A Readily Synthesis of Oxygen Vacancy Induced

You might also like

Download as pdf or txt
Download as pdf or txt
You are on page 1of 10

Chemical Engineering Journal 396 (2020) 125263

Contents lists available at ScienceDirect

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. Chemical Engineering Journal 396 (2020) 125263

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- HRTEM, XPS, EPR, UV–vis DRS, PL spectra and electrochemical de-
trogen fixation under mild reaction conditions is an attractive one due tections. The photocatalytic activity of as-synthesized catalysts was
to its lower energy consumption [4]. Therefore, efficient, stable and evaluated by N2 photofixation under ambient conditions and the pos-
sustainable photocatalysts of nitrogen fixation are earnestly desired [5]. sible mechanism was also discussed.
Graphitic carbon nitride (g-C3N4), a versatile metal-free n-type
semiconductor with facile synthesis, reliable physico-chemical stability, 2. Experimental section
medium band gap and “renewability from organic”, has shown a great
potential in many aspects especially for photocatalytic nitrogen fixation 2.1. Materials and chemicals
[6–8]. Nevertheless, the fast recombination rate of charge carriers is
always an inherent deficiency for pure g-C3N4, which inevitably limit Urea (≥99.5%), ethanol (≥99.8%), Indium chloride(InCl3,
its practical applications [9]. However, modification of g-C3N4 with ≥99.9%) and Triethanolamine(≥99.5%) were purchased from
semiconductor to construct heterojunction is one of the controllable Shanghai Macklin Biochemical Technology Co., Ltd. Nafion® 117 so-
and effective way to improve its photocatalytic activity [1,10]. Hadi lution (5 wt%) were purchased from Shanghai Aladdin Industrial Co.,
et al. [11] reported that using carbon dots and CdS nanoparticles to Ltd. Other materials were purchased from Sinopharm Chemical Reagent
decorate g-C3N4 can increase the mobility of electrons during the cat- Co., Ltd and all reagents were used as received without further pur-
alytic reaction. The obtained CDs/CdS/g-C3N4 exhibited excellent N2 ifications.
fixation performance. Xiao et al. [12] proposed the bridged SiW12 could
improve the adsorption and activation of nitrogen, which greatly up- 2.2. Synthesis of OV-In(OH)3/CN photocatalysts samples
shift the reduction of nitrogen to ammonia on g-C3N4. Mou et al. [9]
compared five different g-C3N4/metal oxide composites prepared by Pure g-C3N4 was prepared by reported thermal polymerization
deep eutectic solvents method and confirmed that the efficient inter- method from urea[21]. The designed of OV-In(OH)3/CN composites
facial interaction between the g-C3N4 nanosheets and metal oxide na- were then prepared as following steps. Firstly, 0.097 g InCl3 and 0.6 g
noparticles can promote the transfer efficiency of charge carriers, which PVP were dissolved into 100 mL of deionized water under vigorous
resulted in promotion for ammonia generation. stirring and 0.5 g as prepared g-C3N4 sample was subsequently dis-
In(OH)3 is also an emerging n-type semiconductor and has been persed in above mixed solution. Then, dilute NH3 solution was added
extensively studied in many fields of photochemistry. Owning to its drop-wise to it at room temperature until pH reached to 8.5. Subse-
wide bandgap (~5.2 eV), In(OH)3 is also usually used to fabricate quently, 2 mL of 40% glyoxal aqueous solution was injected into the
heterostructured photocatalysts with other semiconductors for photo- mixture. After stirring for 4 h at 60℃, the final resulting sample was
activity amelioration, including AgPO4 [13], In2O3 [14], ZnIn2S4 [15] obtained after centrifugation, alternately several times washing with
and Bi2MoO6 [16], but In(OH)3 /g-C3N4 heterojunction has not been deionized water and ethanol and drying at 60℃.The weight ratio of
reported yet. Moreover, hydroxides or oxides with high valence metal indium to g-C3N4 in obtained above sample was 1%, so it was denoted
ions, like In(OH)3, are easy to be created vacancies with reductants as OV-In/CN-1. Three more samples, OV-In/CN-3, OV-In/CN-5 and OV-
during chemical precipitation synthesis [17,18]. And the existence of In/CN-0 containing 3 wt%, 5 wt% and without indium, were also
vacancies would notably result into a superior photocatalytic activity prepared as the same process. For comparison, In(OH)3 / g-C3N4
by preventing the recombination of photogenerated charge carriers composites, containing 3 wt% indium but without oxygen vacancy on
[19,20]. But to the best of our knowledge, use of vacancy-induced In In(OH)3, was also synthesized in the absence of glyoxal, denoted as In/
(OH)3 as one of the component to composite of other semiconductors CN-3. Schematic diagram of preparation process was shown in Fig. 1.
for improvement has rarely been reported either.
In this work, we reported a readily synthesis of oxygen vacancy- 2.3. Characterization
induced In(OH)3 /carbon nitride heterojunction (OV-In(OH)3/CN) at
60℃and under atmospheric pressure. The In(OH)3 nanoparticles gen- The crystalline structures and phase compositions of the samples
erated on the surfaces of g-C3N4 via a facile in-situ growth process, and were investigated by a Shimadzu 6100 X-ray diffractometer (XRD) with
the oxygen vacancy was simultaneously etched by introducing glyoxal a Cu Kα radiation flux (λ = 0.15418 nm, 35 kV, 200 mA) at a scanning
as the reductant. The morphologies, structure and optical properties of rate of 6° min −1 in the 2θ range of 10-80°. The micro-morphologies of
the OV-In(OH)3/CN were characterized by XRD, BET, FT-IR, TGA, the samples were determined by means of the JEOL-2100F TEM

2
J. Fan, et al. Chemical Engineering Journal 396 (2020) 125263

(120 kV). The components amount of all samples were determined by loss between 480 and 680 °C because of the decomposition of the g-
TG analysis on a Mettler-Toledo STAR TG instrument at a heating rate C3N4 nanosheets [29]. The remaining mass of pure g-C3N4 sample al-
of 10 °C min –1 in oxygen with a 100 mL/min flow rate. The BET surface most equal to zero and remaining mass percentage for In/CN-3, OV-In/
area and pore sizes measurements were performed by using a CN-1, OV-In/CN-3 and OV-In/CN-5 was 3.13%, 1.29%, 3.21% and
Quantachrome ASAP2020 BET instrument at 77 K. The composition 5.39%, which was the weight of the residual In2O3. The conversion to
and surface properties were investigated using an ESCALAB 250Xi X- In2O3 from In(OH)3 can be reflected on the curve of OV-In/CN-3 and
ray photoelectron spectroscopy (XPS) measurement with Al Kα X-ray OV-In/CN-5, just like an increase of weight loss rate between 285 and
(hν = 1486.6 eV) radiation. The existence of oxygen vacancies and 312 °C [24,30]. Finally, the calculated accurate weight percentages (wt
reactive species were analysed by an Albutran AXM-09 Electron spin %) of In(OH)3 in all samples were 3.74% for In/CN-3, 1.54% for OV-In/
resonance (ESR) spectroscopy. For characteristics of semiconductor, the CN-1, 3.83% for OV-In/CN-3 and 6.44% for OV-In/CN-5. Furthermore,
UV–vis diffuse reflectance spectra (DRS) were performed on a Hitachi the mass loss of the composites occurred at lower temperature than that
3010 spectrophotometer at wavelengths of 200–800 nm with BaSO4 as of pure g-C3N4, which was attributed to catalytic oxidation by metal
the reflectance standard. The steady-state photoluminescence (PL) oxides at high temperatures [31,32].
spectra were collected on a Hitachi F-4600 fluorescence spectro- N2 adsorption–desorption isotherms were measured to investigate
photometer under excitation at 370 nm and the time-resolved fluores- the textural properties of the prepared photocatalysts, and the results
cence emission decay spectra was detected using an Edinburgh were shown in Table 1 and Fig. S1. All isotherms showed type IV, in-
Analytical FLS1000 time-domain fluorescence spectrophotometer. dicating the presence of mesopores [33]. The BET specific surface areas
Photoelectrochemical measurements were measured using 0.1 M (SBET) of pure g-C3N4, In/CN-3, OV-In/CN-1, OV-In/CN-3 and OV-In/
Na2SO4 as an electrolyte solution on a CHI 660 electrochemical work- CN-5 was 26.37, 51.64, 48.27, 57.19 and 63.08 m2/g, while their total
station with a three-electrode cell system. The Pt wire and Ag/AgCl was pore volume was 0.114, 0.237, 0.202, 0.253 and 0.287 cm3/g, re-
used as the counter and the reference electrode, respectively. The spectively. It can be seen that the SBET and pore volume of all com-
working electrode was an FTO coating some samples on, the prepara- posite samples does not increased proportionally with the In(OH)3
tion and testing methods of it were same as those of Zhang et al[10]. content, which could be attributed to the aggregates of In(OH)3 parti-
cles on g-C3N4 [34].
2.4. Nitrogen photofixation testing 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
All nitrogen photofixation experiments were conducted in a double- image of g-C3N4 displayed an irregular stacked layer plates. The TEM
walled quartz reactor under the irradiation of a 300 W Xe lamp with a images of In/CN-3 and OV-In/CN-3 were shown in Fig. 4b and Fig. 4d.
420 nm cutoff filter (light density 100 mW /cm−2). The temperature of It can be seen that In(OH)3 particles were uniformly distributed on the
reactor was maintained at 25℃ by water circulation in the outer jacket. surface of g-C3N4 sheet with a little aggregates. The average size of In
Typically, 0.1 g of photocatalyst was dispersed into 100 mL deionized (OH)3 particle both in In/CN-3 and OV-In/CN-3 was similar, estimated
water in the reactor assisted by ultrasound. And 5 mL of triethanola- to be 5 ~ 25 nm, which was attributed to short crystal ripening time
mine was added to the suspension, as a hole scavenger. High-purity N2 and may confirm that the size would not be affected by the addition of
was bubbled through the suspension at a flow rate of 100 mL /min. glyoxal [35]. As can be seen from HRTEM images (Fig. 4c, e and f),
After 1 h of dark bubbling, the visible light irradiation was turned on lattice fringes with spacing values of 0.282 nm can be observed, cor-
and 3 mL of suspension was gathered as the sample at 1 h time inter- responding to (2 2 0) crystal plane of cubic In(OH)3. And there was a
vals. It was monitored by Nessler's reagent method to determine the clear phase interface between g-C3N4 and In(OH)3, which was favorable
concentration of NH4+ after filtered through a 0.22 μm membrane for heterojunction construction [16,36]. It was worth noticing that
filter. 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
3. Results and discussion 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
3.1. Structure and morphology composites and revealed their distribution furtherly.
XPS analysis was performed to identify the element composition and
The XRD analysis was used to investigate the crystalline structure of surface chemical state of pure g-C3N4, In/CN-3 and OV-In/CN-3 sam-
the as-prepared catalysts (Fig. 2a). All patterns of the synthesized ples. The survey XPS spectra revealed that C, N, O and In elements were
composites displayed two clear diffraction peaks at 13.1° and 27.7°, constituent elements of the composites (Fig. S2). The high resolution
which are accordance with the (1 0 0) and (0 0 2) planes of g-C3N4 spectra of C 1 s, N 1 s, O 1 s and In 3d were shown in Fig. 5. As can be
(JCPDS 87–1526) [22]. The results revealed that the original frame- seen in Fig. 5a, the C 1 s spectra for pure g-C3N4 and OV-In/CN-3 both
work of g-C3N4 would not be destroyed during the synthesis process. showed two peaks located at 284.8 and 288.3 eV, corresponding to C–C
However, almost no obvious peak of In(OH)3 (JCPDS No 76–1464) can bonds of surface absorbed carbon and the sp2 hybridized nitrogen (N-
be observed because of its low contents, small particle size or low C = N) in the framework of g-C3N4, respectively[37]. Meanwhile, the N
crystallinity [23,24]. Meanwhile, the chemical functional groups of the 1 s spectrum of pure g-C3N4 (Fig. 5b) can be deconvoluted into three
solids were further confirmed by FTIR spectra. As it can be seen in main peaks at 398.7 (N1), 399.1 (N2) and 400.7 eV (N3), which were
Fig. 2b, all composites showed the similar characteristic absorption respectively ascribed to N-sp2C, N–H, and N-(C)3 bond in layered
peaks like g-C3N4, including a board peaks between 3000 and structure. Compared with pure g-C3N4, the N2 and N3 peaks of OV-In/
3400 cm−1 (indicating N–H band), several peaks located in the range of CN-3 shifted towards higher binding energy to 400.0 and 401.1 eV due
1240–1650 cm−1 (typical stretching modes of C-N heterocycles) and a to the interactions between g-C3N4 and In(OH)3 to form the hetero-
sharp peak at 810 cm−1 (vibration of triazine rings) [25,26]. Other- junction [38,39]. In the O 1 s spectrum of In/CN-3 (Fig. 5c), two peaks
wise, there are little absorption features of In(OH)3 displayed among at 531.4 and 533.2 eV corresponded to the lattice oxygen of In(OH)3
them, demonstrating no change of the layer structure of g-C3N4 by and absorbed hydroxyl groups on the surface of g-C3N4 and In
combination with low amount of In(OH)3 [27,28], which corresponded (OH)3[24,40]. While in that of OV-In/CN-3, another new peak ap-
well to the XRD analysis. peared at 531.8 eV, which may be attributed to the surface oxygen from
The composition and In(OH)3 contents in the prepared composites oxygen vacancies of In(OH)3 [38,41]. Moreover, compared with that of
were determined by the thermogravimetric analysis (TGA). As can be In/CN-3, the In 3d high resolution spectra of OV-In/CN-3 sample
seen in Fig. 3, the TGA curves of all samples showed an obvious weight (Fig. 5d) exhibited that both of the two characteristic peaks moved to

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

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. 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.

References

[1] Q. Liu, L. Ai, J. Jiang, MXene-derived TiO2@C/g-C3N4 heterojunctions for highly


efficient nitrogen photofixation, J. Mater. Chem. A 6 (2018) 4102–4110.
[2] P.C. Dos Santos, R.Y. Igarashi, H.-I. Lee, B.M. Hoffman, L.C. Seefeldt, D.R. Dean,
Substrate interactions with the nitrogenase active site, Accounts Chem. Res. 38
(2005) 208–214.
[3] S. Sun, X. Li, W. Wang, L. Zhang, X. Sun, Photocatalytic robust solar energy re-
duction of dinitrogen to ammonia on ultrathin MoS2, Appl. Catal. B-Environ. 200
(2017) 323–329.
[4] J. Ge, L. Zhang, J. Xu, Y. Liu, D. Jiang, P. Du, Nitrogen photofixation on holey g-
C3N4 nanosheets with carbon vacancies under visible-light irradiation, Chinese
Chem. Lett. (2019).
[5] Y. Nishibayashi, Recent progress in transition-metal-catalyzed reduction of mole-
cular dinitrogen under ambient reaction conditions, Inorg. Chem. 54 (2015)
9234–9247.
[6] D. Masih, Y. Ma, S. Rohani, Graphitic C3N4 based noble-metal-free photocatalyst
systems: A review, Appl. Catal. B-Environ. 206 (2017) 556–588.
[7] Y. Wang, X. Wang, M. Antonietti, Polymeric graphitic carbon nitride as a hetero-
geneous organocatalyst: from photochemistry to multipurpose catalysis to sus-
tainable chemistry, Angew. Chem. 51 (2012) 68–89.
[8] M. Volokh, G. Peng, J. Barrio, M. Shalom, Carbon Nitride Materials for Water
Splitting Photoelectrochemical Cells, Angew. Chem. 58 (2019) 6138–6151.
[9] H. Mou, J. Wang, D. Zhang, D. Yu, W. Chen, D. Wang, T. Mu, A one-step deep
eutectic solvent assisted synthesis of carbon nitride/metal oxide composites for
photocatalytic nitrogen fixation, J. Mater. Chem. A 7 (2019) 5719–5725.
[10] H. Zhang, W. Tian, L. Zhou, H. Sun, M. Tade, S. Wang, Monodisperse Co3O4
quantum dots on porous carbon nitride nanosheets for enhanced visible-light-driven
water oxidation, Appl. Catal. B-Environ. 223 (2018) 2–9.
[11] H. Diarmand-Khalilabad, A. Habibi-Yangjeh, D. Seifzadeh, S. Asadzadeh-
Khaneghah, E. Vesali-Kermani, g-C3N4 nanosheets decorated with carbon dots and
CdS nanoparticles: Novel nanocomposites with excellent nitrogen photofixation
ability under simulated solar irradiation, Ceram. Int. 45 (2019) 2542–2555.
[12] C. Xiao, L. Zhang, K. Wang, H. Wang, Y. Zhou, W. Wang, A new approach to en-
Fig. 10. (a) TPD spectra of the as-prepared pure g-C3N4, In/CN-3 and OV-In/ hance photocatalytic nitrogen fixation performance via phosphate-bridge: a case
study of SiW12/K-C3N4, Appl. Catal. B-Environ. 239 (2018) 260–267.
CN-3 samples, (b) The Kubelka-Munk plot used to estimate band gap energies of
[13] J. Guo, S. Ouyang, H. Zhou, T. Kako, J. Ye, Ag3PO4/In(OH)3 Composite
pure g-C3N4 and OV-In(OH)3, (c) VB-XPS spectra of pure g-C3N4 and OV-In(OH) Photocatalysts with Adjustable Surface-Electric Property for Efficient
3. Photodegradation of Organic Dyes under Simulated Solar-Light Irradiation, J. Phys.
Chem. C 117 (2013) 17716–17724.
[14] C. Shifu, Y. Xiaoling, Z. Huaye, L. Wei, Preparation, characterization and activity
interests or personal relationships that could have appeared to influ- evaluation of heterostructure In2O3 /In(OH)3 photocatalyst, J. Hazard. Mater. 180
ence the work reported in this paper. (2010) 735–740.
[15] Y. Li, Y. Hou, Q. Fu, S. Peng, Y.H. Hu, Oriented growth of ZnIn2S4/In(OH)3 het-
erojunction by a facile hydrothermal transformation for efficient photocatalytic H2
Acknowledgements production, Appl. Catal. B-Environ. 206 (2017) 726–733.
[16] T. Hu, H. Li, Z. Liang, N. Du, W. Hou, Facile synthesis of indium hydroxide na-
nosheet/bismuth molybdate hierarchical microsphere heterojunction with en-
This study was supported by the National Key Research and hanced photocatalytic performance, J. Colloid Interf. Sci. 545 (2019) 301–310.
Development Plan of China (grant numbers 2017YFC0806305) and the [17] S. Yu, Y. Zhang, F. Dong, M. Li, T. Zhang, H. Huang, Readily achieving con-
centration-tunable oxygen vacancies in Bi2O2CO3: Triple-functional role for
Natural Science Foundation of China (grant numbers 51508564).

9
J. Fan, et al. Chemical Engineering Journal 396 (2020) 125263

efficient visible-light photocatalytic redox performance, Appl. Catal. B-Environ. 226 [35] K.A. Ramisetty, Å.C. Rasmuson, Controlling the Product Crystal Size Distribution by
(2018) 441–450. Strategic Application of Ultrasonication, Cryst. Growth Des. 18 (2018) 1697–1709.
[18] V. Markevich, I. Hawkins, A. Peaker, K. Emtsev, V. Emtsev, V. Litvinov, L. Murin, [36] B. Liang, D. Han, C. Sun, W. Zhang, Q. Qin, Deposition of ZnO flowers on the surface
L. Dobaczewski, Vacancy–group-V-impurity atom pairs in Ge crystals doped with P, of g-C3N4 by solid phase reaction, Funct. Mater. Lett. 11 (2018) 1850020.
As, Sb, and Bi, Phys. Rev. B 70 (2004) 235213. [37] H. Yu, R. Shi, Y. Zhao, T. Bian, Y. Zhao, C. Zhou, G.I. Waterhouse, L.Z. Wu,
[19] M. Liang, T. Borjigin, Y. Zhang, B. Liu, H. Liu, H. Guo, Controlled assemble of C.H. Tung, T. Zhang, Alkali-assisted synthesis of nitrogen deficient graphitic carbon
hollow heterostructured g-C3N4@CeO2 with rich oxygen vacancies for enhanced nitride with tunable band Structures for efficient visible-light-driven hydrogen
photocatalytic CO2 reduction, Appl. Catal. B-Environ. 243 (2019) 566–575. evolution, Adv. Mater. 29 (2017) 1605148.
[20] Y.-X. Pan, Z.-Q. Sun, H.-P. Cong, Y.-L. Men, S. Xin, J. Song, S.-H. Yu, Photocatalytic [38] F. Zhang, L. Huang, P. Ding, C. Wang, Q. Wang, H. Wang, Y. Li, H. Xu, H. Li, One-
CO2 reduction highly enhanced by oxygen vacancies on Pt-nanoparticle-dispersed step oxygen vacancy engineering of WO3-x /2D g-C3N4 heterostructure: Triple ef-
gallium oxide, Nano Res. 9 (2016) 1689–1700. fects for sustaining photoactivity, J. Alloy. Compd. 795 (2019) 426–435.
[21] Z. Zhao, J. Fan, X. Deng, J. Liu, One-step synthesis of phosphorus-doped g-C3N4 [39] W. Wang, J. Fang, S. Shao, M. Lai, C. Lu, Compact and uniform TiO2@g-C3N4 core-
/Co3O4 quantum dots from vitamin B12 with enhanced visible-light photocatalytic shell quantum heterojunction for photocatalytic degradation of tetracycline anti-
activity for metronidazole degradation, Chem. Eng. J. 360 (2019) 1517–1529. biotics, Appl. Catal. B-Environ. 217 (2017) 57–64.
[22] P. Qiu, C. Xu, H. Chen, F. Jiang, X. Wang, R. Lu, X. Zhang, One step synthesis of [40] Y. Deng, L. Tang, C. Feng, G. Zeng, Z. Chen, J. Wang, H. Feng, B. Peng, Y. Liu,
oxygen doped porous graphitic carbon nitride with remarkable improvement of Y. Zhou, Insight into the dual-channel charge-charrier transfer path for nonmetal
photo-oxidation activity: Role of oxygen on visible light photocatalytic activity, plasmonic tungsten oxide based composites with boosted photocatalytic activity
Appl. Catal. B-Environ. 206 (2017) 319–327. under full-spectrum light, Appl. Catal. B-Environ. 235 (2018) 225–237.
[23] Y. Jiao, Q. Huang, J. Wang, Z. He, Z. Li, A novel MoS2 quantum dots (QDs) deco- [41] K.-Y. Chen, C.-C. Hsu, H.-C. Yu, Y.-M. Peng, C.-C. Yang, Y.-K. Su, The effect of
rated Z-scheme g-C3N4 nanosheet/N-doped carbon dots heterostructure photo- oxygen vacancy concentration on indium gallium oxide solar blind photodetector,
catalyst for photocatalytic hydrogen evolution, Appl. Catal. B-Environ. 247 (2019) IEEE T. Electron Dev. 65 (2018) 1817–1822.
124–132. [42] O. Martin, A.J. Martin, C. Mondelli, S. Mitchell, T.F. Segawa, R. Hauert, C. Drouilly,
[24] B. Hu, M. Hu, Q. Guo, K. Wang, X. Wang, In-vacancy engineered plate-like In(OH)3 D. Curulla-Ferre, J. Perez-Ramirez, Indium Oxide as a Superior Catalyst for
for effective photocatalytic reduction of CO2 with H2O vapor, Appl. Catal. B- Methanol Synthesis by CO2 Hydrogenation, Angew. Chem. 55 (2016) 6261–6265.
Environ. 253 (2019) 77–87. [43] T. Yan, J. Long, X. Shi, D. Wang, Z. Li, X. Wang, Efficient photocatalytic degradation
[25] H. Zhao, H. Yu, X. Quan, S. Chen, Y. Zhang, H. Zhao, H. Wang, Fabrication of of volatile organic compounds by porous indium hydroxide nanocrystals, Environ.
atomic single layer graphitic-C3N4 and its high performance of photocatalytic dis- Sci. Technol. 44 (2010) 1380–1385.
infection under visible light irradiation, Appl. Catal. B-Environ. 152–153 (2014) [44] J. Liqiang, Q. Yichun, W. Baiqi, L. Shudan, J. Baojiang, Y. Libin, F. Wei,
46–50. F. Honggang, S. Jiazhong, Review of photoluminescence performance of nano-sized
[26] Y.-P. Yuan, L.-S. Yin, S.-W. Cao, L.-N. Gu, G.-S. Xu, P. Du, H. Chai, Y.-S. Liao, C. Xue, semiconductor materials and its relationships with photocatalytic activity, Sol.
Microwave-assisted heating synthesis: a general and rapid strategy for large-scale Energ. Mat. Sol. C. 90 (2006) 1773–1787.
production of highly crystalline g-C3N4 with enhanced photocatalytic H2 produc- [45] Q. Wang, W. Wang, L. Zhong, D. Liu, X. Cao, F. Cui, Oxygen vacancy-rich 2D/2D
tion, Green Chem. 16 (2014) 4663–4668. BiOCl-g-C3N4 ultrathin heterostructure nanosheets for enhanced visible-light-driven
[27] S. Liu, H. Zhu, W. Yao, K. Chen, D. Chen, One step synthesis of P-doped g-C3N4 with photocatalytic activity in environmental remediation, Appl. Catal. B-Environ. 220
the enhanced visible light photocatalytic activity, Appl. Surf. Sci. 430 (2018) (2018) 290–302.
309–315. [46] N.J. Bell, Y.H. Ng, A. Du, H. Coster, S.C. Smith, R. Amal, Understanding the en-
[28] T. Chen, W. Quan, L. Yu, Y. Hong, C. Song, M. Fan, L. Xiao, W. Gu, W. Shi, One-step hancement in photoelectrochemical properties of photocatalytically prepared TiO2-
synthesis and visible-light-driven H2 production from water splitting of Ag quantum reduced graphene oxide composite, J. Phys. Chem. C 115 (2011) 6004–6009.
dots/g-C3N4 photocatalysts, J. Alloy. Compd. 686 (2016) 628–634. [47] H. Yu, Y. Zhao, C. Zhou, L. Shang, Y. Peng, Y. Cao, L.-Z. Wu, C.-H. Tung, T. Zhang,
[29] S. Asadzadeh-Khaneghah, A. Habibi-Yangjeh, M. Abedi, Decoration of carbon dots Carbon quantum dots /TiO2 composites for efficient photocatalytic hydrogen evo-
and AgCl over g-C3N4 nanosheets: Novel photocatalysts with substantially im- lution, J. Mater. Chem. A 2 (2014) 3344–3351.
proved activity under visible light, Sep. Purif. Technol. 199 (2018) 64–77. [48] H. Wang, D. Yong, S. Chen, S. Jiang, X. Zhang, W. Shao, Q. Zhang, W. Yan, B. Pan,
[30] H. Zhu, X. Wang, Z. Wang, C. Yang, F. Yang, X. Yang, Self-assembled 3D micro- Y. Xie, Oxygen-Vacancy-Mediated Exciton Dissociation in BiOBr for Boosting
flowery In(OH)3 architecture and its conversion to In2O3, J. Phys. Chem. C 112 Charge-Carrier-Involved Molecular Oxygen Activation, J. Am. Chem. Soc. 140
(2008) 15285–15292. (2018) 1760–1766.
[31] H. Liu, Z. Jin, Z. Xu, Z. Zhang, D. Ao, Fabrication of ZnIn2S4–g-C3N4 sheet-on-sheet [49] D. Rayner, A. Szabo, Time resolved fluorescence of aqueous tryptophan, Can. J.
nanocomposites for efficient visible-light photocatalytic H2-evolution and de- Chem. 56 (1978) 743–745.
gradation of organic pollutants, RSC Adv. 5 (2015) 97951–97961. [50] G. Dong, W. Ho, C. Wang, Selective photocatalytic N2 fixation dependent on g-C3N4
[32] S. Liu, S. Wang, Y. Jiang, Z. Zhao, G. Jiang, Z. Sun, Synthesis of Fe2O3 loaded porous induced by nitrogen vacancies, J. Mater. Chem. A 3 (2015) 23435–23441.
g-C3N4 photocatalyst for photocatalytic reduction of dinitrogen to ammonia, Chem. [51] H. Li, J. Shang, Z. Ai, L. Zhang, Efficient Visible Light Nitrogen Fixation with BiOBr
Eng. J. 373 (2019) 572–579. Nanosheets of Oxygen Vacancies on the Exposed 001 Facets, J. Am. Chem. Soc. 137
[33] S. Cho, J.-W. Jang, K.-J. Kong, E.S. Kim, K.-H. Lee, J.S. Lee, Anion-Doped Mixed (2015) 6393–6399.
Metal Oxide Nanostructures Derived from Layered Double Hydroxide as Visible [52] H. Hirakawa, M. Hashimoto, Y. Shiraishi, T. Hirai, Photocatalytic conversion of
Light Photocatalysts, Adv. Funct. Mater. 23 (2013) 2348–2356. nitrogen to ammonia with water on surface oxygen vacancies of titanium dioxide, J.
[34] J.L. Gunjakar, I.Y. Kim, J.M. Lee, N.-S. Lee, S.-J. Hwang, Self-assembly of layered Am. Chem. Soc. 139 (2017) 10929–10936.
double hydroxide 2D nanoplates with graphene nanosheets: an effective way to [53] S. Cao, B. Fan, Y. Feng, H. Chen, F. Jiang, X. Wang, Sulfur-doped g-C3N4 nanosheets
improve the photocatalytic activity of 2D nanostructured materials for visible light- with carbon vacancies: General synthesis and improved activity for simulated solar-
induced O2 generation, Energ. Environ. Sci. 6 (2013) 1008. light photocatalytic nitrogen fixation, Chem. Eng. J. 353 (2018) 147–156.

10

You might also like