Chemical Engineering Journal 414 (2021) 128773

Contents lists available at ScienceDirect

Chemical Engineering Journal

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

Understanding the key role of vanadium in p-type BiVO4 for

photoelectrochemical N2 fixation
Yajie Bai a, 1, Jianmin Lu b, 1, Hongye Bai a, Zhenyuan Fang c, Fagen Wang a, Ying Liu a,
Dongtian Sun a, Bifu Luo a, Weiqiang Fan a, *, Weidong Shi a, *
a
School of Chemistry and Chemical Engineering, Jiangsu University, Zhenjiang 212013, PR China
b
State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, 116023, PR China
c
School of Chemistry, Beihang University, Beijing 100191, PR China

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

Keywords: The photoelectrochemical N2 reduction reaction (PEC NRR) is extremely charming to the synthetic ammonia
Photoelectrochemistry (NH3), for its mild operating conditions and low carbon footprint. Taking account of the strong chemical
p-type BiVO4 inertness of N2 and competitive hydrogen evolution reaction, it is necessary to explore a robust and stable
N2 reduction reaction
photoelectrocatalyst. Herein, a robust p-type BiVO4 (p-BiVO4) photocathode is firstly reported for NRR under
Ammonia synthesis
ambient conditions. Interestingly, V sites are proved as the mainly ideal active center for N2 adsorption/acti­
Active sites
vation based on the density functional theory (DFT) calculations. The ammonia evolution rate (VNH3:11.6 ×
10− 8 mol h− 1 cm− 2) and Faradaic efficiency (16.2%) were obtained at − 0.1 V vs. RHE in 0.1 M Li2SO4 solution,
outperforming most of the photoelectrocatalysts reported thus far. Moreover, the 1H nuclear magnetic resonance
result confirmed that the source of N was completely from the feeding N2 gas. This work provided a new op­
portunity to tap the V-based photocathode in the field of PEC NRR.

1. Introduction [19,20]. However, the efficiency and durability of the photoelectrodes

As an indispensable chemical feedstock to human society, ammonia
(NH3) plays a significant role in industry and agriculture [1–5]. Yet, the
commercial NH3 synthesis is dominantly achieved by the preeminent
Haber-Bosch (HB) process under the harsh reaction conditions
(650–750 K, 150–350 bar) [6,7]. The preparation and compression of
the precursors (H2 and N2) consume approximately 2% of global fossil
fuels, which leads to the large emissions of greenhouse gases [8–11]. For
example, Wang et al. reported a highly efficient and sustainable NH3
synthesis strategy by inhibiting competitive hydrogen evolution reac­
tion (HER) under mild conditions [12–14]. Thus far, various advanced
methods have been proposed to promote N2 conversion to NH3, such as
biochemical, electrochemical, photocatalytic and photoelectrochemical
(PEC) strategies [15–18]. These technologies are energy-efficient and
without massive CO2 production. Especially, PEC N2 reduction reaction
(NRR) usually exhibits remarkable catalytic performance due to the
synergetic effect of photocatalysis and electrochemistry in the synthesis
of NH3, which has aroused our great interest in further exploration
are required to be improved to render PEC NRR economically viable.
As N2 is an extremely stable molecule, designing photocathode with
excellent adsorption/activation ability of N2 is critically important
[21,22]. Recently, the emergence of photocathode materials with
abundant reaction sites provides new opportunities and challenges in
the field of PEC NRR. In particular, V-based material has become a
promising catalyst for N2 fixation, since vanadium nitrogenase is acted
as a primary component of N2 cycle in nature [23], which could effec­
tively inhibit the competitive HER [16]. As a kind of transition metal
element, V’s unoccupied 3d orbit provides a great convenience for N2
adsorption and served as the bridge to enable the transfer of photoex­
cited electrons from catalyst to N2 molecules, that’s why the NRR of V-
based catalysts is relatively efficient [24–26]. Up to now, a series of
materials based on V element have been reported in the NRR field, such
as V-TiO2 (VNH3:1.04 × 10− 6 mol h− 1 mg–1cat; FE = 15.3%), NV
(VNH3:3.02 × 10− 7 mol h− 1 cm− 2; FE = 2.25%) and VO2 (VNH3:8.74 ×
10− 7 mol h− 1 mg–1cat; FE = 3.97%) [27–29]. The obvious discrepancies
in Faraday efficiency and VNH3 further reveal that the chemical

* Corresponding authors.
E-mail addresses: fwq4993329@ujs.edu.cn (W. Fan), swd1978@ujs.edu.cn (W. Shi).
1
These authors contributed equally to this work.

https://doi.org/10.1016/j.cej.2021.128773
Received 4 November 2020; Received in revised form 12 January 2021; Accepted 27 January 2021
Available online 2 February 2021
1385-8947/© 2021 Elsevier B.V. All rights reserved.
Y. Bai et al.
environment of V element actually dominates the overall NRR perfor­
mance. As we known, BiVO4 is a desirable matrix for locating V element,
since it takes a nature of low-cost and superior physicochemical per­
formance; and BiVO4 has been widely applied in contaminants degra­
dation, water splitting and CO2 reduction [30–33]. However, BiVO4
commonly forms as n-type semiconductor in most cases and is selected
as the matrix for fabricating photoanode in PEC system, hardly suitable
for the protonation reaction and NH3 production [34]. Therefore, the
fabrication of p-type BiVO4 (p-BiVO4) through feasible method has
become fairly charming but challenging to in-depth explore the practical
application for PEC NRR.
Herein, we successfully fabricated a p-BiVO4 photocathode for effi­
cient PEC NRR via a simple hydrothermal process. The p-BiVO4 photo­
cathode exhibits the excellent performance at the low potential of − 0.1
V vs. RHE toward PEC NRR: a pretty high FE (16.2%) and an ideal VNH3
(11.6 × 10− 8 mol h− 1 cm− 2). Based on the XPS and EPR characteriza­
tion, the two typical factors oxygen vacancy and N element for boosting
NRR have been excluded in our work. The calculations of density
functional theory (DFT) further reveal that V and Bi both contribute to
the adsorption and activation of N2, and the V sites take the dominant
role for PEC NRR, which is consistent with the results of XPS and EPR.
This study provides a new insight on developing efficient and stable
photoelectrocatalysts for N2 fixation.
2. Experimental section
2.1. Chemicals and reagents
Ethylenediaminetetraacetic acid disodium (EDTA-2Na), ammonium
metavanadate (NH4VO3), Bismuth nitrate pentahydrate (Bi
(NO3)3⋅5H2O), potassium sodium tartrate (NaKC4H4O6), Nessler’s re­
agent, hydrogen nitrate (HNO3, 65% ~ 68%), sodium hydroxide
(NaOH), ammonium chloride (NH4Cl) and anhydrous ethanol were
obtained from Sinopharm Chemical Reagent Co., Ltd. Li2SO4 and were
purchased from Aladdin Ltd. (Shanghai, China). All chemical reagents
were used as purchased without further purification. The FTO glass
substrates used in the experiment were previously ultrasonically cleaned
in acetone or ethanol for 25 min, respectively.
2.2. Synthesis of p-BiVO4
1.9404 g Bi(NO3)3⋅5H2O and 1.4888 g EDTA-2Na were dispersed in
40 mL diluted HNO3 solution (2 mol L− 1) and dissolved completely by
ultrasound, which was designated as solution A. Then, 0.4676 g NH4VO3
and 1.4888 g EDTA-2Na were dispersed in 80 mL NaOH solution (3.2 g
of NaOH dissolved in 80 mL deionized water) and dissolved completely
by ultrasound, which is entitled as solution B. The A and B solution were
transferred to a stainless-steel Teflon-lined autoclave (volume of 200
mL) with the FTO glass and kept at 160 ◦ C for 12 h. The synthesized p-
BiVO4 samples were washed with deionized water for several times and
dried at room temperature.
2.3. Characterizations of p-BiVO4
The phase compositions and crystal structures of the samples were
analysed by the X-ray diffraction (XRD) patterns using a Bruker D8
advance X-ray diffractometer in the range of 10◦ –80◦ . Raman spectra
were measured on a DXR (Thermo Scientific) spectrometer. The mor­
phologies were characterized by a field emission scanning electronic
microscopy (FESEM, Hitachi Japan). Transmission electron microscopy
(TEM) and high resolution TEM (HRTEM) was carried out (JEM-2100F,
Japan) with an accelerating voltage of 200 kV. The elemental chemical
compositions and states of the samples were obtained by X-ray photo­
electron spectroscopy (XPS VG, Physical Electrons Quantum 2000
Scanning Esca Microprobe, Al Ka radiation). Mott-Schottky data were
measured by electrochemical instrumentation (Princeton, VersaSTAT3)
2
Chemical Engineering Journal 414 (2021) 128773
in a standard three-electrode configuration. The absorption perfor­
mances of N2 were measured by Temperature-programmed desorption
(TPD Micromeritics AutoChem II 2920). The UV–vis diffuse reflection
spectroscopy (DRS) was tested by UV–vis 2550 (Shimadzu, Japan). The
functional groups were examined by Fourier transform infrared (FTIR,
Nexus 470, Thermo Electron Corporation) using the KBr pellet technique
at room temperature.
2.4. Photoelectrochemical measurements
The performance of PEC NRR was carried out in a three-electrode
system (H-type two-compartment cell) with N2-saturated 0.1 M Li2SO4
solutions under a 300 W xenon lamp (radiation intensity: 100 mW
cm− 2), including p-BiVO4 working electrode, Pt sheets (1 cm × 1 cm)
counter electrode and Ag/AgCl (saturated KCl electrolyte) reference
electrode. A schematic diagram of PEC NRR configuration is shown in
Scheme S1. Linear-sweep-voltammetry (LSV) curves were measured at a
scanning rate of 50 mV/s. The blank experiment was carried out with Ar
instead of N2. Before LSV measurement, N2 was introduced into the 0.1
M Li2SO4 cathode chamber continuously bubbling for 1 h uniformly,
then kept throughout the process of PEC NRR to maintain N2 saturation.
2.5. Determination of NH3
The rate of ammonia (VNH3) was analysed by Nessler’s reagent
spectrophotometry. Details are as follows: 1 mL of potassium sodium
tartrate solution and 1.5 mL of Nessler’s reagent were added to 50 mL of
PEC NRR electrolyte taken out from the reactor and stood for 10 min.
The UV–Vis absorbance of NH+ 4 in the electrolyte was measured at 420
nm. In Fig. S1, the concentration-absorbance standard curve is a linear
fitting curve (Y = 2152.557X + 0.003, R2 = 0.982) obtained by fitting
the standard ammonium chloride solution of different concentration
(average value obtained by multiple measurements) with the corre­
sponding absorbance by measuring. The VNH3 formation can be calcu­
lated by the following formula:
VNH3 = CNH3 × V/(A × t)
Assuming that three electrons are needed to generate a molecule
NH3, FE in 0.1 M Li2SO4 can be calculated by the following formula:
FE = 3 × F × CNH3 × V/(17 × Q) × 100%
Among them, CNH3 is the measured concentration of NH3, V is the
volume of reaction liquid, A is the area of catalyst, t is the reaction time,
F is the Faraday constant (96485 C mol− 1), Q is the total electricity
consumption.
2.6. Determination of N2H4
N2H4 was estimated through Watt and Chrisp method. A color re­
agent contains 5.99 g para-(dimenthylamino) benzaldehyde, 30 mL
concentrated HCl and 300 mL ethanol. Typically, the standard
concentration-absorbance curve was measured by UV–vis spectropho­
tometer at 455 nm with a series of standard N2H4 solutions (0.0, 0.2, 0.4,
0.6, 0.8, 1.0 and 2.0 μg mL− 1). 10 mL electrolyte solution after PEC NRR
was mixed with 10 mL as-prepared color reagent and stayed for15 mi­
nutes. Then the UV–vis absorbance of N2H4 in the electrolyte solution
was tested and the concentration was determined from the standard
concentration-absorbance curve.
15
2.7. N2 isotope labelling experiments
In order to confirm the source of N in NH3 produced by PEC NRR,
isotopic labelling experiments with either 15N2 or 14N2 as the feeding
gas. The Ar was bubbled for 1 h before the reaction to avoid the inter­
ference of 14N2 in the air. After the reaction, 1H nuclear magnetic
Y. Bai et al. Chemical Engineering Journal 414 (2021) 128773

Fig. 1. (a) Schematic illustration for the synthesis of p-BiVO4. (b) XRD, (c) SEM, (d) TEM and (e) HRTEM images for p-BiVO4. (f) HAADF-STEM images of p-BiVO4
and corresponding EDX mapping images for (g) Bi (green), (h) V (red), and (i) O (blue).

resonance (100 μL D2O and 50 μL DMSO) was used to detect the
concentrated electrolyte.
2.8. Theoretical calculation method
We have used the Vienna Ab Initio Package (VASP) [35,36] to
perform all the density functional theory (DFT) calculations within the
generalized gradient approximation (GGA) using the PBE formulation
[37]. We have chosen the projected augmented wave (PAW) potentials
[38,39] to describe the ionic cores and take valence electrons into
account using a plane wave basis set with a kinetic energy cutoff of 400
eV. Partial occupancies of the Kohn-Sham orbitals were allowed using
the Gaussian smearing method and a width of 0.05 eV. The electronic
energy was considered self-consistent when the energy change was
smaller than 10− 7 eV. A geometry optimization was considered
convergent when the energy change was smaller than 10− 6 eV.
Grimme’s DFT-D3 methodology [40] was used to describe the dispersion
interactions among all the atoms in the bulk unit cells and surface
models of interest. This unit cell was used to construct the BiVO4 (1 0 1)
surface with a p (1 × 1) periodicity in the x, y directions and 2

3
Y. Bai et al. Chemical Engineering Journal 414 (2021) 128773

Fig. 2. XPS spectra for p-BiVO4: (a) Bi 4f, (b) V 2p, (c) O 1s regions. (d) UV–vis absorption spectra and Tauc plots. Mott-Schottky plot at different frequency: (e) p-
BiVO4, (f) n-type BiVO4.

stoichiometric layers in the z direction, separated by a 15 Å of vacuum in
the z direction between the slab and its periodic images. Both the Bi-
terminated BiVO4 (1 0 1) surface and the V-terminated one contain 8
Bi, 8 V and 32 O atoms; and both have the lattice constants of a =
9.6803 Å, b = 7.2383 Å, c = 23.4109 Å, and α = β = γ = 90◦ . The 3 × 4 ×
1 Monkhorst-Pack k-point mesh of Brillouin zone was used for k-point
sampling in the following surface calculations. During structural opti­
mizations, the top stoichiometric layer was allowed to relax, while the
bottom one was fixed to their bulk positions. The adsorption energy
(Eads) of an adsorbate was defined as:

4
Y. Bai et al. Chemical Engineering Journal 414 (2021) 128773

Fig. 3. Performance of the p-BiVO4 for PEC NRR. (a) LSV curves of p-BiVO4 in Ar (purple line) and N2 (black line: in light; grey: in dark) saturated 0.1 M Li2SO4
solutions at room temperature and corresponding VNH3. Inset: 1H NMR spectra of the electrolyte fed by 15N2 or 14N2 during PEC NRR. (b) VNH3 in N2 and Ar at­
mosphere. (c) VNH3 of p-BiVO4 at different potentials under illumination and (d) corresponding Faradaic efficiencies. (e) Time-dependent current density curve of p-
BiVO4 at − 0.1 V for 12 h (0.1 M Li2SO4). (f) VNH3 in different cycle number at − 0.1 V vs. RHE.

5
Y. Bai et al.
Fig. 4. (a) FT-IR spectra for standard NH4Cl and Li2SO4 reaction solution dripped with HCl. (b) UV–vis absorption spectrum for the electrolytes estimated by the Watt
and Chrisp method (after being electrolyzed at − 0.1 V vs. RHE for 2 h).
Eads = EA/S − EA(g) − ES
where EA/S, EA(g), ES represent the total energies of an adsorbate on
BiVO4 (1 0 1) surface, an adsorbate in gas phase and a clean BiVO4 (1 0 1)
surface, respectively.
3. Results and discussion
The scheme for fabricating p-BiVO4 photocathode by a simple hy­
drothermal method is illustrated in Fig. 1a [34]. The standard test
electrode was further prepared by cutting p-BiVO4 sample into suitable
pieces (as shown in Fig. S2a). The crystallographic structures and phase
purities of samples were firstly investigated by the X-ray diffraction
(XRD). As shown in Fig. 1b, two sharp reflections at 18.1◦ and 48.1◦
could be indexed to (1 0 1) and (3 1 2) diffraction peaks of BiVO4 (JCPDS
No. 14-0133), respectively. Raman spectroscopy measurements also
provide strong evidence for the successful preparation of the samples.
Seven dominant peaks at 62 cm− 1, 111 cm− 1, 248 cm− 1, 367 cm− 1, 730
cm− 1, 760 cm− 1 and 855 cm− 1 are appropriately allocated to BiVO4
(Fig. S2b) [41]. The results of Raman spectroscopy, X-ray diffraction
(XRD) and energy dispersive spectroscopy (Fig. S3) clearly validate that
BiVO4 has been successfully prepared on the surface of the FTO
substrate.
Then, the morphology was characterized by scanning electron mi­
croscopy (SEM) and Transmission electron microscopy (TEM). As shown
in the Fig. 1c, the obvious “four petal flowers” nanocubes were observed,
and BiVO4 were regularly distributed on the FTO substrate. Trans­
mission electron microscopy (TEM) (Fig. 1d) and High-resolution TEM
(HRTEM) images (Fig. 1e) presented the resolved lattice fringes with
distance of 0.49 nm, which corresponds to the (1 0 1) plane of tetragonal
BiVO4. Finally, HAADF-TEM and the corresponding EDX mapping im­
ages (Fig. 1f–i) further supplement the successful configuration of p-
BiVO4.
The X-ray photoelectron spectroscopy (XPS) of the sample denote the
presence of Bi, V and O elements in the p-BiVO4. It is worth noting that
the signal of N element was not been detected, so the interference of N
element on subsequent PEC NRR can be eliminated (Fig. S4) [42]. It can
be clearly seen that the binding energies of 159.2 and 164.5 eV can
correspond to Bi 4f7/2 and Bi 4f5/2 respectively, which is well attributed
to the characteristic peak of Bi3+ in p-BiVO4 (Fig. 2a) [43]. As shown in
Fig. 2b, the peaks of 516.8 and 524.3 eV can be assigned to V2p3/2 and V
6
Chemical Engineering Journal 414 (2021) 128773
2p5/2, which are the characteristic peaks of V3+ in p-BiVO4 [44]. The O
1s spectrum (Fig. 2c) contains two components around 529.9 and 530.8
eV, corresponding to lattice oxygen and adsorbed oxygen, respectively
[45]. The electron paramagnetic resonance (EPR) spectra of p-BiVO4 are
also provided in Fig. S5, and there is no characteristic peak attributable
to oxygen vacancy (OV) [46], which is consistent with the XPS spectra of
O 1s. The above results revealed that the PEC NRR performance was not
influenced by oxygen vacancy, which is often a key factor in some
previous reports [47–49]. This brings convenience for reducing the pa­
rameters considered in the subsequent theoretical calculation. The op­
tical and electrical properties of the sample were studied by UV–vis
diffuse reflectance spectra (DRS) and Mott-Schottky plots. It is clear that
the sample show typical semiconductor absorption of tetragonal zircon
BiVO4 with the bandgap of 2.62 eV (Fig. 2d) [34]. In Fig. 2e, we further
studied the electronic band structure by Mott-Schottky plots, and the
negative slope reveals the p-type characteristics of the sample (As shown
in Fig. 2f, the Mott-Schottky plots of BiVO4 with a positive slope, which
is typical of n-type BiVO4 semiconductor).
The PEC NRR activity of p-BiVO4 was evaluated in a high N2-satu­
rated 0.1 M Li2SO4 solutions using a three-electrode system (H-type cell
equipped) and the schematic diagram of PEC NRR configuration has
been shown in Scheme S1. Before LSV measurement, 0.1 M Li2SO4 was
purging with N2 for 1 h, and N2 was continuously bubbling into the
cathode gas chamber uniformly throughout the process of PEC NRR to
maintain N2-saturated. In order to confirm the source of N in NH3 pro­
duced by PEC NRR, some necessary comparative experiments were
carried out. When Ar replaced N2 as the feeding gas, a lower current
density (scanning rate of 50 mV/s) was obtained, and no apparent NH3
was detected (Fig. 3a and b). In order to confirm the source of N in NH3
produced by PEC NRR, isotopic labelling experiments with either 15N2
or 14N2 as the feeding gas were carried out. When 15N2 is provided as the
only feeding gas, there is only a double signal, indicating that the NH3
product of the electrolyte is completely from the supplied N2, because
there is no typical triple peak signal of 14N2 (insert Fig. 3a) [50]. The
NH3 generation rates were analysed by using Nessler’s reagent spec­
trophotometry that VNH3 (11.6 × 10− 8 mol h− 1 cm− 2) and Faraday ef­
ficiency (16.2%) of NH3 formation reached the maximum at − 0.1 V vs.
RHE (Fig. 3c and d). Therefore, the point potential is set as the optimum
potential for further exploration and reaction. The photocurrent-time
curves are used to investigate the charge transfer process of the sam­
ple, at − 0.1 V vs. RHE with repeated on/off cycles, as shown in Fig. S6.
The current is significantly stronger in the light than in the dark, which
Y. Bai et al. Chemical Engineering Journal 414 (2021) 128773

Fig. 5. (a) N2-TPD profiles for p-BiVO4. (b) Gibbs free energy diagrams of N2 adsorption on two active sites (Bi, V) for p-BiVO4. (c) Gibbs free energy diagrams for
PEC NRR on p-BiVO4 (1 0 1) surface at Bi and V sites. (d) Schematic diagram of PEC NRR mechanism and electron transfer process.

7
Y. Bai et al.
proves that the process of N2 fixation is the result of photo-electric
synergy. Compared with most NRR in previous reports, p-BiVO4 ex­
hibits superior VNH3 and Faraday efficiency (Table S1). It is well known
that the durability of NH3 production is a vital parameter affecting the
application, the recycling experiments were carried out for p-BiVO4 at
− 0.1 V vs. RHE. The corresponding current density appeared no obvious
fluctuation in the long-term PEC NRR process (Fig. 3e and Fig. S7).
Meanwhile, after six consecutive cycles, no significant decline was
observed in VNH3 and Faraday efficiency (Fig. 3f). In addition, surface
composition and oxidation state comparison of p-BiVO4 before/after
PEC NRR through XPS spectra indicate no obvious changes (Fig. S8),
respectively. This means that the crystal structure type of BiVO4
photocathode surface did not change during the process of PEC NRR.
The above results revealed that the robust durability of p-BiVO4 for PEC
NRR. In order to study the product of PEC NRR qualitatively, we tested
the reaction solution by Fourier transform infrared (FT-IR) spectrum
(Fig. 4a), which is in good agreement with the FT-IR characteristic peak
of the standard NH4Cl, further confirming that NH3 was indeed gener­
ated in the PEC NRR process. In addition, the possible by-product (N2H4)
was detected by Watt and Chrisp method (Fig. S9), but there was no
N2H4 detected in the electrolyte of PEC NRR (Fig. 4b), suggesting that
the p-BiVO4 has excellent selectivity toward NH3.
The adsorption is considered to be the key step to activate N2 in the
process of PEC NRR. The temperature-programmed desorption (TPD)
measurements were carried out to understand the chemical adsorption
capacity of N2 on the surface of p-BiVO4 (Fig. 5a). The strong peak
centered at ~242 ◦ C could be ascribed to the chemical adsorption. Thus,
the chemical adsorption takes a dominant role, which is consistent with
the research results of N2-TPD reported in the literature [51]. In order to
get a deeper understanding of the possible NRR mechanism on p-BiVO4,
we further carried out the difference of NRR process at Bi and V sites on
the (1 0 1) plane of p-BiVO4 by density functional theory (DFT) calcu­
lations. The chemisorption of N2 on the surface of p-BiVO4 is viewed as
the key of NRR kinetics. The insert Fig. 5b clarifies the free energy ab­
sorption of N2 on the possible active sites (Bi, V). It can be observed that
the adsorption energy of V (ΔG = − 0.89 eV) is significantly higher than
that of Bi (− 0.18 eV), indicating that NRR tends to spontaneously adsorb
on the V site of p-BiVO4. In Fig. 5c, the decisive reaction step of NRR
process is determined by *N2 to *NNH (this step shows the uphill
pathway and the rest of the hydrogenation process is spontaneous
downhill). The relatively low free energy of V site (ΔG = 1.4 eV) in­
dicates that the effective adsorption of N2 on V is the main reason for
promoting NRR (free energy of Bi: ΔG = 2.4 eV). It is worth noting that
the steps from *NH3 to NH3 (g) exhibits a high energy barrier in both
reaction pathways, which is determined by the high solubility of NH3 in
solution and does not belong to NRR step [52]. According to the above
experimental results, Fig. 5d illustrated the possible mechanism of PEC
NRR activity for the p-BiVO4. Firstly, the electrons in the valence band
(VB) of p-BiVO4 are excited into the conduction band (CB) to generate
electron-hole pairs. At the same time, the negative external bias con­
sumes photogenerated holes in the p-BiVO4, which can effectively pro­
mote the separation of electron-hole inhibits the recombination of
photogenerated carries. The photo-electric synergistic process promotes
the PEC NRR more effectively. V provides the main active site for the
adsorption of N2 and electrons. The 3d empty orbitals of V act as electron
acceptors to prevent the recombination of photoinduced electrons and
holes in p-BiVO4.
4. Conclusions
In summary, we have revealed that p-BiVO4 can be successfully
applied in PEC NRR. Specifically, the p-BiVO4 photocathode exhibits
excellent performance in the VNH3 (11.6 × 10− 8 mol h− 1 cm− 2) and
Faradaic efficiency (16.2%) at the low potential of − 0.1 V vs. RHE,
indicating that p-BiVO4 could be considered as a highly efficient and
durable catalyst. The isotope tracing experiments prove that the
8
Chemical Engineering Journal 414 (2021) 128773
detected NH3 are entirely derived from N2 PEC NRR. Besides, the DFT
results demonstrate that V site works as critical activation site of N––N
–
triple bond, and further confirm that the adsorption process from N2 to
*N2 is the rate-limiting step of the whole reaction. This innovative study
not only provides a coveted catalysis for PEC NRR, but also paves an
exciting avenue for the development and storage of solar energy.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgements
The authors are grateful for the National Natural Science Foundation
of China (22075112 and 21671083) and the Six Talent Peaks Project in
Jiangsu Province (XCL-019).
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.cej.2021.128773.
References
[1] X. Lv, F. Wang, J. Du, Q. Liu, Y. Luo, S. Lu, G. Chen, S. Gao, B. Zheng, X. Sun, Sn
dendrite for electrocatalytic N2 reduction to NH3 under ambient conditions sustain,
Energy Fuels 4 (2020) 4469–4472.
[2] F. Lü, S. Zhao, R. Guo, J. He, X. Peng, H. Bao, J. Fu, L. Han, G. Qi, J. Luo, X. Tang,
X. Liu, Nitrogen-coordinated single Fe sites for efficient electrocatalytic N2 fixation
in neutral media, Nano Energy 61 (2019) 420–427.
[3] X. Cheng, J. Wang, W. Xiong, T. Wang, T. Wu, S. Lu, G. Chen, S. Gao, X. Shi,
Z. Jiang, X. Niu, X. Sun, Greatly enhanced electrocatalytic N2 reduction over V2O3/
C by P doping, ChemNanoMat 6 (2020) 1315–1319.
[4] C. Li, D. Ma, S. Mou, Y. Luo, B. Ma, S. Lu, G. Cui, Q. Li, Q. Liu, X. Sun, Porous
LaFeO3 nanofiber with oxygen vacancies as an efficient electrocatalyst for N2
conversion to NH3 under ambient conditions, J. Energy Chem. 50 (2020) 402–408.
[5] C. Li, J. Yu, Li. Yang, J. Zhao, W. Kong, T. Wang, A. M. Asiri, Q. Li, X. Sun, Spinel
LiMn2O4 nanofiber: an efficient electrocatalyst for N2 reduction to NH3 under
ambient conditions, Inorg. Chem. 58 (2019) 9597− 9601.
[6] T. Wu, H. Zhao, X. Zhu, Z. Xing, Q. Liu, T. Liu, S. Gao, S. Lu, G. Chen, A.M. Asiri,
Y. Zhang, X. Sun, Identifying the origin of Ti3+ activity toward enhanced
electrocatalytic N2 reduction over TiO2 nanoparticles modulated by mixed-valent
copper, Adv. Mater. 32 (2020) 2000299.
[7] L. Xia, B. Li, Y. Zhang, R. Zhang, L. Ji, H. Chen, G. Cui, H. Zheng, X. Sun, F. Xie,
Q. Liu, Cr2O3 nanoparticle-reduced graphene oxide hybrid: a highly active
electrocatalyst for N2 reduction at ambient conditions, Inorg. Chem. 58 (2019)
2257–2260.
[8] Z. Jin, C. Liu, Z. Liu, J. Han, Y. Fang, Y. Han, Y. Niu, Y. Wu, C. Sun, Y. Xu, Rational
design of hydroxyl-rich Ti3C2Tx mxene quantum dots for high-performance
electrochemical N2 reduction, Adv. Energy Mater. 10 (2020) 2000797.
[9] C. Lv, C. Yan, G. Chen, Y. Ding, J. Sun, Y. Zhou, G.H. Yu, An amorphousnoble-
metal-free electrocatalyst that enables nitrogen fixation under ambient conditions,
Angew. Chem. Int. Ed. 57 (2018) 6073–6076.
[10] J. Liu, W. Kong, Z. Jin, Y. Han, J. Sun, L. Ma, Y. Niu, Y. Xu, MoFe nitrogenase-
mimic electrocatalyst for nitrogen fixation with high faradaic efficiency, J. Mater.
Chem. A 8 (2020) 19278–19282.
[11] X. Zhu, S. Mou, Q. Peng, Q. Liu, Y. Luo, G. Chen, S. Gao, X. Sun, Aqueous
electrocatalytic N2 reduction for ambient NH3 synthesis: recent advances in
catalysts developing and performances boosting, J. Mater. Chem. A 8 (2020)
1545–1556.
[12] G. Chen, Y. Yuan, H. Jiang, S. Ren, L. Ding, L. Ma, T. Wu, J. Lu, H. Wang,
Electrochemical reduction of nitrate to ammonia via direct eight-electron transfer
using a copper-molecular solid catalyst, Nat. Energy 5 (2020) 605–613.
[13] H. Cheng, P. Cui, F. Wang, L. Ding, H. Wang, High efficiency electrochemical
nitrogen fixation achieved with a lower pressure reaction system by changing the
chemical equilibrium, Angew. Chem. Int. Ed. 58 (2019) 15541–15547.
[14] L. Zhang, L. Ding, G. Chen, X. Yang, H. Wang, Ammonia synthesis under ambient
conditions: selective electroreduction of dinitrogen to ammonia on black
phosphorus nanosheets, Angew. Chem. Int. Ed. 58 (2019) 2612–2616.
[15] Y. Lee, P. Boonmongkolras, E. Son, J. Kim, S. Lee, S. Kuk, J. Ko, B. Shin, C. Park,
Unbiased biocatalytic solar-to-chemical conversion by FeOOH/BiVO4/perovskite
tandem structure, Nat. Commun. 9 (2018) 4208.
[16] X. Guo, J. Gu, S. Lin, S. Zhang, Z. Chen, S. Huang, Tackling the activity and
selectivity challenges of electrocatalysts toward the nitrogen reduction reaction via
atomically dispersed biatom catalysts, J. Am. Chem. Soc. 142 (2020) 5709–5721.
Y. Bai et al.
[17] Y. Shiraishi, M. Hashimoto, K. Chishiro, K. Moriyama, S. Tanaka, T. Hirai,
Photocatalytic dinitrogen fixation with water on bismuth oxychloride in chloride
solutions for solar-to-chemical energy conversion, J. Am. Chem. Soc. 142 (2020)
7574–7583.
[18] D. Liu, J. Wang, S. Bian, Q. Liu, Y. Gao, X. Wang, P. Chu, X. Yu,
Photoelectrochemical synthesis of ammonia with black phosphorus, Adv. Funct.
Mater. 7 (2020) 2002731.
[19] W. Ye, M. Arif, X. Fang, M.A. Mushtaq, X. Chen, D. Yan, An efficient
photoelectrochemical route for the ambient reduction of N2 to NH3 based on
nanojunctions assembled from MoS2 nanosheets and TiO2, ACS Appl. Mater.
Interfaces 11 (2019) 28809–28817.
[20] Manh-Hiep Vu, Mohan Sakar, Sayed Ali Hassanzadeh-Tabrizi, Trong-On Do, Photo
(electro)catalytic nitrogen fixation: problems and possibilities, Adv. Mater.
Interfaces 6 (12) (2019) 1900091, https://doi.org/10.1002/admi.201900091.
[21] Q. Cheng, C. Hu, G. Wang, Z. Zou, H. Yang, L. Dai, Carbon-defect-driven electroless
deposition of pt atomic clusters for highly efficient hydrogen evolution, J. Am.
Chem. Soc. 142 (2020) 5594–5601.
[22] M. Ma, X. Han, H. Li, X. Zhang, Z. Zheng, L. Zhou, J. Zheng, Z. Xie, Q. Kuang,
L. Zheng, Tuning electronic structure of PdZn nanocatalyst via acidetching strategy
for highly selective and stable electrolytic nitrogen fixation under ambient
conditions, Appl. Catal. B-Environ. 265 (2020), 118568.
[23] R. Zhang, J. Han, B. Zheng, X. Shi, A.M. Asirid, X. Sun, Metal–organic framework-
derived shuttle-like V2O3/C for electrocatalytic N2 reduction under ambient
conditions, Inorg. Chem. Front. 6 (2019) 391–395.
[24] A.J. Medford, M.C. Hatzell, Photon-driven nitrogen fixation: current progress,
thermodynamic considerations, and future outlook, ACS Catal. 7 (2017)
2624–2643.
[25] F. Chang, Y. Guan, X. Chang, J. Guo, P. Wang, W. Gao, G. Wu, J. Zheng, X. Li,
P. Chen, Alkali and alkaline earth hydrides-driven N2 activation and
transformation over Mn nitride catalyst, J. Am. Chem. Soc. 140 (2018)
14799–14806.
[26] J. Zhang, Y. Ji, P. Wang, Q. Shao, Y. Li, X.Q. Huang, Adsorbing and activating N2
on heterogeneous Au–Fe3O4 nanoparticles for N2 fixation, Adv. Funct. Mater. 30
(2019) 1906579.
[27] T. Wu, W. Kong, Y. Zhang, Z. Xing, J. Zhao, T. Wang, X. Shi, Y. Luo, X. Sun, Greatly
enhanced electrocatalytic n2 reduction on TiO2 via V doping, Small Methods 3
(2019) 2366–9608.
[28] R. Zhang, Y. Zhang, X. Ren, G. Cui, A.M. Asiri, B. Zheng, X. Sun, High-efficiency
electrosynthesis of ammonia with high selectivity under ambient conditions
enabled by VN nanosheet array, ACS Sustain. Chem. Eng. 6 (2018) 9545–9549.
[29] R. Zhang, H. Guo, L. Yang, Y. Wang, Z. Niu, H. Huang, H. Chen, L. Xia, T. Li, X. Shi,
X. Sun, B. Li, Q. Liu, Electrocatalytic N2 fixation over VO2 hollow microsphere at
ambient conditions, Chem. Electro Chem. 6 (2018) 1014–1018.
[30] J. Bian, J. Feng, Z. Zhang, Z. Li, Y. Zhang, Y. Liu, S. Ali, Y. Qu, L. Bai, J. Xie, D.
Y. Tang, X. Li, F. Bai, J. Tang, L. Jing, Dimension-matched zinc phthalocyanine/
BiVO4 ultrathin nanocomposites for CO2 reduction as efficient wide-visible-light-
driven photocatalysts via a cascade charge transfer, Angew. Chem. Int. Ed. 58
(2019) 10873–10878.
[31] J.X. Yao, D. Bao, Q. Zhang, M. Shi, Y. Wang, R. Gao, J.M. Yan, Q. Jiang, Tailoring
oxygen vacancies of BiVO4 toward highly efficient noble-metal-free electrocatalyst
for artificial N2 fixation under ambient conditions, Small Methods 3 (2018)
1800333.
[32] D.K. Lee, K. Choi, Enhancing long-term photostability of BiVO4 photoanodes for
solar water splitting by tuning electrolyte composition, Nat. Energy 3 (2018)
53–60.
[33] K. Pingmuang, J. Chen, W. Kangwansupamonkon, G.G. Wallace, S. Phanichphant,
A. Nattestad, Composite photocatalysts containing BiVO4 for degradation of
cationic dyes, Sci. Rep. 7 (2017) 2045–2322.
Chemical Engineering Journal 414 (2021) 128773
[34] J. Wang, Y. Song, J. Hu, Y. Lia, Z. Wang, P. Yang, Q. Ma, Q. Che, Y. Dai, B. Huang,
Photocatalytic hydrogen evolution on P-type tetragonal zircon BiVO4, Appl. Catal.
B-Environ. 251 (2019) 94–101.
[35] G. Kresse, J. Furthmu¨ller, Efficiency of Ab-initio total energy calculations for
metals and semiconductors using a plane-wave basis set, Comput. Mater. Sci. 6
(1996) 15− 50.
[36] G. Kresse, J. Furthmu¨ller, Efficient iterative schemes for ab initio total-energy
calculations using a plane-wave basis set, Phys. Rev. B 54 (1996) 11169− 11186.
[37] J.P. Perdew, K. Burke, M. Ernzerhof, Generalized gradient approximation made
simple, Phys. Rev. Lett. 77 (1996) 3865–3868.
[38] G. Kresse, D. Joubert, From ultrasoft pseudopotentials to the projector augmented-
wave method, Phys. Rev. B 59 (1999) 1758–1775.
[39] P. E. Blo¨chl, Projector augmented-wave method, Phys. Rev. B 50 (1994)
17953− 17979.
[40] S. Grimme, J. Antony, S. Ehrlich, H.J. Krieg, A consistent and accurate Ab Initio
parametrization of density functional dispersion correction (DFT-D) for the 94
elements H-Pu, Chem. Phys. 132 (2010), 154104.
[41] Z. Fang, Y. Bai, L. Li, D. Li, Y. Huang, R. Chen, W. Fan, W. Shi, In situ constructing
intramolecular ternary homojunction of carbon nitride for effcient photoinduced
molecular oxygen activation and hydrogen evolution, Nano Energy 75 (2020),
104865.
[42] R. Frost, D. Henry, M. Weier, W. Martens, Raman spectroscopy of three
polymorphs of BiVO4: clinobisvanite, dreyerite and pucherite, with comparisons to
(VO4)3-bearing minerals: namibite, pottsite and schumacherite, J. Raman
Spectrosc. 37 (2006) 722–732.
[43] Y. Zhang, L. Shi, Z. Geng, T. Ren, Z. Yang, the improvement of photocatalysis O2
production over BiVO4 with amorphous FeOOH shell modification, Sci. Rep. 9
(2019) 19090.
[44] F. Li, Dennis Y. Leung, Highly enhanced performance of heterojunction Bi2S3/
BiVO4 photoanode for photoelectrocatalytic hydrogen production under solar light
irradiation, Chem. Eng. Sci. 211 (2020), 115266.
[45] H. He, S. Berglund, Al.J.E. Rettie, W.D. Chemelewski, P. Xiao, Y. Zhang, C.B.
Mullins, Synthesis of BiVO4 nanoflake array films for photoelectrochemical water
oxidation, J. Mater. Chem. A 2 (2014) 9371− 9379.
[46] N. Zhang, A. Jalil, D. Wu, S. Chen, Y. Liu, C. Gao, W. Ye, Z. Qi, H. Ju, C. Wang,
X. Wu, L. Song, J. Zhu, Y. Xiong, Refining defect states in W18O49 by Mo doping: a
strategy for tuning N2 activation towards solar-driven nitrogen fixation, J. Am.
Chem. Soc. 140 (2018) 9434–9443.
[47] Y. Bai, H. Bai, K. Qu, F. Wang, P. Guan, D. Xu, W. Fan, W. Shi, In-situ approach to
fabricate BiOI photocathode with oxygen vacancies: understanding the N2 reduced
behavior in photoelectrochemical system, Chem. Eng. J. 362 (2019) 349–356.
[48] Y. Wang, M. Shi, D. Bao, F. Meng, Q. Zhang, Y. Zhou, K. Liu, Y. Zhang, J. Wang,
Z. Chen, D. Liu, Z. Jiang, M. Luo, L. Gu, Q. Zhang, X. Cao, Y. Yao, M. Shao,
Y. Zhang, X. Zhang, J. Chen, J. Yan, Q. Jiang, Generating defect-rich bismuth for
enhancing rate of nitrogen electroreduction to ammonia, Angew. Chem. Int. Ed. 58
(2019) 9464–9469.
[49] X. Xue, R. Chen, H. Chen, Y. Hu, Q. Ding, Z. Liu, L. Ma, G. Zhu, W. Zhang, Q. Yu,
J. Liu, J. Ma, Z. Jin, Oxygen vacancy engineering promoted photocatalytic
ammonia synthesis on ultrathin two-dimensional bismuth oxybromide nanosheets,
Nano Lett. 18 (2018) 7372–7377.
[50] S. Liu, M. Wang, T. Qian, H. Ji, J. Liu, C. Yan, Facilitating nitrogen accessibility to
boron-rich covalent organic frameworks via electrochemical excitation for efficient
nitrogen fixation, Nat. Commun. 10 (2019) 1–9.
[51] C. Li, T. Wang, Z. Zhao, W. Yang, J. Li, A. Li, Z. Yang, G.A. Ozin, J. Gong, Promoted
fixation of molecular nitrogen with surface oxygen vacancies on plasmon-enhanced
TiO2 photoelectrodes, Angew. Chem. Int. Ed. 57 (2018) 5278–5282.
[52] C. He, Z. Wu, L. Zhao, M. Ming, Y. Zhang, Y. Yi, J. Hu, Identification of FeN4 as an
efficient active site for electrochemical N2 reduction, ACS Catal. 9 (2019)
7311–7317.