Photoelectrocatalytic hydrogen production photoelectrode Ni-Mo-B combined TNTs and preparation method thereof
By using Ni-Mo-B combined with TNTs in photoelectrodes to regulate the electronic structure of metals and carriers, the problems of slow reaction kinetics and high overpotentials in electrocatalytic decomposition of water hydrogen production technology are solved, and the problem of slow reaction kinetics and high overpotentials in electrocatalytic decomposition of water hydrogen production technology is achieved. The effect of high-efficiency photoelectrocatalytic decomposition of water to produce hydrogen.
Patent Information
- Application Number
- CN202411303144.4
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-09-19
- Publication Date
- 2024-12-13
AI Technical Summary
The electrocatalytic decomposition of water hydrogen production technology has problems such as slow reaction kinetics and high overpotentials, which leads to a reduced energy conversion efficiency and an increase in electrical energy consumption, limiting the development of this technology.
TiO2 nanotubes were prepared by photoelectrode Ni-Mo-B combined with TNTs by anodizing method, and non-metallic B and bimetallic NiMo alloys were modified on their surface by one-step electrodeposition method to regulate the d-electron structure and light of metals. The electronic structure on the surface of the electrode forms an ionic metal-boride bond to improve catalytic performance.
It effectively reduces the HER overpotential, improves the activity and stability of photoelectrocatalytic hydrogen evolution, and realizes high-efficiency photoelectrocatalytic decomposition of water to produce hydrogen, significantly improving catalytic performance and active sites.
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Figure CN119121309A_ABST
Abstract
Description
Technical Field
[0001] The present invention relates to the technical field of photoelectrocatalytic hydrogen production, and in particular to a composite photoelectrode with adjustable electronic structure and a construction method thereof, in particular to a photoelectrocatalytic hydrogen production photoelectrode Ni-Mo-B combined with TNTs and a preparation method thereof. Background Art
[0002] Due to the increasingly serious environmental pollution caused by the extensive use of fossil energy, the development of green and renewable energy is imperative, and hydrogen is a promising clean energy.
[0003] At present, the technology of producing hydrogen by electrocatalytic water decomposition has the advantages of sustainability, environmental protection, and wide application, and will play an important role in the future hydrogen economy. However, this technology still has problems of slow reaction kinetics and high overpotential, which will lead to lower energy conversion efficiency and increased electricity consumption, thereby increasing production costs.
[0004] As global energy shortages and environmental issues become increasingly severe, the concept of "hydrogen economy" has gained more and more widespread recognition.
[0005] However, the current electrocatalytic hydrogen production electrode catalysts still have key problems such as slow carrier diffusion on the electrode surface, few catalytic active sites, and high HER overpotential, which restrict the further development of this technology.
[0006] Therefore, we need to propose a photoelectrode Ni-Mo-B combined with TNTs and its preparation method to effectively reduce the HER overpotential, improve the photoelectrocatalytic hydrogen evolution activity, and realize efficient photoelectrocatalytic water decomposition to produce hydrogen. Summary of the invention
[0007] The purpose of the present invention is to provide a photoelectrode Ni-Mo-B combined with TNTs for photoelectrocatalytic hydrogen production and a preparation method thereof, which regulates the d electronic structure of the metal; the strong interaction between the metal and the carrier regulates the electronic structure of the photoelectrode surface, thereby improving the catalytic performance; the hydrogen evolution active site of the catalyst is increased, the electronic structure is regulated, the HER overpotential is reduced, and excellent HER catalytic activity and stability are exhibited, so as to solve the problems raised in the above-mentioned background technology.
[0008] To achieve the above-mentioned purpose, the present invention provides the following technical scheme: a photoelectrode Ni-Mo-B combined with TNTs for photoelectrocatalytic hydrogen production, comprising TiO2 nanotubes prepared by an anodic oxidation method, and non-metallic B and bimetallic NiMo alloy, wherein the non-metallic B and bimetallic NiMo alloy are coated on the surface of the TiO2 nanotubes by a one-step electrodeposition method, wherein the non-metallic B is used to regulate the electronic structure of the bimetallic NiMo alloy, and the bimetallic NiMo alloy is used to regulate the d electronic structure of the metal, and the non-metallic B atoms are combined with the Ni and Mo transition metals in the bimetallic NiMo alloy to form ionic metal-boride bonds.
[0009] The present invention also provides a method for preparing a photoelectrode Ni-Mo-B combined with TNTs for photoelectrocatalytic hydrogen production, which is used to prepare the above-described photoelectrode Ni-Mo-B combined with TNTs for photoelectrocatalytic hydrogen production, comprising the following steps: S1, preparing TNTs by anodization method; S2, using electrochemical precipitation method to prepare Ni-Mo-B / TNTs composite photoelectrode based on TNTs; S3. Detection of the photoelectrochemical properties of Ni-Mo-B / TNTs composite photoelectrode.
[0010] Preferably, in step S1, the preparation method of TNTs is as follows: S11, cutting the Ti sheet into a size of 1 cm×2 cm, first grinding the Ti sheet with sandpaper to remove surface oxides, and then ultrasonically cleaning it with anhydrous ethanol and acetone for 30 min respectively; S12, placing the cleaned Ti sheet in a polytetrafluoroethylene beaker filled with a mixed solution of HF:HNO3:H2O with a volume ratio of 1:4:5, soaking for 1 minute for polishing, and then rinsing with pure water; S13, using a mixture of 100 mL of pure water, 100 mL of glycerol and 1.13 g of NH4F as an electrolytic solution, a Pt sheet as a cathode, and a polished Ti sheet as an anode, and electrolyzing for 1 h at a voltage of 20 V; S14, clean with pure water and ultrasonic for 1 min, and finally calcine at 450°C for 2 h in a muffle furnace to obtain TiO2 nanotubes.
[0011] Preferably, in step S2, the preparation method of the Ni-Mo-B / TNTs composite photoelectrode is as follows: S21, dissolve 10.00 mmol of NiCl2·6H2O, 3.50 mmol of Na2MoO4·2H2O, 12.48 mmol of Na2B4O7·10H2O and 10.00 mmol of C6H8O7·H2O in 50 mL of ultrapure water and stir for 30 min to form an electrolyte; S22, using a three-electrode system, with TiO2 nanotube photoelectrode as the working electrode, Pt wire as the counter electrode, and saturated calomel electrode as the reference electrode, constant potential deposition was performed at a voltage of -1.1 V relative to the saturated calomel electrode for 60 min to obtain a semi-finished Ni-Mo-B / TNTs composite photoelectrode; S23. After the deposition is completed, the semi-finished Ni-Mo-B / TNTs composite photoelectrode is cleaned several times with anhydrous ethanol and ultrapure water, and finally dried in a vacuum drying oven at 60°C for 2 h to obtain a Ni-Mo-B / TNTs composite photoelectrode.
[0012] Preferably, in step S3, the photoelectrochemical performance detection of the Ni-Mo-B / TNTs composite photoelectrode includes a photoelectrochemical characterization test and a photoelectrocatalytic activity test, and the photoelectrochemical characterization test and the photoelectrocatalytic activity test are both performed at room temperature using a standard three-electrode system.
[0013] Preferably, the photoelectrochemical characterization test method of the Ni-Mo-B / TNTs composite photoelectrode is as follows: A1, Ni-Mo-B / TNTs composite photoelectrode as working electrode, Pt wire as counter electrode, Hg / HgO electrode as reference electrode, 1 mol KOH solution as electrolyte; A2, 1mV s -1 The iR-corrected linear sweep voltammogram was measured at a scan rate of , and the Tafel slope of the sample was calculated according to the formula η = blog(j) + a; A3. Cyclic voltammetry was used to measure the double-layer capacitance of the sample in the non-Faraday range at different scan rates, and the electrochemically active specific surface area was calculated.
[0014] Preferably, in the formula η=b log(j)+a, η represents overpotential, a represents Tafel constant, b represents Tafel slope, and j represents current density; In step A3, the scan rates were 20 mV s -1 , 40 mV s -1 , 60 mV s -1 , 80 mV s -1 , 100 mV s -1 and 120 mV s -1 .
[0015] Preferably, the photoelectrocatalytic activity test of the Ni-Mo-B / TNTs composite photoelectrode is carried out in an H-type electrolytic cell with a circulating water cooling interlayer, and the method is as follows: B1. Place the PEC photoelectric system in a metal dark box to prevent external light from affecting the test process; B2, using a three-electrode working system, with 1 mol KOH solution as the electrolyte, Ni-Mo-B / TNTs as the working electrode, Pt wire as the counter electrode, Hg / HgO electrode as the reference electrode, and a xenon lamp light source to simulate sunlight; B3. Control the distance between the catalytic electrode and the light source to be 10 cm, apply bias voltage to the working electrode for hydrogen evolution treatment, and use a gas chromatograph equipped with a thermal conductivity detector to measure the H2 production.
[0016] Compared with the prior art, the present invention has the following beneficial effects: 1. In the Ni-Mo-B combined with TNTs composite photoelectrode of the present invention, the alloying effect of the bimetallic NiMo regulates the d electronic structure of the metal; the strong interaction between the metal and the carrier regulates the electronic structure of the photoelectrode surface, thereby improving the catalytic performance; 2. The doping of non-metallic B in the present invention further regulates the electronic structure of the NiMo alloy. The transition metal atoms show electron-deficient characteristics. The B atoms combine with the Ni and Mo transition metals by forming ionic metal-boride bonds. The inherent charge transfer characteristics of the B atoms can significantly increase the electron density of the metal active sites, which is more conducive to promoting the adsorption and desorption of the intermediate H* on the catalyst surface, thereby reducing the HER overpotential. BRIEF DESCRIPTION OF THE DRAWINGS
[0017] Figure 1 It is a flowchart of the present invention; Figure 2 A flowchart of the process of preparing TNTs according to the present invention; Figure 3 A flowchart of the process of preparing Ni-Mo-B / TNTs composite photoelectrode according to the present invention; Figure 4 A flowchart of the photoelectrochemical characterization test of the present invention; Figure 5 It is a flowchart of the photoelectrocatalytic activity test of the present invention; Figure 6 XRD diagrams of the monomer and composite catalyst of the present invention; Figure 7 is a scanning electron microscope image of the TNTs of the present invention; Figure 8 This is a scanning electron microscope image of Ni-Mo-B / TNTs of the present invention; Fig. 9 The LSV curve diagram of the monomer and composite catalytic electrode of the present invention; Fig.10 It is a schematic diagram of the test data of the electrochemical active area of the composite catalytic electrode of the present invention; Fig.11 This is the XPS spectrum of the Ni 2p region of the present invention; Fig.12 This is the XPS spectrum of the Mo 3d region of the present invention; Fig.13 A bar graph showing the test data of the photoelectrocatalytic H2 production activity of the present invention; Fig.14 It is a curve chart of the stability test data of the composite catalyst photoelectrode of the present invention. DETAILED DESCRIPTION
[0018] The following will be combined with the drawings in the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.
[0019] See also Figure 1-14 The present invention provides a technical solution: a photoelectrode Ni-Mo-B combined with TNTs for photoelectrocatalytic hydrogen production, comprising TiO2 nanotubes prepared by an anodic oxidation method, and non-metallic B and bimetallic NiMo alloys, wherein the non-metallic B and bimetallic NiMo alloys are coated on the surface of the TiO2 nanotubes by a one-step electrodeposition method, wherein the non-metallic B is used to regulate the electronic structure of the bimetallic NiMo alloy, and the bimetallic NiMo alloy is used to regulate the d electronic structure of the metal, and the non-metallic B atoms are combined with the Ni and Mo transition metals in the bimetallic NiMo alloy to form ionic metal-boride bonds.
[0020] The present invention also provides a method for preparing a photoelectrode Ni-Mo-B combined with TNTs for photoelectrocatalytic hydrogen production, which is used to prepare the above-described photoelectrode Ni-Mo-B combined with TNTs. In order to construct a new photoelectrode, it is necessary to improve its photoelectrocatalytic water decomposition hydrogen production ability from the following three aspects: (1) establish a transmission channel to improve the carrier transmission efficiency; (2) increase the electrochemical active area and increase the catalytic active sites; (3) regulate the electronic structure of the catalyst to improve the hydrogen evolution ability, including the following steps: S1, preparing TNTs by anodization method; S2, using electrochemical precipitation method to prepare Ni-Mo-B / TNTs composite photoelectrode based on TNTs; S3. Detection of the photoelectrochemical properties of Ni-Mo-B / TNTs composite photoelectrode.
[0021] Photoelectrocatalytic water splitting technology combines solar water splitting technology and electrocatalytic water splitting technology to produce hydrogen. This technology can utilize the synergistic effect of semiconductor solar photocatalysis and electrocatalysis to increase the reaction kinetics rate, reduce the overpotential of the electrochemical hydrogen evolution (HER) process, and effectively save electricity.
[0022] Among the photoelectrode materials developed in recent years, array-type photoelectrodes such as TiO2 nanotubes (TNTs) not only have a large specific surface area and high absorbance, but also their unique array structure can provide a high-speed channel for electron transmission in the vertical direction, thereby improving the charge transfer efficiency of the photoelectrode. Therefore, they are widely used in the field of photoelectrocatalysis.
[0023] Among hydrogen evolution catalyst materials, compared with precious metal catalysts such as Pt, transition metals such as Ni, Fe, Co, Mo, etc. have the advantages of adjustable structure, stable performance, and abundant reserves. They have shown great potential in the fields of electrocatalysis, photocatalysis, and photoelectrocatalytic water decomposition to produce hydrogen, and have become a research hotspot in the field of photo(electro)catalytic water decomposition to produce hydrogen.
[0024] In response to the problems of slow reaction kinetics and high overpotential in the process of electrocatalytic water decomposition to produce hydrogen, this method uses TiO2 nanotubes as the photoelectrode substrate material to improve the optical absorption and electron transport properties of the catalytic material; uses non-metal B to regulate the electronic structure of the transition metal NiMo alloy, optimizes the interaction between the metal and the carrier, and regulates the electronic structure of the photoelectrode surface, thereby effectively reducing the HER overpotential, improving the photoelectrocatalytic hydrogen evolution activity, and achieving efficient photoelectrocatalytic water decomposition to produce hydrogen, laying a theoretical foundation for the application of photoelectrocatalytic water decomposition to produce hydrogen.
[0025] In step S1, the preparation method of TNTs is as follows: S11, cutting the Ti sheet into a size of 1 cm×2 cm, first grinding the Ti sheet with sandpaper to remove surface oxides, and then ultrasonically cleaning it with anhydrous ethanol and acetone for 30 min respectively; S12, placing the cleaned Ti sheet in a polytetrafluoroethylene beaker filled with a mixed solution of HF:HNO3:H2O with a volume ratio of 1:4:5, soaking for 1 minute for polishing, and then rinsing with pure water; S13, using a mixture of 100 mL of pure water, 100 mL of glycerol and 1.13 g of NH4F as an electrolytic solution, a Pt sheet as a cathode, and a polished Ti sheet as an anode, and electrolyzing for 1 h at a voltage of 20 V; S14, clean with pure water and ultrasonic for 1 min, and finally calcine at 450°C for 2 h in a muffle furnace to obtain TiO2 nanotubes.
[0026] In step S2, the preparation method of the Ni-Mo-B / TNTs composite photoelectrode is as follows: S21, dissolve 10.00 mmol of NiCl2·6H2O, 3.50 mmol of Na2MoO4·2H2O, 12.48 mmol of Na2B4O7·10H2O and 10.00 mmol of C6H8O7·H2O in 50 mL of ultrapure water and stir for 30 min to form an electrolyte; S22, using a three-electrode system, with TiO2 nanotube photoelectrode as the working electrode, Pt wire as the counter electrode, and saturated calomel electrode as the reference electrode, constant potential deposition was performed at a voltage of -1.1 V relative to the saturated calomel electrode for 60 min to obtain a semi-finished Ni-Mo-B / TNTs composite photoelectrode; S23. After the deposition is completed, the semi-finished Ni-Mo-B / TNTs composite photoelectrode is cleaned several times with anhydrous ethanol and ultrapure water, and finally dried in a vacuum drying oven at 60°C for 2 h to obtain a Ni-Mo-B / TNTs composite photoelectrode.
[0027] It is noted that Ni / TNTs and Ni-Mo / TNTs photoelectrodes are also prepared by the same method; the electrolyte for preparing Ni / TNTs contains only NiCl2·6H2O (i.e., the electrolyte contains only Ni), and the electrolyte for preparing Ni-Mo / TNTs does not contain Na2B4O7·10H2O (i.e., the electrolyte does not contain B).
[0028] The Ni-Mo-B / TNTs composite photoelectrode prepared by this method has the following advantages: Non-metallic B and transition metal NiMo alloy were modified onto the surface of TiO2 nanotubes by a one-step electrodeposition method to prepare the photoelectrode Ni-Mo-B / TNTs for photoelectrocatalytic hydrogen production.
[0029] The efficient charge transfer rate of the TiO2 nanotube array structure and the strong interaction between the metal NiMo alloy and the carrier are used to establish a channel for rapid charge transfer, thereby improving the charge migration rate in the photoelectrochemical process of the composite photoelectrode.
[0030] The bimetallic NiMo alloy effect is used to regulate the metal d electronic structure, and the strong interaction between the metal and the carrier TNTs is used to regulate the electronic structure of the photoelectrode surface to improve the photoelectrocatalytic hydrogen evolution activity.
[0031] The synergistic effect of non-metallic B and NiMo alloy increases the hydrogen evolution active sites of the catalyst, improves the hydrogen adsorption and desorption performance during the photoelectrocatalytic process, and reduces the HER overpotential.
[0032] The resulting Ni-Mo-B / TNTs composite photoelectrode with high charge transfer efficiency and high catalytic activity was used for the study of photoelectrocatalytic H2 production.
[0033] In step S3, the photoelectrochemical performance detection of the Ni-Mo-B / TNTs composite photoelectrode includes a photoelectrochemical characterization test and a photoelectrocatalytic activity test, both of which are tested on an electrochemical workstation (CHI 660E, Shanghai Chenhua) using a standard three-electrode system at room temperature.
[0034] The photoelectrochemical characterization test method of the Ni-Mo-B / TNTs composite photoelectrode is as follows: A1, Ni-Mo-B / TNTs composite photoelectrode as working electrode, Pt wire as counter electrode, Hg / HgO electrode as reference electrode, 1 mol KOH solution as electrolyte; A2, 1mV s -1 The iR-corrected linear sweep voltammogram (LSV) was measured at a scan rate of , and the Tafel slope of the sample was calculated according to the formula η = blog(j) + a; A3. Cyclic voltammetry was used to measure the double layer capacitance (Cdl) of the samples in the non-Faraday range at different scan rates, and the electrochemically active specific surface areas (ECSAs) were calculated.
[0035] In the formula η=b log(j)+a, η represents the overpotential, a represents the Tafel constant, b represents the Tafel slope, and j represents the current density; In step A3, the scan rates were 20 mV s -1 , 40 mV s -1 , 60 mV s -1 , 80 mV s -1 , 100 mV s -1 and 120 mV s -1 .
[0036] The photoelectrocatalytic activity test of the Ni-Mo-B / TNTs composite photoelectrode was carried out in an H-type electrolytic cell with a circulating water cooling interlayer, and the method was as follows: B1. Place the PEC photoelectric system in a metal dark box to prevent external light from affecting the test process; B2, a three-electrode working system was used, with 1 mol KOH solution as the electrolyte, Ni-Mo-B / TNTs as the working electrode, Pt wire as the counter electrode, Hg / HgO electrode as the reference electrode, and a xenon lamp light source was used to simulate sunlight; the light source used was a 500 W CHF500 xenon lamp from Beijing Changtuo Technology Co., Ltd. B3. The distance between the catalytic electrode and the light source was controlled to be 10 cm, and a bias voltage was applied to the working electrode for hydrogen evolution treatment using the electrochemical workstation IT mode. The H2 production was determined using a Beijing Puxi G5 gas chromatograph equipped with a thermal conductivity detector.
[0037] In the photoelectrochemical characterization test of Ni-Mo-B / TNTs composite photoelectrode, the frequency range of electrochemical impedance spectroscopy (EIS) measurement was 1-10 5 Hz, amplitude 1 mV; Mott Schottky (MS) measurement frequency is 1000 Hz. All electrode potentials are converted to the reversible hydrogen electrode (RHE) potential, E(RHE) = E(Hg / HgO) + 0.098 + 0.059pH.
[0038] Compared with the existing technologies and products, the present invention has the following beneficial effects: In the Ni-Mo-B / TNTs composite photoelectrode, the alloying effect of the bimetallic NiMo regulates the d-electronic structure of the metal; the strong interaction between the metal and the carrier regulates the electronic structure of the photoelectrode surface, thereby improving the catalytic performance.
[0039] The doping of non-metallic B further regulates the electronic structure of NiMo alloy. B atoms combine with Ni and Mo transition metals by forming ionic metal-boride bonds. Transition metal atoms exhibit electron-deficient characteristics, while the inherent charge transfer characteristics of B atoms can significantly increase the electron density of metal active sites, which is more conducive to promoting the adsorption and desorption of intermediate H* on the catalyst surface, thereby reducing the HER overpotential. .
[0040] The synergistic effect of non-metallic B and NiMo alloy increases the active sites of hydrogen evolution of the catalyst, regulates the electronic structure, reduces the HER overpotential, and exhibits excellent HER catalytic activity and stability. The research results highlight the potential of non-metallic synergistic transition metal alloy co-modified photoelectrode materials as photoelectrocatalytic water decomposition hydrogen production.
[0041] Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that various changes, modifications, substitutions and variations may be made to the embodiments without departing from the principles and spirit of the present invention, and that the scope of the present invention is defined by the appended claims and their equivalents.
Claims
1. A photoelectrode Ni-Mo-B combined with TNTs for photoelectrocatalytic hydrogen production, characterized in that: It includes TiO2 nanotubes prepared by an anodic oxidation method, and non-metallic B and bimetallic NiMo alloy. The non-metallic B and bimetallic NiMo alloy are coated on the surface of the TiO2 nanotubes by a one-step electrodeposition method. The non-metallic B is used to regulate the electronic structure of the bimetallic NiMo alloy. The bimetallic NiMo alloy is used to regulate the d electronic structure of the metal. The non-metallic B atoms combine with Ni and Mo transition metals in the bimetallic NiMo alloy to form ionic metal-boride bonds.
2. A method for preparing a photoelectrode Ni-Mo-B combined with TNTs for photoelectrocatalytic hydrogen production, which is used to prepare a photoelectrode Ni-Mo-B combined with TNTs for photoelectrocatalytic hydrogen production according to claim 1, characterized in that: The steps include: S1, preparing TNTs by anodization method; S2, using electrochemical precipitation method to prepare Ni-Mo-B / TNTs composite photoelectrode based on TNTs; S3. Detection of the photoelectrochemical properties of Ni-Mo-B / TNTs composite photoelectrode.
3. The method for preparing a photoelectrode Ni-Mo-B combined with TNTs for photoelectrocatalytic hydrogen production according to claim 2, characterized in that: In step S1, the preparation method of TNTs is as follows: S11, cutting the Ti sheet into a size of 1 cm×2 cm, first grinding the Ti sheet with sandpaper to remove surface oxides, and then ultrasonically cleaning it with anhydrous ethanol and acetone for 30 min respectively; S12, placing the cleaned Ti sheet in a polytetrafluoroethylene beaker filled with a mixed solution of HF:HNO3:H2O with a volume ratio of 1:4:5, soaking for 1 minute for polishing, and then rinsing with pure water; S13, using a mixture of 100 mL of pure water, 100 mL of glycerol and 1.13 g of NH4F as an electrolytic solution, a Pt sheet as a cathode, and a polished Ti sheet as an anode, and electrolyzing for 1 h at a voltage of 20 V; S14, clean with pure water and ultrasonic for 1 min, and finally calcine at 450°C for 2 h in a muffle furnace to obtain TiO2 nanotubes.
4. The method for preparing a photoelectrode Ni-Mo-B combined with TNTs for photoelectrocatalytic hydrogen production according to claim 3, characterized in that: In step S2, the preparation method of the Ni-Mo-B / TNTs composite photoelectrode is as follows: S21, dissolve 10.00 mmol of NiCl2·6H2O, 3.50 mmol of Na2MoO4·2H2O, 12.48 mmol of Na2B4O7·10H2O and 10.00 mmol of C6H8O7·H2O in 50 mL of ultrapure water and stir for 30 min to form an electrolyte; S22, using a three-electrode system, with TiO2 nanotube photoelectrode as the working electrode, Pt wire as the counter electrode, and saturated calomel electrode as the reference electrode, constant potential deposition was performed at a voltage of -1.1 V relative to the saturated calomel electrode for 60 min to obtain a semi-finished Ni-Mo-B / TNTs composite photoelectrode; S23. After the deposition is completed, the semi-finished Ni-Mo-B / TNTs composite photoelectrode is cleaned several times with anhydrous ethanol and ultrapure water, and finally dried in a vacuum drying oven at 60°C for 2 h to obtain a Ni-Mo-B / TNTs composite photoelectrode.
5. The method for preparing a photoelectrode Ni-Mo-B combined with TNTs for photoelectrocatalytic hydrogen production according to claim 4, characterized in that: In step S3, the photoelectrochemical performance detection of the Ni-Mo-B / TNTs composite photoelectrode includes a photoelectrochemical characterization test and a photoelectrocatalytic activity test, and the photoelectrochemical characterization test and the photoelectrocatalytic activity test are both tested at room temperature using a standard three-electrode system.
6. The method for preparing a photoelectrode Ni-Mo-B combined with TNTs for photoelectrocatalytic hydrogen production according to claim 5, characterized in that: The photoelectrochemical characterization test method of the Ni-Mo-B / TNTs composite photoelectrode is as follows: A1, Ni-Mo-B / TNTs composite photoelectrode as working electrode, Pt wire as counter electrode, Hg / HgO electrode as reference electrode, 1 mol KOH solution as electrolyte; A2, 1mV s -1 The iR-corrected linear sweep voltammogram was measured at a scan rate of , and the Tafel slope of the sample was calculated according to the formula η = blog(j) + a; A3. Cyclic voltammetry was used to measure the double-layer capacitance of the sample in the non-Faraday range at different scan rates, and the electrochemically active specific surface area was calculated.
7. The method for preparing a photoelectrode Ni-Mo-B combined with TNTs for photoelectrocatalytic hydrogen production according to claim 6, characterized in that: In the formula η=b log(j)+a, η represents the overpotential, a represents the Tafel constant, b represents the Tafel slope, and j represents the current density; In step A3, the scan rates were 20 mV s -1 , 40 mV s -1 , 60 mV s -1 , 80 mV s -1 , 100mV s -1 and 120 mV s -1 .
8. The method for preparing a photoelectrode Ni-Mo-B combined with TNTs for photoelectrocatalytic hydrogen production according to claim 5, characterized in that: The photoelectrocatalytic activity test of the Ni-Mo-B / TNTs composite photoelectrode was carried out in an H-type electrolytic cell with a circulating water cooling interlayer, and the method was as follows: B1. Place the PEC photoelectric system in a metal dark box to prevent external light from affecting the test process; B2, using a three-electrode working system, with 1 mol KOH solution as the electrolyte, Ni-Mo-B / TNTs as the working electrode, Pt wire as the counter electrode, Hg / HgO electrode as the reference electrode, and a xenon lamp light source to simulate sunlight; B3. Control the distance between the catalytic electrode and the light source to be 10 cm, apply bias voltage to the working electrode for hydrogen evolution treatment, and use a gas chromatograph equipped with a thermal conductivity detector to measure the H2 production.