CN105986292B - Preparation method of cobalt-nickel double-layer hydroxide modified titanium dioxide nanotube array and application of photoelectrochemical hydrolysis hydrogen production - Google Patents

Preparation method of cobalt-nickel double-layer hydroxide modified titanium dioxide nanotube array and application of photoelectrochemical hydrolysis hydrogen production Download PDF

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CN105986292B
CN105986292B CN201610037434.8A CN201610037434A CN105986292B CN 105986292 B CN105986292 B CN 105986292B CN 201610037434 A CN201610037434 A CN 201610037434A CN 105986292 B CN105986292 B CN 105986292B
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nanotube array
tio
cobalt
array electrode
titanium dioxide
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CN105986292A (en
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李士阔
陈炜健
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Anhui University
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    • Y02E60/30—Hydrogen technology
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Abstract

The invention discloses a preparation method of a titanium dioxide nanotube array electrode modified by cobalt and nickel double-layer hydroxide and application of photoelectrochemical hydrolysis hydrogen production. By electrochemical deposition on TiO2The wall of the nanotube is quickly and controllably modified with cobalt and nickel double-layer hydroxide. The reaction process is fast and efficient, and CoNi-LDHs is in TiO2The covering density of the nanotube surface is controllable. The modification of CoNi-LDHs obviously improves TiO2The absorption efficiency of the nano tube to ultraviolet light prolongs the service life of photo-generated electrons, accelerates the separation of the photo-generated electrons and holes, and the clean contact interface between the photo-generated electrons and the holes is also favorable for the transfer of the photo-generated electrons. The TiO modified by the cobalt and nickel double-layer hydroxide is quickly and controllably synthesized2The new method of the heterogeneous nanotube array electrode is convenient to operate, easy to industrialize and has important application value.

Description

Preparation method of cobalt-nickel double-layer hydroxide modified titanium dioxide nanotube array and application of photoelectrochemical hydrolysis hydrogen production
Technical Field
The invention belongs to the field of synthesis of inorganic semiconductor nano materials, and relates to titanium dioxide (TiO) modified by cobalt-nickel double hydroxide (CoNi-LDHs)2) Nanotube (TiO)2A preparation method of a @ CoNi-LDHs) array electrode and application thereof in photoelectrochemical hydrolysis hydrogen production.
Background
The discovery of TiO was first reported by professors Fujishima A and Honda K, university of Tokyo, Japan, since 19722The phenomenon that a single crystal electrode photocatalytically decomposes water to generate hydrogen begins, and a hydrogen production technology by photolysis of water has attracted extensive attention. As a method for preparing hydrogen, a clean energy, by directly utilizing solar energy, the development of a technology for photolyzing water becomes more and more important in the age with resource shortage. More and more semiconductor materials are used as electrode materials for photolyzing water, such as ZnO and Fe2O3，TiO2，WO3And the like, the main research direction is devoted to improving the absorption of visible light by these semiconductor materials and the photoelectric conversion efficiency thereof.
TiO2The semiconductor material is widely applied to the fields of gas sensing, piezoelectric materials, photocatalysts and the like as a stable semiconductor material with excellent electrochemical properties. TiO 22The forbidden band width of the solar cell is 3.2eV, the band gap is wide, and the light absorption range of the solar cell is limited in an ultraviolet region (only occupies solar energy)Total energy 5%), very fast photoproduction electron-hole recombination under illumination condition and low photoelectrocatalysis activity, so TiO is directly used2As a photo anode material, it is difficult to efficiently utilize sunlight. A number of methods have been used to modify TiO2And the absorption and utilization of visible light are improved, wherein a method for enhancing the photoelectric conversion efficiency by depositing cobalt and nickel double-layer hydroxide on the surface of a nano array is greatly developed. The cobalt and nickel double-layer hydroxide expands the absorption area of light on one hand, and on the other hand, due to the photoelectrocatalysis activity of the cobalt and nickel double-layer hydroxide, the absorption of visible light by the material can be promoted, the separation and transfer of photoproduction electrons in the material are accelerated, and the photoelectrochemical activity of the material can be obviously improved. Therefore, a simple, controllable and easy-to-operate TiO for synthesizing cobalt-nickel double-layer hydroxide by electrochemical deposition is developed2The method of the nano array has important theoretical research value and practical application significance.
Disclosure of Invention
In view of the above, the present invention provides a cobalt-nickel double hydroxide (CoNi-LDHs) modified titanium dioxide (TiO)2) Hetero nanotubes (i.e., TiO)2A preparation method of a @ CoNi-LDHs) array electrode and application thereof in photoelectrochemical hydrolysis hydrogen production.
In order to achieve the purpose, the invention adopts the following technical scheme:
TiO modified by cobalt and nickel double-layer hydroxide2The preparation method of the nanotube array electrode is characterized by comprising the following steps of:
(1) the cleaned titanium sheet is put into hexanediol water solution dissolved with ammonium fluoride for secondary anode oxidation reaction, and the sample obtained after the reaction is cleaned and then put into a vacuum drying oven for vacuum drying, thus obtaining TiO growing on the titanium sheet substrate in situ2A nanotube array;
(2) placing the sample obtained in the step (1) in a muffle furnace for high-temperature annealing treatment to obtain TiO with good crystallinity2A nanotube array;
(3) TiO obtained in the step (2)2Soaking the nanotube array in Co-Ni containing electrolyte solution for some time and with three electrodesThe system is subjected to electrochemical deposition to obtain TiO2The @ CoNi-LDHs heterogeneous nanotube array electrode.
The TiO modified by cobalt and nickel double-layer hydroxide2The preparation method of the nanotube array electrode is characterized by comprising the following steps: the amount of the ammonium fluoride in the step (1) is 0.1 to 10.0 g.
The TiO modified by cobalt and nickel double-layer hydroxide2The preparation method of the nanotube array electrode is characterized by comprising the following steps: the volume of the hexanediol in the step (1) is 10-90ml, the volume of the water is 0-10ml, and the total volume of the hexanediol aqueous solution dissolved with the ammonium fluoride is 100 ml.
The TiO modified by cobalt and nickel double-layer hydroxide2The preparation method of the nanotube array electrode is characterized by comprising the following steps: in the step (1), the constant voltage of the first anodic oxidation reaction is 10-80V, and the reaction time is 0.5-5 h; the constant voltage of the second anodic oxidation reaction is 20-80V, and the reaction time is 0.5-6 h. The vacuum drying temperature in the step (1) is 10-80 ℃, and the time is 1-12 h.
The TiO modified by cobalt and nickel double-layer hydroxide2The preparation method of the nanotube array electrode is characterized by comprising the following steps: the calcination time in the muffle furnace in the step (2) is 10-120min, and the calcination temperature is 100-800 ℃.
The TiO modified by cobalt and nickel double-layer hydroxide2The preparation method of the nanotube array electrode is characterized by comprising the following steps: CoCl described in step (3)2·6H2O、Ni(NO3)2·6H2The concentration of the O electrolyte solution is 1mM-50mM, the volume is 50ml, the electrochemical deposition time is 5-600s, and the constant potential is-2.0-0V.
The TiO modified by the cobalt and nickel double-layer hydroxide2The preparation method of the nanotube array is characterized by comprising the following steps: CoNi-LDHs flaky nano-particles are mainly deposited on TiO2The sample has larger absorption of light in an ultraviolet region at the tube wall and the top end of the nanotube.
The TiO modified by the cobalt and nickel double-layer hydroxide2The application of the nanotube array electrode in the field of photoelectrochemical hydrolysis hydrogen production.
TiO modified by cobalt and nickel double-layer hydroxide2The preparation method of the nanotube array electrode comprises the following steps:
(1) carrying out secondary anodic oxidation reaction on the cleaned titanium sheet in hexanediol water solution dissolved with ammonium fluoride, carrying out surface treatment on the reacted sample, and then drying in a vacuum drying oven to obtain TiO vertically growing on the titanium sheet substrate2A nanotube array precursor;
(2) placing the sample obtained in the step (1) in a muffle furnace for high-temperature annealing treatment to obtain TiO with good crystallinity2A nanotube array;
(3) TiO obtained in the step (2)2Soaking the nanotube array in electrolyte solution for a period of time, and preparing the TiO modified by the cobalt and nickel double hydroxide by an electrodeposition method2Heterogeneous nanotube array electrodes.
The amount of the ammonium fluoride in the step (1) is 0.1 to 10.0 g.
The volume of the hexanediol in the step (1) is 10-90ml, the volume of the water is 0-10ml, and the total volume of the solution is 100 ml.
In the step (1), the constant voltage of the anodic oxidation reaction is 10-80V, and the reaction time is 0.5-5 h.
The vacuum drying temperature in the step (1) is 20-80 ℃, and the time is 1-12 h.
The calcination time in the muffle furnace in the step (2) is 30-120min, and the calcination temperature is 400-800 ℃.
CoCl described in step (3)2·6H2O、Ni(NO3)2·6H2The O electrolyte solution has a concentration of 1mM-50mM and a volume of 50 ml.
The electrochemical deposition time in the step (3) is 5-600s, and the constant potential is-2.0-0V.
The prepared TiO modified by cobalt and nickel double-layer hydroxide2The maximum absorption peak of the nanotube array electrode is in the ultraviolet region.
The cobalt-nickel double-layer hydroxide modified TiO provided by the invention2Nanotube array electrode vs. original TiO2Nanotube array electrodesThe stability, the photoelectric conversion efficiency and the like of the electrode are remarkably improved.
The invention develops a TiO modified by quickly and controllably synthesizing cobalt-nickel double-layer hydroxide by using an electrochemical deposition method2A method of nanotube array electrodes. CoNi-LDHs flaky nano-particles are directly deposited on TiO2Nanotube walls and tops. LDHs and TiO2The clean contact interface is beneficial to the rapid separation and transfer of photo-generated electrons and the improvement of the photoelectrochemical activity of the composite electrode.
Compared with the prior art, the invention provides the TiO modified by the quickly and controllably synthesized cobalt and nickel double hydroxide2A novel method for nanotube array electrodes. The electrochemical deposition process is not only fast and efficient, but also CoNi-LDHs flaky nano particles are coated on TiO2The surface coverage density of the nanotube is controllable, and the good contact between the nanotube and the nanotube is more beneficial to the transmission of photo-generated electrons, so that the photoelectrochemical activity of the material can be obviously improved. Has important application prospect in the preparation of clean energy. The TiO modified by the cobalt and nickel double hydroxide is quickly and controllably synthesized2The new method of the heterogeneous nanotube array electrode is convenient to operate, easy to industrialize and has important application value.
Drawings
FIG. 1 is TiO2SEM pictures of nanotube arrays.
FIG. 2 is TiO2SEM picture of @ CoNi-LDHs heterogeneous nanotube array.
FIG. 3 is TiO2SEM pictures of nanotube array cross-section.
FIG. 4 is TiO2SEM picture of the section of the @ CoNi-LDHs heterogeneous nanotube array.
FIG. 5 is TiO2Nanotube array and TiO2And Raman spectrogram of the @ CoNi-LDHs heterogeneous nanotube array.
FIG. 6 is TiO2Nanotube array electrode and TiO2And linear scanning voltammetry curve of the @ CoNi-LDHs heterogeneous nanotube array electrode under the illumination condition.
FIG. 7 is TiO2Nanotube array electrode and TiO2@ CoNi-LDHs heterogeneous nanotube array electrodeA polar photolytic water efficiency spectrum.
FIG. 8 is TiO2Nanotube array electrode and TiO2The electron life spectrogram of the @ CoNi-LDHs heterogeneous nanotube array electrode.
FIG. 9 is TiO2Nanotube array electrode and TiO2And (3) an IPCE spectrogram of the @ CoNi-LDHs heterogeneous nanotube array electrode.
FIG. 10 is TiO2Nanotube array electrode and TiO2The stability spectrogram of the @ CoNi-LDHs heterogeneous nanotube array electrode.
FIG. 11 is TiO2Nanotube array electrode and TiO2The current-time spectrogram of the @ CoNi-LDHs heterogeneous nanotube array electrode under different light intensities.
FIG. 12 is TiO2Nanotube array electrode and TiO2And the solid ultraviolet-visible spectrum of the @ CoNi-LDHs heterogeneous nanotube array electrode.
FIG. 13 is TiO2Nanotube array electrode and TiO2And the fluorescence spectrogram of the @ CoNi-LDHs heterogeneous nanotube array electrode.
FIG. 14 is TiO2Nanotube array electrode and TiO2The light capture efficiency spectrogram of the @ CoNi-LDHs heterogeneous nanotube array electrode.
FIG. 15 is an enlarged view of a single nanotube and TiO2The mechanism of the @ CoNi-LDHs heterogeneous nanotube array electrode is shown schematically.
Detailed Description
The following further illustrates the related aspects of the invention in connection with specific examples. It should be noted that these examples are only for illustrating the present invention and are not to be construed as limiting the scope of the present invention, and that various changes or modifications of the present invention can be made by those skilled in the art after reading the contents of the present invention, which also fall within the scope of the claims appended to the present application.
Example 1
The smooth ground titanium plate (1 × 3 cm)2) The surface was cleaned and dried in air. Dissolving 0.5g ammonium fluoride in 100mL hexanediol water solution, stirring well, immersing one end of cleaned titanium sheet into the above solutionThe other end is clamped by an electrode clamp of a constant potential rectifier, and the voltage is controlled at 50V for 2 h. Taking out the sample, alternately washing with ethanol and deionized water, and drying for 5h at 60 ℃ in a vacuum drying oven. Putting into a muffle furnace, and treating at 600 ℃ for 2 h. CoCl was then prepared at 5mM concentrations2·6H2O、Ni(NO3)2·6H2And (4) mixing the solution O, putting 50mL of the mixed solution into a beaker, and electrodepositing for 5s under the constant potential of-1V of a three-electrode system. Taking out the sample, alternately cleaning the sample by using ethanol and deionized water, and storing the sample in a vacuum drying oven. FIG. 1 shows the TiO prepared2SEM pictures of nanotube arrays. Illustrating that at a very small magnification, TiO2The nanotube array still maintains regular morphology. FIG. 2 is TiO2SEM picture of @ CoNi-LDHs heterogeneous nanotube array. It can be seen that CoNi-LDHs nano-particles uniformly grow on TiO2The surface of the nanotubes. FIG. 3 is TiO2SEM pictures of nanotube array cross-section. It can be seen that TiO2The nanotube array has uniform and regular appearance. FIG. 4 is TiO2SEM picture of the section of the @ CoNi-LDHs heterogeneous nanotube array. Shows that the CoNi-LDHs nano-particles uniformly grow on TiO2The walls of the nanotubes. FIG. 5 is TiO2Nanotube array and TiO2And Raman spectrogram of the @ CoNi-LDHs nanotube array. It can be found that the CoNi-LDHs nanoparticles deposit on TiO2After nanotube coating, TiO2The raman characteristic peak intensity of (a) is changed. FIG. 6 is TiO2Nanotube array and TiO2Linear sweep voltammogram of the @ CoNi-LDHs nanotube array under light conditions. Illustrating that under light conditions, TiO2The @ CoNi-LDHs heterogeneous nanotube array electrode has larger photocurrent. FIG. 7 is TiO2Nanotube array electrode and TiO2And (3) a photolysis water efficiency spectrogram of the @ CoNi-LDHs nanotube array electrode. It can be found that TiO2The water photolysis efficiency of the @ CoNi-LDHs nanotube array electrode is as high as 1.01 percent, which is the original TiO2The photolysis efficiency of the nanotube array electrode is 3.3 times that of water. FIG. 8 is TiO2Nanotube array electrode and TiO2The electron life spectrogram of the @ CoNi-LDHs heterogeneous nanotube array electrode. After the CoNi-LDHs nano-particles are modified, the electron life is obviously prolonged. FIG. 9 is TiO2Nanotube array electrode and TiO2And (3) an IPCE spectrogram of the @ CoNi-LDHs heterogeneous nanotube array electrode. The introduction of CoNi-LDHs nano-particles can improve the photoelectric conversion efficiency. FIG. 10 is TiO2Nanotube array electrode and TiO2The stability spectrogram of the @ CoNi-LDHs heterogeneous nanotube array electrode. The deposition of the CoNi-LDHs nano-particles shows that the stability of the material is obviously improved. FIG. 11 is TiO2Nanotube array electrode and TiO2The current-time spectrogram of the @ CoNi-LDHs heterogeneous nanotube array electrode under different light intensities. The modified electrode was shown to have excellent responsiveness to light intensity. FIG. 12 is TiO2Nanotube array electrode and TiO2And the solid ultraviolet-visible spectrum of the @ CoNi-LDHs heterogeneous nanotube array electrode. Indicating TiO2The @ CoNi-LDHs nanotube material shows obvious enhanced absorption in the ultraviolet region. FIG. 13 is TiO2Nanotube array electrode and TiO2And the fluorescence spectrogram of the @ CoNi-LDHs heterogeneous nanotube array electrode. The separation capability of photoproduction electrons and holes is obviously enhanced after CoNi-LDHs modification. FIG. 14 is TiO2Nanotube array electrode and TiO2The light capture efficiency spectrogram of the @ CoNi-LDHs heterogeneous nanotube array electrode. Shows that the CoNi-LDHs modification obviously enhances TiO2Absorption of ultraviolet light by the nanotube array.
Example 2
The smooth ground titanium plate (1 × 3 cm)2) The surface was cleaned and dried in air. 0.5g of ammonium fluoride was dissolved in 100mL of an aqueous hexanediol solution, and the solution was stirred uniformly, and one end of the cleaned titanium plate was immersed in the solution, and the other end was held by an electrode holder of a potentiostat, and the voltage was controlled at 50V for 2 hours. Taking out the sample, alternately washing with ethanol and deionized water, and drying for 5h at 60 ℃ in a vacuum drying oven. Putting into a muffle furnace, and treating at 600 ℃ for 2 h. CoCl was then prepared at 5mM concentrations2·6H2O、Ni(NO3)2·6H2And (4) mixing the solution O, putting 50mL of the mixed solution into a beaker, and electrodepositing the mixed solution for 20s under the constant potential of-1V of a three-electrode system. Taking out the sample, alternately cleaning the sample by using ethanol and deionized water, and storing the sample in a vacuum drying oven.
Example 3
The smooth ground titanium plate (1 × 3 cm)2) The surface was cleaned and dried in air. 0.5g of ammonium fluoride was dissolved in 100mL of an aqueous hexanediol solution, and the solution was stirred uniformly, and one end of the cleaned titanium plate was immersed in the solution, and the other end was held by an electrode holder of a potentiostat, and the voltage was controlled at 50V for 2 hours. Taking out the sample, alternately washing with ethanol and deionized water, and drying for 5h at 60 ℃ in a vacuum drying oven. Putting into a muffle furnace, and treating at 600 ℃ for 2 h. CoCl was then prepared at 5mM concentrations2·6H2O、Ni(NO3)2·6H2And (4) mixing the solution O, putting 50mL of the mixed solution into a beaker, and electrodepositing the mixed solution for 30s under the constant potential of-1V of a three-electrode system. Taking out the sample, alternately cleaning the sample by using ethanol and deionized water, and storing the sample in a vacuum drying oven.
Example 4
The smooth ground titanium plate (1 × 3 cm)2) The surface was cleaned and dried in air. 0.5g of ammonium fluoride was dissolved in 100mL of an aqueous hexanediol solution, and the solution was stirred uniformly, and one end of the cleaned titanium plate was immersed in the solution, and the other end was held by an electrode holder of a potentiostat, and the voltage was controlled at 50V for 2 hours. Taking out the sample, alternately washing with ethanol and deionized water, and drying for 5h at 60 ℃ in a vacuum drying oven. Putting into a muffle furnace, and treating at 600 ℃ for 2 h. CoCl was then prepared at 5mM concentrations2·6H2O、Ni(NO3)2·6H2And (4) mixing the solution O, putting 50mL of the mixed solution into a beaker, and electrodepositing for 60s under the constant potential of-1V of a three-electrode system. Taking out the sample, alternately cleaning the sample by using ethanol and deionized water, and storing the sample in a vacuum drying oven.
Example 5
The smooth ground titanium plate (1 × 3 cm)2) The surface was cleaned and dried in air. 0.5g of ammonium fluoride was dissolved in 100mL of an aqueous hexanediol solution, and the solution was stirred uniformly, and one end of the cleaned titanium plate was immersed in the solution, and the other end was held by an electrode holder of a potentiostat, and the voltage was controlled at 50V for 2 hours. Taking out the sample, alternately washing with ethanol and deionized water, and drying for 5h at 60 ℃ in a vacuum drying oven. Placing into muffle furnace at 600 deg.CAnd (5) warming for 2 h. CoCl was then prepared at 5mM concentrations2·6H2O、Ni(NO3)2·6H2And (4) mixing the solution O, putting 50mL of the mixed solution into a beaker, and electrodepositing the mixed solution for 120s under the constant potential of-1V of a three-electrode system. Taking out the sample, alternately cleaning the sample by using ethanol and deionized water, and storing the sample in a vacuum drying oven.
Example 6
The smooth ground titanium plate (1 × 3 cm)2) The surface was cleaned and dried in air. 0.5g of ammonium fluoride was dissolved in 100mL of an aqueous hexanediol solution, and the solution was stirred uniformly, and one end of the cleaned titanium plate was immersed in the solution, and the other end was held by an electrode holder of a potentiostat, and the voltage was controlled at 50V for 2 hours. Taking out the sample, alternately washing with ethanol and deionized water, and drying for 5h at 60 ℃ in a vacuum drying oven. Putting into a muffle furnace, and treating at 600 ℃ for 2 h. CoCl was then prepared at 5mM concentrations2·6H2O、Ni(NO3)2·6H2And (4) mixing the solution O, putting 50mL of the mixed solution into a beaker, and electrodepositing for 300s under the constant potential of-1V of a three-electrode system. Taking out the sample, alternately cleaning the sample by using ethanol and deionized water, and storing the sample in a vacuum drying oven.
Example 7
The smooth ground titanium plate (1 × 3 cm)2) The surface was cleaned and dried in air. 0.5g of ammonium fluoride was dissolved in 100mL of an aqueous hexanediol solution, and the solution was stirred uniformly, and one end of the cleaned titanium plate was immersed in the solution, and the other end was held by an electrode holder of a potentiostat, and the voltage was controlled at 50V for 2 hours. Taking out the sample, alternately washing with ethanol and deionized water, and drying for 5h at 60 ℃ in a vacuum drying oven. Putting into a muffle furnace, and treating at 600 ℃ for 2 h. CoCl was then prepared at 5mM concentrations2·6H2O、Ni(NO3)2·6H2And O, mixing the solution, placing 50mL of the solution in a beaker, and electrodepositing the solution for 600s under the constant potential of-1V of a three-electrode system. Taking out the sample, alternately cleaning the sample by using ethanol and deionized water, and storing the sample in a vacuum drying oven.
Example 8
The smooth ground titanium plate (1 × 3 cm)2) After surface cleaning, in the airDrying in air. 0.5g of ammonium fluoride was dissolved in 100mL of an aqueous hexanediol solution, and the solution was stirred uniformly, and one end of the cleaned titanium plate was immersed in the solution, and the other end was held by an electrode holder of a potentiostat, and the voltage was controlled at 50V for 2 hours. Taking out the sample, alternately washing with ethanol and deionized water, and drying for 5h at 60 ℃ in a vacuum drying oven. Putting into a muffle furnace, and treating at 600 ℃ for 2 h. CoCl was then prepared at a concentration of 10mM2·6H2O、Ni(NO3)2·6H2And (4) mixing the solution O, putting 50mL of the mixed solution into a beaker, and electrodepositing the mixed solution for 30s under the constant potential of-1V of a three-electrode system. Taking out the sample, alternately cleaning the sample by using ethanol and deionized water, and storing the sample in a vacuum drying oven.
Example 9
The smooth ground titanium plate (1 × 3 cm)2) The surface was cleaned and dried in air. 0.5g of ammonium fluoride was dissolved in 100mL of an aqueous hexanediol solution, and the solution was stirred uniformly, and one end of the cleaned titanium plate was immersed in the solution, and the other end was held by an electrode holder of a potentiostat, and the voltage was controlled at 50V for 2 hours. Taking out the sample, alternately washing with ethanol and deionized water, and drying for 5h at 60 ℃ in a vacuum drying oven. Putting into a muffle furnace, and treating at 600 ℃ for 2 h. CoCl was then prepared at 15mM each2·6H2O、Ni(NO3)2·6H2And (4) mixing the solution O, putting 50mL of the mixed solution into a beaker, and electrodepositing the mixed solution for 30s under the constant potential of-1V of a three-electrode system. Taking out the sample, alternately cleaning the sample by using ethanol and deionized water, and storing the sample in a vacuum drying oven.
Example 10
The smooth ground titanium plate (1 × 3 cm)2) The surface was cleaned and dried in air. 0.5g of ammonium fluoride was dissolved in 100mL of an aqueous hexanediol solution, and the solution was stirred uniformly, and one end of the cleaned titanium plate was immersed in the solution, and the other end was held by an electrode holder of a potentiostat, and the voltage was controlled at 50V for 2 hours. Taking out the sample, alternately washing with ethanol and deionized water, and drying for 5h at 60 ℃ in a vacuum drying oven. Putting into a muffle furnace, and treating at 600 ℃ for 2 h. CoCl was then prepared at a concentration of 30mM each2·6H2O、Ni(NO3)2·6H2And (4) mixing the solution O, putting 50mL of the mixed solution into a beaker, and electrodepositing the mixed solution for 30s under the constant potential of-1V of a three-electrode system. Taking out the sample, alternately cleaning the sample by using ethanol and deionized water, and storing the sample in a vacuum drying oven.
Example 11
The smooth ground titanium plate (1 × 3 cm)2) The surface was cleaned and dried in air. 0.5g of ammonium fluoride was dissolved in 100mL of an aqueous hexanediol solution, and the solution was stirred uniformly, and one end of the cleaned titanium plate was immersed in the solution, and the other end was held by an electrode holder of a potentiostat, and the voltage was controlled at 50V for 2 hours. Taking out the sample, alternately washing with ethanol and deionized water, and drying for 5h at 60 ℃ in a vacuum drying oven. Putting into a muffle furnace, and treating at 600 ℃ for 2 h. CoCl was then prepared at a concentration of 60mM2·6H2O、Ni(NO3)2·6H2And (4) mixing the solution O, putting 50mL of the mixed solution into a beaker, and electrodepositing the mixed solution for 30s under the constant potential of-1V of a three-electrode system. Taking out the sample, alternately cleaning the sample by using ethanol and deionized water, and storing the sample in a vacuum drying oven.
Example 12
The smooth ground titanium plate (1 × 3 cm)2) The surface was cleaned and dried in air. 0.5g of ammonium fluoride was dissolved in 100mL of an aqueous hexanediol solution, and the solution was stirred uniformly, and one end of the cleaned titanium plate was immersed in the solution, and the other end was held by an electrode holder of a potentiostat, and the voltage was controlled at 50V for 2 hours. Taking out the sample, alternately washing with ethanol and deionized water, and drying for 5h at 60 ℃ in a vacuum drying oven. Putting into a muffle furnace, and treating at 600 ℃ for 2 h. CoCl was then prepared at a concentration of 60mM2·6H2O、Ni(NO3)2·6H2And (4) mixing the solution O, putting 50mL of the mixed solution into a beaker, and electrodepositing the mixed solution for 30s under the constant potential of a three-electrode system of-0.5V. Taking out the sample, alternately cleaning the sample by using ethanol and deionized water, and storing the sample in a vacuum drying oven.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (7)

1. A preparation method of a titanium dioxide heterogeneous nanotube array electrode modified by cobalt and nickel double-layer hydroxide is characterized by comprising the following steps:
(1) the cleaned titanium sheet is put into hexanediol water solution dissolved with ammonium fluoride for secondary anode oxidation reaction, and the sample obtained after the reaction is cleaned and then put into a vacuum drying oven for vacuum drying, thus obtaining TiO growing on the titanium sheet substrate in situ2A nanotube array;
(2) placing the sample obtained in the step (1) in a muffle furnace for high-temperature annealing treatment to obtain TiO with good crystallinity2A nanotube array;
(3) TiO obtained in the step (2)2Soaking the nanotube array in an electrolyte solution containing cobalt and nickel for a period of time, and performing electrochemical deposition by adopting a three-electrode system to obtain TiO2The @ CoNi-LDHs heterogeneous nanotube array electrode;
CoCl in the cobalt and nickel-containing electrolyte solution in the step (3)2·6H2O、Ni(NO3)2·6H2The concentration of O is 1mM-50mM, the volume is 50ml, the electrochemical deposition time is 5-600s, and the constant potential is-2.0-0V.
2. The method for preparing the cobalt-nickel double-layer hydroxide modified titanium dioxide heterogeneous nanotube array electrode according to claim 1, wherein the method comprises the following steps: the amount of the ammonium fluoride in the step (1) is 0.1 to 10.0 g.
3. The method for preparing the cobalt-nickel double-layer hydroxide modified titanium dioxide heterogeneous nanotube array electrode according to claim 1, wherein the method comprises the following steps: the volume of the hexanediol in the step (1) is 10-90ml, the volume of the water is 0-10ml, and the total volume of the hexanediol aqueous solution dissolved with the ammonium fluoride is 100 ml.
4. The method for preparing the cobalt-nickel double-layer hydroxide modified titanium dioxide heterogeneous nanotube array electrode according to claim 1, wherein the method comprises the following steps: in the step (1), the constant voltage of the first anodic oxidation reaction is 10-80V, and the reaction time is 0.5-5 h; the constant voltage of the second anodic oxidation reaction is 20-80V, the reaction time is 0.5-6h, the vacuum drying temperature in the step (1) is 10-80 ℃, and the time is 1-12 h.
5. The method for preparing the cobalt-nickel double-layer hydroxide modified titanium dioxide heterogeneous nanotube array electrode according to claim 1, wherein the method comprises the following steps: the calcination time in the muffle furnace in the step (2) is 10-120min, and the calcination temperature is 100-800 ℃.
6. The cobalt-nickel double-layer hydroxide modified titanium dioxide heterogeneous nanotube array electrode prepared by the method of any one of claims 1 to 5, which is characterized in that: CoNi-LDHs flaky nano-particles are mainly deposited on TiO2The sample has larger absorption of light in an ultraviolet region at the tube wall and the top end of the nanotube.
7. The cobalt-nickel double hydroxide modified titanium dioxide heterogeneous nanotube array electrode of claim 6 is applied to the field of photoelectrochemistry hydrolysis hydrogen production.
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