Renewable Energy 188 (2022) 132e144

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Renewable Energy
journal homepage: www.elsevier.com/locate/renene

Phosphating MIL-53(Fe) as cocatalyst modified porous NiTiO3 for

photocatalytic hydrogen production
Hongying Li, Haiming Gong, Xuqiang Hao, Guorong Wang, Zhiliang Jin*
School of Chemistry and Chemical Engineering, Ningxia Key Laboratory of Solar Chemical Conversion Technology, Key Laboratory for Chemical Engineering
and Technology, State Ethnic Affairs Commission, North Minzu University, Yinchuan, 750021, PR China

a r t i c l e i n f o a b s t r a c t

Article history: Reasonably construct a new type of NiTiO3/Fe2P to modify porous perovskite materials and use simple
Received 28 August 2021 high-temperature phosphating treatments. The results showed that the optimal hydrogen production
Received in revised form performance of NiTiO3/Fe2P reached 299.00 mmol in 5 h, which is 3.68 times that of pure Fe2P. The
14 January 2022
existence of metal-organic framework materials as supporting materials facilitates the dispersed growth
Accepted 2 February 2022
Available online 4 February 2022
of NiTiO3 and Fe2P, and avoids the aggregation of nanorods and particles. The introduction of perovskite
porous nanorods is the reason for the enhanced light absorption capacity of composite materials. In
addition, transition metal phosphide Fe2P as a co-catalyst can serve as an electron trapping center to
Keywords:
MIL-53(Fe)
receive electrons from NiTiO3. Photoluminescence spectroscopy and electrochemical experiments have
Fe2P confirmed that transition metals have good conductivity and can effectively enhance the separation and
NiTiO3 transfer of carriers. Density functional theory calculations are used to calculate the band structure and
Co-catalyst density of states of NiTiO3 and Fe2P. In conclusion, this study provides a new idea for improving the
Hydrogen evolution photocatalytic activity of perovskite materials by modifying porous nanorod NiTiO3 with derivatives of
MOF materials.
© 2022 Elsevier Ltd. All rights reserved.

1. Introduction such as perovskite materials have good research prospects in the

field of photocatalysis due to their simple structure and good sta-
In recent years, environmental pollution and energy shortages bility [4,5]. Nickel titanate (NiTiO3), as one of the perovskite ma-
have become a hot topic. The use of sustainable, pollution-free, and terials, has excellent photocatalytic properties in terms of hydrogen
low-cost new energy sources to replace fossil energy has become a evolution and degradation of harmful substances [6]. For example,
solution to resolve the current environmental degradation problem Jiang et al. significantly increased the number of oxygen vacancies
[1]. Hydrogen energy is considered to be one of the more envi- to form triplet metal oxide phases by doping Nb and Ti3þ and Nb3þ
ronmentally friendly and more effective clean energy sources, sites in the lattice structure of NiTiO3. It provides a new method for
which can be effectively converted from renewable solar energy. the application of NiTiO3 in the field of photocatalysis [7]. Its unique
Since Fujishima and Honda successfully split water into hydrogen narrow bandgap (2.16e2.18 eV) and porous structure provide
and oxygen using TiO2 single crystal electrodes for the first time favorable conditions for the effective absorption of visible light [8].
under ultraviolet light, photocatalytic water splitting technology In addition, the absorbtion and utilization efficiency of photo-
has become the most environmentally friendly, safest, and most catalysts for the visible light and the separation and transfer ability
effective way to solve the energy crisis [2]. However, it is not easy to of carriers are the key links in the whole photocatalytic reaction
achieve high-efficiency photocatalytic activity by itself for most process. Inspired by this, combining the unique porous structure of
semiconductor materials. Hence, the preparation of photocatalysts NiTiO3 with other semiconductor materials can effectively improve
with excellent performance, low price, and high quantum effi- the utilization efficiency of the photocatalyst for visible light, which
ciency have become a huge challenge for this technology [3]. is also one of the strategies to improve the photocatalytic
As we all know, titanium-based oxides and their derivatives performance.
Metal-organic frameworks (MOFs) are materials that use metal
ions and organic ligands as coordination networks. It has broad
* Corresponding author. application prospects in gas storage, separation, catalysis, etc [9,10].
E-mail address: [email protected] (Z. Jin).

https://doi.org/10.1016/j.renene.2022.02.009
0960-1481/© 2022 Elsevier Ltd. All rights reserved.
H. Li, H. Gong, X. Hao et al. Renewable Energy 188 (2022) 132e144

MOFs can be photoexcited through light absorption by metal oxide 2. Experimental section
nodes or organic linkers, and MIL-53(Fe) possesses the same
properties [11,12]. MIL-53(Fe) is a semiconductor which forms a 2.1. Preparation of MIL-53(Fe)
conduction band due to the empty d-metal track and the LUMO of
the organic linker. This feature is similar to the conduction band of The preparation process of MIL-53(Fe) refers to previous work
TiO2 semiconductor consists of empty Ti 3d orbitals [13]. Therefore, reports [24]. In a typical process, 10 mmol FeCl3$6H2O and 10 mmol
MIL-53(Fe) is widely used in the fields of organic degradation and terephthalic acid were added to 50 mL of DMF solution with
photocatalysis [14e16]. Even so, the rapid recombination of photo- continuous stirring for 30 min to fully dissolve. Subsequently, the
generated charges and limited light capture of MOFs materials still solution was transferred to a polytetrafluoroethylene lined auto-
show low photocatalytic performance [17]. Therefore, preparing clave with a volume of 80 mL, and the temperature was maintained
MOFs derived materials and combining them with other functional at 150  C for 24 h. After the reaction was completed, it was cooled to
materials can make up for the shortcomings of low carrier sepa- room temperature, washed with DMF solution and and ethanol,
ration efficiency and weak light trapping ability. then dried at 60  C overnight.
Co-catalyst can promote the transfer of light-induced carriers
and provide reactive sites for the hydrogen evolution reaction. The 2.2. Preparation of Fe2P
co-catalyst with excellent preparation performance can be used as
a proton capture center to promote the reduction reaction of pro- The preparation of Fe2P uses the above-mentioned MIL-53(Fe)
tons. Generally speaking, precious metal materials such as plat- as the precursor material. 0.2 g of MIL-53(Fe) and 1 g of sodium
inum and gold have high activity, high stability, high conductivity, hypophosphite are ground in a mortar to make them evenly mixed.
and selectivity and are often used as co-catalyst [18]. However, The ground mixture was placed in a magnetic boat and calcined in a
precious metal materials are expensive and have low reserves, tube furnace. The calcination temperature was set at 300  C for 2 h,

which is not conducive to sustainable development research. and the calcination rate was 5 C/min. The entire calcination pro-
Therefore, looking for alternatives to precious metal materials such cess was carried out in a nitrogen atmosphere.
as non-metallic materials (metal phosphides, carbides, borides, and
transition metal sulfides) as co-catalysts can effectively enhance
2.3. Preparation of NiTiO3
the activity of the photocatalyst. Among them, transition metal
phosphide are considered to be the preferred materials for co-
2.49 g Ni(CH3COO)2$4H2O and 3.40 mL Ti(OCH2CH2CH2CH3)4
catalysts due to their abundant resources, low cost, and simple
were dissolved in 60 mL ethylene glycol and stir for 5 h. After
preparation. After theoretical calculations, it is concluded that the
centrifugation, a green gelatinous substance was obtained.
transition metal exhibits zero-valent metal characteristics similar
Then,the green gelatinous substance was transferred to a muffle
to Pt [19]. In addition, the negative charge carried by the P element 
furnace and calcined at 700  C for 4 h at a heating rate of 2 C/min.
in the transition metal phosphide can effectively capture protons to
Finally, a yellow powder is obtained.
promote the hydrogen adsorption of the active center. For example,
NixP [20], CoP [21], Cu3P [22] and other metal phosphide materials
have been proved to have broad development prospects in the field 2.4. Preparation of NiTiO3/Fe2P
of photocatalysis. Fe element, as one of the most stored elements on
the earth, has low cost and good stability at room temperature. The preparation process of the NiTiO3/Fe2P is similar to the Fe2P
Based on a series of advantages of the Fe element, ferrous phos- method, and the specific process is as follows: 0.2 g NiTiO3, 1 g
phide (Fe2P) has the potential as a non-noble metal co-catalyst to sodium hypophosphite and a certain mass of MIL-53(Fe) were
promote the separation and transfer of photogenerated carriers in mixed and ground uniformly, placed in a magnetic boat and
the reaction system [23]. The derivative of MIL-53(Fe) is obtained calcined in a tube furnace. The calcined black samples were washed
by phosphating treatment, which enhances the conductivity of the with deionized water and ethanol and dried overnight. According
material based on its original advantages. to the different dosages of MIL-53(Fe), the composite samples with
In this work, the porous materials NiTiO3 and MIL-53(Fe) are different ratios were named as 5-NFP, 10-NFP, 20-NFP and 30-NFP.
phosphatized by the calcination method to obtain NiTiO3/Fe2P. The The specific dosage of the samples were shown in the following
special structure of the porous material is beneficial to increase the Table 1. The preparation process of the photocatalyst was shown in
visible light absorption capacity of the photocatalyst. At the same Scheme 1.
time, the close contact between the transition metal Fe2P derived
from the Fe-based metal-organic framework and NiTiO3 can 2.5. Characterization
effectively separate and transfer the photogenerated carrier current
to participate in its reaction. In addition, the framework structure of The X-ray diffraction spectra of MIL-53(Fe), Fe2P, NiTiO3 and x-
the metal-organic framework provides a growth substrate for the NFP were investigated under the conditions of the voltage of 40 keV
dispersed growth of NiTiO3 and Fe2P. It is worth noting that Fe2P and current of 40 mA (XRD, Rigaku RINT-2000, Cu Ka radiation).
with good electrical conductivity was derived from MIL-53(Fe) as a Scanning electron microscope (SEM, Zeiss Evo 10) and transmission
cocatalyst to improve the hydrogen evolution performance of the electron microscope (TEM, Tecnai G2-TF30) were used to observe
composites. The ultraviolet diffuse reflection test shows that the
composite material has the strongest visible light absorption ca-
Table 1
pacity. Fluorescence test and photoelectrochemical test further The content of each component in the precursor.
prove that the existence of transition metal Fe2P as a transfer bridge
of photo-generated electrons effectively promotes the separation Sample NiTiO3 (mg) MIL-53(Fe) (mg) NaH2PO2$H2O (mg)

and transfer of electron-hole pairs, which is further conducive to 5-NFP 200 10 1000
the progress of photocatalytic redox reactions. This work provides a 10-NFP 200 20 1000
20-NBP 200 40 1000
new idea for the application of metal-organic frameworks in the
30-NBP 200 60 1000
field of photocatalysis.

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H. Li, H. Gong, X. Hao et al. Renewable Energy 188 (2022) 132e144

Scheme 1. Preparation process of NiTiO3/Fe2P.

and record the micro morphology of the prepared samples. X-ray electrode, and the conductive glass coated with the sample is used
photoelectron spectroscopy (XPS, ESCALAB 250Xi) was used to as the working electrode. The preparation process of the working
study the surface valence state and element composition of the electrode can be simply described as: Firstly, 5 mg of catalysts and
samples. The nitrogen adsorption and desorption isotherms of the 10 mL of 10% Nafion solution were ultrasonically dispersed for
samples were measured with an ASAP 2020 M instrument at 77 K, 30 min to form a uniform suspension. Subsequently, the FTO glass
and the results were analyzed using the Brunauer Emmett Teller (1  2 cm2) was washed with detergent (isopropanol, acetic acid
(BET) equation. The ultraviolet diffuse reflectance spectrum reflects solution, ethanol and water). Finally, the suspension containing the
the optical properties of the material. The UV diffuse reflectance sample was dropped uniformly on the FTO glass sheet with an area
spectra of MIL-53(Fe), Fe2P, NiTiO3 and 20-NFP were obtained on of 1  1 cm2, and the working electrode was obtained after drying.
the UV-2550 (Shimadzu) spectrometer, and BaSO4 was used as a
background reference during the test. The photoluminescence (PL)
2.8. Computational details
and time-resolved photoluminescence (TRPL) spectra of the ma-
terial were obtained using the FluoroMAX-4 spectrometer (Horiba,
The structures of NiTiO3 and Fe2P were optimized by spin-
France).
polarized density functional calculations, and the energy band
structures and density of states of the samples were studied. The
2.6. Photocatalytic hydrogen evolution experiments plane wave cut-off energy of NiTiO3 and Fe2P is set to 500 eV and
400 eV, and the energy convergence threshold of the self-
The 62 mL quartz reaction flask (PCX50A Discover) and a 5W consistent field is 1.00  105 eV. In addition, the exchange cor-
LED lamp were used as the reactor and simulated light source to relation potential is described by the Perdew-Burke-Ernzerhof
conduct kinetic experiments on the samples. The amount of pho- (PBE) functional in Generalized Gradient Approximation (GGA).
tocatalyst and EY sensitizer used in the reaction was 10 mg and At the same time, the Monkhorst-Pack grid composed of 6x6x6 k-
20 mg, respectively. Meanwhile, a 30 mL triethanolamine solution points is used for geometric optimization and electronic structure
(TEOA, 15% v/v, pH ¼ 10) was used as a sacrificial reagent to calculations.
participate in the reaction. Before the reaction flask is put into the
nine-channel reaction system, the powder samples in the flask are
3. Results and discussion
uniformly dispersed by ultrasound, and the air in the sealed reactor
is discharged with N2. The results of hydrogen production were
3.1. XRD analysis
analyzed by gas chromatography (Tianmei GC7900, TCD, 13Xcol-
umn, N2 as carrier). Extract 0.5 mL of gas into the instrument every
In Fig. 1(a), the crystal phase structure of the NiTiO3 and Fe2P
1 h.
prepared by X-ray diffraction analysis was discussed in detail.
Comparing the standard cards of NiTiO3 (PDF#17e617), it is found
2.7. Photoelectrochemical measurements that NiTiO3 has a better crystal structure, and the diffraction peaks
correspond well to the crystal faces in the standard cards. Among
The samples were subjected to photoelectrochemical mea- them, the peaks at 2q ¼ 24.14 , 33.02 , 35.60 , 40.82 , 49.37,
surement on an electrochemical analyzer (VersaStat4-400, 54.10 , 62.42 and 64.13 correspond to (0 1 2), (1 0 4), (1 1 0), (1 1 3),
Advanced Measurement Technology, Inc). The entire electro- (0 2 4), (1 1 6), (2 1 4) and (0 3 0) crystal planes, further indicating
chemical test process is carried out in a standard three-electrode the successful preparation of NiTiO3. The Fe2P obtained by phos-
system, with 0.2 M Na2SO4 solution as the electrolyte. The light phating with MIL-53(Fe) as the precursor not only corresponds well
source was a 300 W Xenon lamp with a 420 nm filter. The platinum to the standard card but also did not detect the peaks of MIL-53(Fe),
electrode in the three-electrode system is used as a pair of elec- indicating that Fe2P was successfully obtained (PDF#85e1727).
trodes, the saturated calomel electrode is used as the reference Obviously, Fe2P has a relatively obvious diffraction peak at 40.20 ,
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H. Li, H. Gong, X. Hao et al. Renewable Energy 188 (2022) 132e144

Fig. 1. XRD patterns of (a) NiTiO3 and Fe2P; (b) MIL-53(Fe), NiTiO3, Fe2P and x-NFP.

which is attributed to its (1 1 1) crystal plane. The crystal phase regular block structure. The size of MIL-53(Fe) is about
structure of the prepared composite material is shown in Fig. 1(b). 5 mm  6 mm, corresponding to its shorter and longer edges. As
Among them, MIL-53(Fe) has typical diffraction peaks at 2q ¼ 9.26 , shown in Fig. 2(b), as one of the most common perovskite mate-
18.51 and 27.87. The position of the diffraction peaks are consis- rials, NiTiO3 exhibits a porous rod-like structure with a size smaller
tent with previous reports [24]. The shape of the diffraction peaks than MIL-53(Fe). The length of each hollow rod is about 2 mme3 mm
of the composite materials is roughly similar to that of NiTiO3. With and the diameter is about 500 nm. The results of scanning electron
the increase of Fe2P content, the intensity of the diffraction peak microscopy confirmed that the size of MIL-53(Fe) is larger than that
attributable to the (2 0 1) crystal plane of Fe2P gradually increases, of NiTiO3, and it can be used as a growth substrate to disperse and
which further illustrates the successful recombination of NiTiO3 grow NiTiO3 on the surface. After processing MIL-53(Fe) by high-
and Fe2P. temperature phosphating, it was found that its original
morphology had changed. The particles appearing on the surface of
3.2. Morphology and structure MIL-53(Fe) are due to the destruction of the original framework
structure by high temperature treatment to generate Fe2P nano-
The microscopic morphology of the sample is one of its particles, as shown in Fig. 2(c). Fig. 2(d) shows that MIL-53(Fe) has
important properties. Therefore, in-depth exploration of the sur- achieved the advantages of a metal-organic framework material as
face morphology of MIL-53(Fe), Fe2P, NiTiO3 and 20-NFP uses a support material. NiTiO3 porous nanorods and Fe2P nanoparticles
scanning electron microscopy and transmission electron micro- were dispersed and grown on the surface of MIL-53(Fe), further
scopy. The morphology modification of photocatalyst is also one of demonstrating the successful preparation of composite materials.
the important strategies to improve the catalytic performance of The TEM spectra further confirmed the surface morphology of
single materials. In Fig. 2(a), the MIL-53(Fe) presents a smooth MIL-53(Fe), Fe2P, NiTiO3 and 20-NFP. As shown in Fig. 3(a), the

Fig. 2. SEM images of (a) MIL-53(Fe); (b) NiTiO3; (c) Fe2P and (d) 20-NFP.

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Fig. 3. (a) TEM image; (b) HRTEM image; (c) EDX spectrum and (d) element mapping of 20-NFP.

morphology of 20-NFP in the TEM spectrum is consistent with the consistent with the EDX spectrum result. Fig. 4(b) shows the fine
SEM spectrum. The black short rod-like structure and nanoparticles spectrum of Ni 2p in NiTiO3 and 20-NFP. There are four typical
are evenly dispersed on the surface of MIL-53(Fe). The existence of peaks in the fine spectrum of NiTiO3 at 855.69 eV, 861.76 eV,
metal organic framework materials can largely avoid the aggrega- 873.31 eV, and 879.77 eV. Among them, the peaks appearing at
tion of NiTiO3 nanorods and Fe2P particles. The presence of lattice 855.69 eV and 873.31 eV are due to Ni 2p3/2 and Ni 2p1/2 of Ni2þ
fringes can be clearly observed in the HRTEM spectrum of the 20- [25,26]. In Fig. 4(c), there are two peaks in the fine spectrum of Ti
NFP in Fig. 3(b). Among them, the darker regions appearing at element. The peak at 458.14 eV and 463.89 eV belong to Ti 2p3/2
lattice spacings of 0.36 nm, 0.27 nm and 0.25 nm belong to the ((TiO2 4þ
3 ) and Ti 2p1/2 (Ti ), respectively [27]. The binding energy at
(012), (104) and (110) crystal planes of NiTiO3, which are confirmed 529.98 eV in the fine oxygen spectrum of pure NiTiO3 is related to
by XRD diffraction pattern. Similarly, the 0.22 nm lattice spacing the O2 ions around the Ti atom, as shown in Fig. 4(d) [25,26]. The
detected in the lighter color area was attributed to the (111) crystal binding energy of Ni, Ti and O in 20-NFP shift slightly to high-angle
plane of Fe2P. Fig. 3(c) and (d) are the EDX diagram and the element directions compared to pure NiTiO3. Similarly, the fine spectra of Fe
mapping of 20-NFP, respectively. The coexistence of Ni, Ti, O, Fe and and P elements in pure Fe2P and 20-NFP were studied. In Fig. 4(e),
P elements can be detected in both spectra, confirming the suc- two spin orbitals are observed in the fine spectrum of Fe 2p. The
cessful synthesis of the 20-NFP. peak of Fe2P at 707.38 eV can be assigned to the formation of FeeP
bond, indicating the successful preparation of Fe2P [28,29]. Another
3.3. X-ray photoelectron spectroscopy analysis peak appearing at 720.28 eV is due to the presence of FeeO species
due to surface oxidation [30]. The Fe 2p spectrum in the 20-NFP has
X-ray photoelectron spectroscopy is a powerful tool for studying two more peaks at 713.31 eV and 725.80 eV. The former is due to
the surface element composition and chemical valence of samples. Fe2P and the latter is due to surface oxidation [31]. In Fig. 4(f), the
The coexistence of Ni, Ti, O, Fe, and P elements in Fig. 4(a) is refined spectra of the P elements of Fe2P and 20-NFP show two
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H. Li, H. Gong, X. Hao et al. Renewable Energy 188 (2022) 132e144

Fig. 4. XPS spectra of NiTiO3, Fe2P and 20-NBP (a) survey spectrum; (b) Ni 2p; (c) Ti 2p; (d) O 1s; (e) Fe 2p; (f) P 2p.

similar peaks. The peak at 129.75 eV after fitting in pure Fe2P is multilayer adsorption characteristics. The inset is the pore size
attributed to P 2p2/1 in the P 2p orbital, indicating the formation of distribution diagram of the samples. The pore size of the sample is
metal phosphide. The other binding energy peak at 133.96 eV is due mainly distributed between 2 and 50 nm, which further confirms
to the phosphorus oxide species generated by the exposure of the that the material has the properties of a mesoporous material. The
material to air [32e34]. The binding energies of Fe and P elements results were shown in Table 2. The surface areas of MIL-53(Fe),
in the composites are shifted to lower angular directions compared NiTiO3, Fe2P and 20-NFP in the table are 9 m2/g, 10 m2/g, 14 m2/g
to pure Fe2P. The decrease in binding energy can also prove that and 7 m2/g, respectively. Obviously, the specific surface area of the
Fe2P can accept electrons from NiTiO3 to perform redox reactions, composite 20-NFP is reduced compared with MIL-53(Fe), NiTiO3
showing its role as a co-catalyst. The binding energy of different and Fe2P, indicating that the phosphating treatment has a certain
elements in the composite material has a slight shift, indicating effect on the surface morphology of the MIL-53(Fe). In addition, the
that there is a strong interaction between the two semiconductors. pore size of 20-NFP is between NiTiO3 and Fe2P, which may be
caused by the accumulation of Fe2P particles and rod-shaped
3.4. The brunauer-emmett-teller analysis NiTiO3.

The specific surface area, pore size and pore volume of MIL- 3.5. Photocatalytic activity and stability
53(Fe), NiTiO3, Fe2P and 20-NFP were analyzed using nitrogen
adsorption and desorption curves. In Fig. 5(a-d), the data curves of The hydrogen evolution kinetics experiments were carried out
MIL-53(Fe), NiTiO3, Fe2P and 20-NFP all show typical IV curve on MIL-53(Fe), NiTiO3, Fe2P and x-NFP to explore the hydrogen
characteristics. Meanwhile, P/P0 has a H3 hysteresis loop at 0.8e1.0, evolution activity. In Fig. 6(a), the hydrogen evolution activity of the
indicating that the material is a mesoporous material with composite material is significantly improved after optimization.
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Fig. 5. N2 adsorptionedesorption isotherms of MIL-53(Fe), Fe2P, NiTiO3 and 20-NFP; pore diameter distribution curve.

The hydrogen evolution of the composites was compared by the content of Hþ in the strong alkaline solution is small, so the
adjusting the content of MIL-53(Fe) precursor in the composites. thermodynamic power for hydrogen evolution is insufficient [36].
The hydrogen production activity of the photocatalyst showed a Therefore, the pH value of the sacrificial reagent is an important
volcanic trend that first gradually increased and then decreased factor affecting the hydrogen evolution activity of the photo-
with the increase of the amount of the precursor MIL-53(Fe), as catalyst. At the same time, the amount of dye sensitizer also has a
shown in Fig. 6(b). The hydrogen evolution of 20-NFP reaches the great influence on the hydrogen production performance of the
highest value (299.00 mmol) when the mass of MIL-53(Fe) is 20% of photocatalyst. In Fig. 6(d), the hydrogen production of the catalyst
that of NiTiO3. In order to further explore the influence of the increases with the addition of EY, because the adsorption of EY
hydrogen production environment on the photocatalyst activity, molecules on the surface of the photocatalyst enhances the ability
the hydrogen production was tested under the conditions of to absorb visible light. The hydrogen production performance of the
different pH values of sacrificial reagents and different EY dosages. catalyst is significantly reduced when the EY addition amount ex-
In Fig. 6(c), 20-NFP showed the best hydrogen production activity ceeds 20 mg. This is because too many EY molecules cover the
under the weakly alkaline conditions of pH ¼ 8. The reason is that active sites on the surface of the photocatalyst, which is not
TEOA is easily protonated in strong acid solutions and neutral so- conducive to the oxidation-reduction reaction [37].
lutions, which affects the photocatalytic reaction [35]. Meanwhile, The stability of the photocatalyst is also one of the important
factors affecting its performance, which is also a prerequisite for the
long-term development of the catalyst, as shown in Fig. 6(e). The
Table 2 stability test of the catalyst lasted for 4 cycles for a total of 20 h.
The SBET, pore volume and pore diameter distribution for the samples. Fresh EY 20 mg was added before the start of each cycle, and ni-
trogen gas was used to remove the hydrogen produced in the
Samples SBET (m2g1)a Pore volume (cm3g1)b Average pore size (nm)b
previous cycle. EY molecules can be degraded under long-term
MIL-53(Fe) 9 0.017 6 light, or the hydrogen evolution performance can be reduced due
Fe2P 10 0.026 9
NiTiO3 14 0.109 29
to the excessive accumulation of EY degradation products. How-
20-NFP 7 0.026 12 ever, the advantages of EY in the photocatalytic reaction process
a still cannot be ignored: (1) The molar absorption coefficient of the
Obtained from BET method.
b
Relative pressure (P/P0) was 0.99. EY molecule is larger and has a wider spectral absorption range; (2)

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Fig. 6. (a) Photocatalytic H2 evolution performances of MIL-53(Fe), Fe2P, NiTiO3 and 20-NFP; (b) H2 evolution rates of x-NFP under visible light irradiation; the effect of (c) PH; (d) EY
on hydrogen production activity of 20-NFP; (e) cycle stability experiments for 20-NFP; (f) Comparison of X-ray diffraction patterns after 5 h.

EY molecules have higher energy than the edge of the semi- the light absorption capacity of the photocatalyst is also one of the
conductor conduction band (lowest unoccupied orbital (LUMO)), important strategies to improve their photocatalytic performance.
which can promote the electron transfer of light-excited EY. As the Fig. 7(a) shows the light response spectrum of MIL-53(Fe), Fe2P,
acceptor of electrons, the photocatalyst has a more positive NiTiO3 and 20-NFP. Apparently, MIL-53(Fe) has stronger light ab-
reduction potential than the dye in order to facilitate the rapid sorption ability than NiTiO3. Among them, the wide absorption
regeneration of the dye; (3) EY can be firmly combined with the edge of NiTiO3 at 410 nm can be attributed to the interaction of O2/
surface of the semiconductor [38]. Therefore, the interaction be- Ti4þ charge transfer [39]. Similarly, two additional peaks appearing
tween EY and photocatalyst is also the reason for determining the at 449 and 510 nm are obtained due to the crystal field splitting of
performance of hydrogen production. The hydrogen evolution ac- NiTiO3 [40]. NiTiO3, a common perovskite material, and its unique
tivity of the composites decreased but was not serious after 20 h. In porous structure can provide an absorption path for light absorp-
Fig. 6e, the X-ray diffraction of the sample after 5 h of hydrogen tion. In addition, MIL-53(Fe) appears in the main absorption band
production was compared with the XRD pattern of the fresh sam- around 400 nm, and the characteristic absorption peak at 443 nm is
ple, and the crystal phase structure did not change significantly, the O(II) / Fe(III) absorption caused by ligand-metal charge
which further confirmed the stability of the sample. transfer (LMCT) [41]. The Fe2P obtained by phosphating treatment
with MIL-53(Fe) as the precursor shows the characteristics of a dark
3.6. Optical performance test of photocatalyst substance and shows good light absorption properties. Most
importantly, 20-NFP exhibited the best light absorption capacity,
The light absorption capacity of MIL-53(Fe), Fe2P, NiTiO3 and 20- indicating that the light absorption ability of the photocatalyst was
NFP were studied by ultraviolet diffuse reflectance test. Improving effectively improved.

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Fig. 7. (a) UVevis DRS spectra of MIL-53(Fe), Fe2P, NiTiO3 and 20-NFP; (b) Band gap energy of NiTiO3.

Additionally, the band gap energy (Eg) of the NiTiO3 was Table 3
calculated using the Kubelka Munk function according to the Kinetic analysis of emission decay for EY, MIL-53(Fe), Fe2P, NiTiO3 and 20-NFP.

relationship between (ahn)1/2 and photon energy (hn), as shown in Samples Lifetime, t [ns] Rel (%) t ave [ns] X2
Fig. 7(b). Hence, the band gap energy of NiTiO3 can be roughly EY t1 ¼ 0.18 A1 ¼ 100 0.18 1.06
estimated to be 2.19 eV, and the obtained value is similar to the MIL-53(Fe) t1 ¼ 4.71 A1 ¼ 0.41 0.21 1.05
value reported in the previous literature [8]. t2 ¼ 0.21 A2 ¼ 99.59
Fe2P t1 ¼ 3.79 A1 ¼ 0.71 0.16 1.31
= t2 ¼ 0.16 A2 ¼ 99.29
ahv ¼ Aðhv  Eg Þn 2
(1) NiTiO3 t1 ¼ 4.60 A1 ¼ 0.63 0.15 0.99
t2 ¼ 0.15 A2 ¼ 99.37
a, ʋ, Eg and A respectively is absorption coefficient, light fre- 20-NFP t1 ¼ 4.87 A1 ¼ 0.58 0.18 1.11
quency, bandgap energy, and a constant. t2 ¼ 0.18 A2 ¼ 99.42

3.7. Photoluminescence analysis

This is because the excited state electrons will fluoresce in the form
The co-catalyst has been proven to promote the transfer of light- of radiation transition and fluorescence and then be quenched,
induced carriers and can capture electrons as reaction sites. which is not conducive to the progress of the photocatalytic reac-
Therefore, the steady-state PL spectra and time-resolved photo- tion [44]. The fluorescence intensity of the EY solution was signif-
luminescence spectra of MIL-53(Fe), Fe2P, NiTiO3 and 20-NFP were icantly reduced after adding the photocatalyst, which proved that
recorded in order to further explore the carrier transfer behavior. In the separation efficiency of electron-hole pairs was effectively
Fig. 8(a), the steady-state spectrum of the samples in the EY solu- improved. The 20-NFP with the best hydrogen production perfor-
tion was obtained at an excitation wavelength of 480 nm. MIL- mance has the lowest fluorescence emission peak, which further
53(Fe), Fe2P, NiTiO3 and 20-NFP have similar emission peaks at shows that 20-NFP can effectively transfer the excited state elec-
539 nm. The recombination of electrons and holes in the photo- trons of EY and accelerate the separation and transfer of carriers.
catalyst is manifested by the intensity of the fluorescence emission The time-resolved fluorescence decay spectrum was obtained
peak. The lower the fluorescence intensity, the higher the separa- by fitting the double exponential decay kinetic function, as shown
tion efficiency of carriers [42]. Among them, the EY solution in Fig. 8(b). The parameters and fluorescence lifetime of the sam-
(1x106 M) has the highest fluorescence emission peak, reflecting ples were shown in Table 3. The EY solution uses a single expo-
the rebound quenching process of excited electrons [43]. It is well nential decay kinetic function to obtain an average life of 0.18 ns
known that electrons transition from the ground state to the [45]. The average lifetimes of Fe2P, NiTiO3 and 20-NFP are 0.16 ns,
excited state after EY is excited by light. However, the excited state 0.15 ns and 0.18 ns, respectively. The increase in the carrier lifetime
electrons cannot be effectively transferred due to the short lifetime. of the composites is related to the improved separation efficiency of

Fig. 8. (a) Steady-state fluorescence spectrum and (b) time-resolved fluorescence emission decay curves of EY, MIL-53(Fe), NiTiO3, Fe2P and 20-NFP.

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H. Li, H. Gong, X. Hao et al. Renewable Energy 188 (2022) 132e144

electrons by the introduction of cocatalysts [46]. density indicates that the Fe2P can effectively capture electrons
X from NiTiO3 for hydrogen evolution reaction, and effectively inhibit
IðtÞ ¼ Ai et=ti (2) the recombination of electrons and holes [47]. In addition, the
i¼1;2 samples were tested by electrochemical impedance spectroscopy,
as shown in Fig. 9(b). Generally speaking, the radius of the Nyquist
P
i¼1;2 Ai t2i curve is related to the rate of charge transfer in the interface re-
< tave > ¼ P (3) action. The smaller the arc radius, the faster the charge transfer
i¼1;2 Ai ti
rate, indicating that the photocatalyst has a higher separation ef-
t1 and t2 are emission lifetimes; A is the corresponding ficiency of photogenerated electrons [48]. The electrochemical
amplitude. impedance radius of the MIL-53(Fe) is the largest, indicating that its
interface resistance is large, which is not conducive to the effective
transfer of electrons, which corresponds to its weak hydrogen
3.8. Electrochemical characterization production performance in TEOA solution. Similarly, NiTiO3 also has
a large charge transfer resistance, which is not conducive to the
To further demonstrate the important role of Fe2P as co- hydrogen evolution reaction. In addition, the electrochemical
catalysts in increasing the separation efficiency of carriers, photo- interface resistance of 20-NFP is the smallest, which means that the
chemical tests (transient photocurrent test (IT), electrochemical charge transfer of the material has been advantageously improved
impedance test (EIS), polarization curve test (LSV) and Mott- [49]. It is further confirmed that Fe2P can be used as the trapping
Schottky test) were performed on MIL-53(Fe), Fe2P, NiTiO3 and center of electrons and promote the transfer of carriers.
20-NFP. As shown in Fig. 9(a), the transient photocurrent response In addition, the polarization curves of different samples were
curves of MIL-53(Fe), Fe2P, NiTiO3 and 20-NFP were obtained with tested. In Fig. 9(c), the 20-NFP working electrode has a lower
on-off cycle light source. It can be seen from the figure that the 20- overpotential than MIL-53(Fe), NiTiO3 and Fe2P. Similarly, Fe2P also
NFP working electrode exhibits the strongest photocurrent has a lower reaction overpotential than its precursor MIL-53(Fe).
response in Na2SO4 electrolyte. The increase in photocurrent

Fig. 9. (a) Transient photocurrent response; (b) Nyquist plots; (c) LSV curves and (def) Mott-Schottky plots for MIL-53(Fe), NiTiO3, Fe2P and 20-NFP.

141
H. Li, H. Gong, X. Hao et al. Renewable Energy 188 (2022) 132e144

From the polarization curve, it can be seen that the reason for the structure of NiTiO3 on the basis of structural optimization. It is
improved conductivity of 20-NFP can be attributed to the good concluded that NiTiO3 is a magnetic semiconductor with an indi-
metal-like properties of Fe2P, which improves the conductivity of rect band gap of 2.038 eV. The theoretical value is smaller than the
the material [50]. The Mott-Schottky test was used to discuss the experimental value (2.19 eV), but the difference is not large. Simi-
semiconductor type and energy band structure of the samples. larly, Fe2P is defined as a magnetic metal, which is consistent with
According to previous literature reports, the slope of the Mott- the metal-like properties and good electrical conductivity of
Schottky curve is negative and it is regarded as a p-type semi- phosphides (in Fig. 10(d)). This result is consistent with that Fe2P
conductor, otherwise, it is regarded as an n-type semiconductor acts as a trapping center for electrons to attract electrons from the
[51]. In Fig. 9(d-f), NiTiO3, MIL-53(Fe) and Fe2P satisfy the charac- conduction band of NiTiO3 for hydrogen evolution reaction. In
teristics of n-type semiconductors. Therefore, the flat band poten- addition, the density of states of NiTiO3 and Fe2P in GGA þ U along
tials of NiTiO3, MIL-53(Fe) and Fe2P relative to the calomel the high symmetry direction is shown in Fig. 10(e-f). The DOS data
electrode are 0.64 eV, 0.43 eV and 0.55 eV, respectively. The can also reveal the bonding behavior of NiTiO3, especially the par-
conduction band potential of the semiconductor is judged accord- tial covalency of the cationic and anionic bonds, which can be
ing to the flat band potential (more negative 0.1 eV or 0.2 eV). further correlated with the intrinsic properties of the material.
According to formula (4), the conduction band potentials of NiTiO3, According to the analysis of the DOS spectrum, it is shown that the
MIL-53(Fe) and Fe2P under the standard hydrogen electrode valence band of NiTiO3 is mainly composed of O 2p states, and the
are 0.60 eV, 0.39 eV and 0.51 eV, respectively. The potential conduction band is mainly composed of Ni 3d states and Ti 3d
energy difference between NiTiO3 and Fe2P confirms that electrons states.
in the conduction band of NiTiO3 can be transferred to the con-
duction band of Fe2P [52]. In addition, formula 5 and the band gap
value of NiTiO3 in the UVevisible diffuse reflectance spectra test are 3.9. Possible photocatalytic mechanism over NiTiO3/Fe2P
used to further obtain the position of the valence band, and the
possible hydrogen production mechanism of the composite mate- In Fig. 11, a possible photocatalytic reaction mechanism was
rial is proposed. proposed for NiTiO3/Fe2P. The carriers in the valence band of the
two semiconductor materials migrate to the conduction band po-
ENHE ¼ ESCE þ 0:24 eV (4) sition under visible light irradiation [55]. The Fe2P has metallic
characteristics and good electrical conductivity, which can effec-
tively transfer electrons from the conduction band of NiTiO3 and
ECB ¼ EVB  Eg (5)
effectively increase the transfer rate of carriers [56]. The lower
Fig. 10 (a, b) shows the optimized model of NiTiO3 and Fe2P. The conduction band position of Fe2P receives electrons from the con-
structure relaxes only when the force on the atoms is less than duction band of NiTiO3 as the active site for the reaction to produce
0.05 eV. As a correction for localized (strongly correlated) electrons, hydrogen. The electrons in the NiTiO3 conductive band are effec-
the Coulomb term was added to Ni, Ti and Fe using the LDA þ U tively separated and transferred, avoiding the recombination of
method. Among them, the d orbitals of Ni and Ti elements in NiTiO3 electrons and holes, enabling them to participate in the redox re-
have U ¼ 4.5 eV, J ¼ 0.9 eV [53]. At the same time, the d orbital of Fe action more effectively [57]. Among them, the holes remaining in
element is set to U ¼ 3.81 eV [54]. Fig. 10(c) shows the band the valence band of NiTiO3 are consumed by TEOA [58,59].

Fig. 10. (a,b) Model structure; (c,d) Band structures and (e,f) Density of states of NiTiO3 and Fe2P.

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H. Li, H. Gong, X. Hao et al. Renewable Energy 188 (2022) 132e144

Fig. 11. Mechanism diagram of NiTiO3/Fe2P.

4. Conclusion Acknowledgements

The NiTiO3/Fe2P with high-efficiency hydrogen production This work was financially supported by the Chinese National
performance was obtained by calcining method. By using MIL- Natural Science Foundation (22062001) and the Graduate Innova-
53(Fe) as the precursor material, the basic structure is basically tion Project of North Minzu University (YCX21135).
maintained after phosphating treatment, which provides the
growth substrate for the dispersion of Fe2P and NiTiO3. Fe2P has
played an important role in the modification of NiTiO3 due to its References
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