suggested that the oxygen showed a significant increase, up to 2.2, 3.5, 4.4 μA/cm2. The results
implied that the oxygen vacancy on In(OH)3 was most likely to play a

4
J. Fan, et al. Chemical Engineering Journal 396 (2020) 125263

a b d(220)=0.282 c

C3N4

In(OH)3
In(OH)3 5 nm
d e f
d(220)=0.282
OV area
OV area

In(OH)3 10 nm 5 nm d(220)=0.282

g C h N i O j In k

250 nm 250 nm 250 nm 250 nm 250 nm

Fig. 4. a) TEM image of pure g-C3N4 sample, b) TEM image of In/CN-3 sample, c) HRTEM image of In/CN-3 sample, d) TEM image of OV-In/CN-3 sample, e, f)
HRTEM image of OV-In/CN-3 sample, g ~ k) High angle annular dark field scanning TEM image and corresponding EDX elemental mapping images of OV-In/CN-3
sample.

key role in separating electron-hole pairs, and OV-In/CN-3 sample may
exhibit an admirable photocatalytic performance due to its effective
separation efficiency.
Generally, the lifetime of charge carrier is related to the probability
of itself to be utilized [48]. With excitation at 440 nm, time-resolved
prompt fluorescence measurements were adopted to determine the
lifetimes of carrier of pure g-C3N4, In/CN-3 and OV-In/CN-3 sample
photocatalysts. The decay spectra were shown in Fig. 8, and the curves
could be fitted well to a double exponential equation [49]:
I = A1 e−t / τ1 + A2 e−t / τ2
And then, the average lifetimes (τa) of the three samples could be
calculated according to following equation and the values were also
attached in Fig. 8.
A1 τ12 + A2 τ22
τa =
A1 τ1 + A2 τ2
Consistently, In/CN-3 sample exhibited a longer lifetime (7.59 ns)
than that of pure g-C3N4 (8.19 ns) but shorter with respect to the OV-
In/CN-3 one (9.75 ns). The slower decay rate of OV-In/CN-3 demon-
strated the promotion of electron transport and migration time, which
was attributed to the “mediated trap” from oxygen vacancy on In(OH)3
[48]. It might be beneficial for composite to achieve photoactivity en-
hancement.
3.3. Photocatalytic performance test
The photocatalytic performance of catalysts was evaluated by
photocatalytic N2 fixation under vis-light irradiation. As shown in
Fig. 9a, the samples of OV-In/CN-1, 3 and 5 displayed markedly higher
NH3 generation efficiency than other photocatalysts, which could
confirm the key role of oxygen vacancies in enhancing the photo-
catalytic activity of catalysts. Among the three samples, OV-In/CN-3
exhibited the highest NH3 generation rate, up to 3.81 mM*h−1*g−1 of
catalyst, representing an excellent nitrogen fixation capacity compared
with others in relevant literature (summarized in Table. 2). Further-
more, the similar low NH3 generation rate of OV-In/CN-0 and pure g-
C3N4 implied that In(OH)3 was also indispensable for photocatalytic
improvement. The effects of N2 and O2 on the photocatalytic N2 fixation
were evaluated. As can be seen in Fig. 9b, when substituting N2 with Ar,
the nitrogen fixation capabilities of OV-In/CN-3 turned negligible,
which confirmed that N2 was is the only N source of NH3 synthesis [50].
The replacement of high-purity N2 with air induced the photocatalytic
efficiency of OV-In/CN-3 dramatically dropped to the same level as In/
CN-3, because the oxygen vacancies would be quenched by oxygen
molecule thus losing the ability to enhance photocatalytic activity [51].
In the following, the dominant active species in the photocatalytic re-
action were determined with quenching experiment. The results
(Fig. 9b) showed that nitrogen photofixation efficiency could be sup-
pressed with the addition of AgNO3, suggesting the photo-generated
electrons were the dominant active species[52].
The chemical stability of the catalysts is evaluated by cycling tests
and concentration of In leaching during the reaction. After six succes-
sive recycles, the N2 fixation performance of OV-In/CN-3 declined
slightly only in the second round and then remained constantly
(Fig. 9c). The concentration of In were always below 4 μg·L-1, just about

5
J. Fan, et al. Chemical Engineering Journal 396 (2020) 125263

a C 1s b N 1s

400.0 eV
OV-In/CN-3

Intensity (a.u.)
Intensity (a.u.)

401.1eV
OV-In/CN-3
C C 284.8 eV N sp2C
N C N 398.7 eV
288.3 eV

N (C)3
400.7 eV N H
399.1 eV
pure g-C3N4 pure g-C3N4

290 288 286 284 282 404 402 400 398 396
Binding Energy (eV) Binding Energy (eV)

c O 1s d 444.5 eV In 3d
531.8 eV 452.0 eV
oxygen vacancy

Intensity (a.u.)
Intensity (a.u.)

OV-In/CN-3
OV-In/CN-3

In OH 531.4 eV 452.4 eV 444.7 eV

In 3d3/2
surface In 3d5/2
OH
533.2 eV
In/CN-3 In/CN-3

537 535 533 531 529 527 459 454 449 444 439
Binding Energy (eV) Binding Energy (eV)
Fig. 5. a) C 1 s high-resolution XPS spectra of pure g-C3N4 and OV-In/CN-3 samples, b) N 1 s high-resolution XPS spectra of pure g-C3N4 and OV-In/CN-3 samples, c)
O 1 s high-resolution XPS spectra of In/CN-3 and OV-In/CN-3 samples, d) In 3d high-resolution XPS spectra of In/CN-3 and OV-In/CN-3 samples.

fixation, N2-TPD experiment was employed and showed in Fig. 10a. It

can be seen that two desorption peaks could be observed in all three
g=2.001 curves of g-C3N4, In/CN-3 and OV-In/CN-3 samples. The first peak
OV-In/CN-3
around 200 °C was the indication of physical adsorption and another
one centered nearby 460 °C was related to the chemisorption of N2
Intensity (a.u.)

[53]. The intensity for first peak of OV-In/CN-3 sample was almost no
difference to that of g-C3N4 and In/CN-3. But there are obvious dif-
ferences in the intensity for the other peak. The 460 °C peak of OV-In/
In/CN-3
CN-3 was much higher than that of In/CN-3, and this peak of In/CN-3
was higher than that of pure g-C3N4. This finding indicated that the
active sites for N2 absorption might be related to ≡In3+ and the surface
oxygen vacancy of OV-In(OH)3, and the oxygen vacancy has a higher
pure g-C3N4 affinity to N2, becoming the dominant site. These more chemisorption
sites is essential for photocatalytic N2 fixation. So it suggested the
reason for the enhancement in photocatalytic activity not only should
be attributed to the ameliorated separation efficiency and lifetime of
3460 3480 3500 3520 3540 3560 charge carrier by oxygen vacancies, but also to the improved chemical
adsorption of N2.
Magnetic field (G) To distinguish the heterojunction type of OV-In(OH)3/CN system,
Fig. 6. EPR spectra of pure g-C3N4, In/CN-3 and OV-In/CN-3 samples. serials of tests were carried out. According to the UV–vis DRS (Fig. 7a),
the band gaps of pure g-C3N4 can be calculated via Kubelka–Munk
method, and the value was 2.80 eV (Fig. 10b). And oxygen vacancy-
1‰ level of the In decorated on g-C3N4 (Fig. 9d). Both results indicated induced In(OH)3 (OV-In(OH)3) displayed two band gap energies of 4.65
that the stability of catalysts was reliable. and 3.74 eV, the latter was related to the vacancy[24]. Meanwhile, the
valence band X-ray photoelectron spectra (VB-XPS) were employed to
find the valence band (VB) position of them. As can be seen in Fig. 10c,
3.4. Photocatalytic mechanism in the OV-In(OH)3/CN system
the valence band edge potential of g-C3N4 and OV-In(OH)3 was 1.95
and 3.04 eV vs NHE, respectively. Based on the equation of
To confirm the effects of oxygen vacancies on the photocatalytic N2

6
J. Fan, et al. Chemical Engineering Journal 396 (2020) 125263

a b
pure g-C3N4
pure g-C3N4
In/CN-3
Absorbance (a.u.)

In/CN-3

Intensity (a.u.)
OV-In/CN-1
OV-In/CN-1
OV-In/CN-3
OV-In/CN-5
OV-In/CN-5
OV-In/CN-3
OV-In(OH)3

250 350 450 550 650 750 400 450 500 550 600
Wavelength (nm) Wavelength (nm)

20000 7.0
c pure g-C3N4
pure g-C 3N4 d pure g-C3N4
In-0.05-C3N4 In/CN-3
pure g-C3N4 OV-In/CN-1
—C3N4

-2 )
In-0.05-C3N4
In/CN-3 5.6
15000 OV-In/CN-3
0.03 OV-In/CN-5
In-0.03-C3N4
In-0.03-C3N4
OV-In/CN-1 Current Density (ȝA cm
-Z'' (Ohm)

4.2
10000 In-0.01-C3N4
OV-In/CN-5

0.03
OV-In/CN-3 2.8

5000
1.4

0 0.0
0 3000 6000 9000 0 25 50 75 100 125
Z' (Ohm) Time/s
Fig. 7. (a) UV–vis DRS spectra (b) PL spectra, (c) EIS Nyquist plots in the dark, and (d) transient photocurrent response of all as-prepared samples.

visible light absorption of In(OH)3, the electrons only could be excited

IJ1/ns(A1/%) IJ2/ns(A2/%) IJa/ns from the VB of g-C3N4 and reach its CB to be received by N2 under vis-
pure g-C3N4 13.85(14.07) 3.35 (85.93) 7.59 light irradiation. Meanwhile, the holes (h+) remained in VB would be
In/CN-3 2.57 (65.32) 10.73(34.68) 8.19 captured by quencher if it exists. It is worth noting that the CB of g-C3N4
OV-In/CN-3 3.92 (74.33) 14.36(25.67) 9.75
is close to the defect energy level of OV-In(OH)3, which contributes
Counts (a.u.)

some electrons at the former easily to transfer to the latter. The electron
at defect energy level would be trapped so that it has a longer lifetime
to be adsorbed by molecular nitrogen [45,51]. And this special migra-
C3N4
pure g-C3 N4
tion process also increases the separation efficiency of electron-hole
In/CN-3 pairs [16]. The detail transfer mechanism of OV-In(OH)3 / g-C3N4
photocatalytic system was described in Fig. 11.
0.03
OV-In/CN-3
Hence, the enhancement mechanism for the high photocatalytic
activity of OV-In(OH)3 / g-C3N4 photocatalytic system could also be
explained. It could be attributed to the efficient interfacial interaction
which because of the proper photoelectric and surface characteristics of
0 10 20 30 40 50 g-C3N4 and OV-In(OH)3. ≡In3+ and surface oxygen vacancy of OV-In
Time /ns (OH)3 provides an effective adsorption site for N2, but it cannot produce
enough photoelectrons because of its weak visible light response, so its
Fig. 8. Time-resolved PL spectra of pure g-C3N4, In/CN-3 and OV-In/CN-3
samples.
photocatalytic activity is poor. g-C3N4 has enough visible light response
to produce photoelectron, but it lacks N2 adsorption site, so its nitrogen
fixation effect is also poor. When they are combined, the adsorbed N2
ECB = Eg − EVB, the conduction band (CB) edges of them were ob- can obtain photoelectrons from g-C3N4 to be reduced. In addition, the
tained, to be −0.85 and −1.61 vs NHE, respectively. Besides, the po- photocatalytic activity of OV-In/CN can be further enhanced due to the
sitions of defect energy level of OV-In(OH)3 could be also calculated to transfer mechanism mentioned above.
be −0.70 eV.
According to above results, the possible transfer mechanism of OV-
In(OH)3 / g-C3N4 could be proposed as follows: due to disability for

7
J. Fan, et al. Chemical Engineering Journal 396 (2020) 125263

1Ar1ambient
20
NH3 Concentration (mmol/L·h)) a pureg-C3N4
pure g-C3N4 In/CN-3
20 b

NH3 Concentration (mmol/L·h))

OV-In/CN-0 OV-In/CN-1 1Air2ambient
OV-In/CN-3 OV-In/CN-5
15 15 1with
3 AgNO3

control
OV-In/CN-3

10 10

dark vis-light dark vis-light

5 5

0 0
-1 0 1 2 3 4 5 -1 0 1 2 3 4 5
Time/h Time/h

5
20
c d
NH3 Concentration (mmol/L·h)

4
15

Leaching In (ȝg/L)
3
10
2

5
1 dark vis-light

0 0
0 5 10 15 20 25 30 -1 0 1 2 3 4 5
Time/h Time/h
Fig. 9. (a) Photocatalytic nitrogen fixation over all as-prepared samples, (b) controlling experiments of nitrogen fixation over OV-In/CN-3 sample, (c) cycle runs for
photocatalytic nitrogen fixation over OV-In/CN-3 sample and (d) the concentration of In leaching during the reaction.

4. Conclusion N2. The OV-In(OH)3 / g-C3N4 heterojunction exhibited excellent pho-

tocatalytic activity for nitrogen fixation and the maximum NH3 gen-
In this study, an oxygen vacancy-induced In(OH)3 /carbon nitride eration rate was achieved by OV-In/CN-3 sample to be
0D/2D heterojunction has been synthesized successfully by generating 3.81 mM*h−1*g−1, which was about 10 times as that of pure g-C3N4
In(OH)3 nanoparticles on g-C3N4 nanosheets in the presence of glyoxal and was also higher than that of other catalysts reported. Besides, the
though a readily precipitation growth method. The existence of oxygen prepared catalysts also showed a good chemical stability after six cy-
vacancies on In(OH)3 was confirmed by HRTEM, XPS and EPR analysis. cles. Foreseeably, this new metal hydroxide /C3N4 heterojunction is a
Although the In(OH)3 in heterojunction cannot produce photo- great potential alternative catalyst in industrialized photocatalytic re-
generated electrons under vis-light irradiation, the oxygen vacancies on duction process in the future.
it will receive and “trap” some excited electrons from g-C3N4, pro-
moting the electron-hole pairs separation efficiency and prolonging the
lifetime of carriers, which were revealed by PL spectra, electrochemical Declaration of Competing Interest
experiments and time-resolved fluorescence spectra. The oxygen va-
cancies on In(OH)3 also could introduce many chemisorption sites for The authors declare that they have no known competing financial

Table 2
Comparison of g-C3N4 based catalysts for photocatalytic nitrogen fixation.
Photocatalyst composite method (temp.) Nitrogen source Light source Hole scavenger NH3 generation rate (mM /h per 1 g Ref.
(power) catalyst)

OVs-In(OH)3/g-C3N4 precipitation(333 K) N2 vis-light(300 W) triethanolamine 3.81 This study

NVs-g-C3N4 calcination(793 K) N2 vis-light(300 W) methanol 1.24 [50]
S doped CVs-g-C3N4 One-step CVD (823 K) Air UV vis-light methanol 5.99 [53]
(500 W)
Fe2O3/g-C3N4 deep eutectic solvent(363 K) before Air UV vis-light methanol 4.38 [9]
polymerization (300 W)
TiO2@C/g-C3N4 one-step calcination(823 K) N2 vis-light(300 W) methanol 0.25 [1]
SiW12/K-C3N4 heat-treated(573 K) N2 UV vis-light none 0.35 [12]
(100 W)

8
J. Fan, et al.
Fig. 10. (a) TPD spectra of the as-prepared pure g-C3N4, In/CN-3 and OV-In/
CN-3 samples, (b) The Kubelka-Munk plot used to estimate band gap energies of
pure g-C3N4 and OV-In(OH)3, (c) VB-XPS spectra of pure g-C3N4 and OV-In(OH)
3.
interests or personal relationships that could have appeared to influ-
ence the work reported in this paper.
Acknowledgements
This study was supported by the National Key Research and
Development Plan of China (grant numbers 2017YFC0806305) and the
Natural Science Foundation of China (grant numbers 51508564).
9
Chemical Engineering Journal 396 (2020) 125263
Fig. 11. Schematic illustration of photocatalytic N2 fixation over OV-In(OH)3/
g-C3N4 system.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://
doi.org/10.1016/j.cej.2020.125263.
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