CN115992367A - High-performance heterojunction Ti-Fe 2 O 3 /CoSe 2 Preparation method and application of photoelectrode film - Google Patents
High-performance heterojunction Ti-Fe 2 O 3 /CoSe 2 Preparation method and application of photoelectrode film Download PDFInfo
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- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical group O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 claims description 3
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- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical group O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 claims description 2
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 2
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- 238000003491 array Methods 0.000 description 1
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- 229910052715 tantalum Inorganic materials 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
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Abstract
The invention discloses a high-performance heterojunction Ti-Fe 2 O 3 /CoSe 2 A preparation method and application of a photoelectrode film. Dissolving ferric salt and urea in deionized water, and adding TiCl 4 The precursor Ti-FeOOH is grown on the conductive glass FTO by a hydrothermal method. Taking out the precursor film, and calcining to obtain Ti-Fe 2 O 3 A nano film. Then dissolving selenium powder in strong alkali solution, adding cobalt salt and disodium ethylenediamine tetraacetate, hydrothermal treatment at 180deg.C for 16h, centrifuging and drying the precipitateDrying to obtain CoSe 2 And (3) powder. By impregnation at Ti-Fe 2 O 3 Film supporting CoSe 2 Finally calcining to obtain Ti-Fe 2 O 3 /CoSe 2 A heterojunction thin film. Ti-Fe prepared by the method of the invention 2 O 3 /CoSe 2 The photoelectric film can effectively improve Fe 2 O 3 And can be used as photoelectrochemistry property and hydrogen production capability of a photoelectrode for decomposing water.
Description
Technical Field
The invention belongs to the technical field of photoelectrochemistry, and in particular relates to a high-performance heterojunction Ti-Fe 2 O 3 /CoSe 2 A photoelectrode film, a preparation method and application thereof.
Background
With the growing global energy demand, environmental problems and energy crisis make development of sustainable and renewable energy technologies imperative. Among them, the solar-driven PEC water splitting technology is considered as a technology for converting solar energy directly into clean, storable fuel (H 2 ) Has important significance for solving the intermittence of solar energy.
Hematite (Fe) 2 O 3 ) Has good optical band gap (1.9-2.2 eV), excellent chemical stability in oxidation environment, is rich in rare earth elements and low in cost, and is widely studied as a photo-anode for water oxidation. Theoretically, the theoretical photocurrent of hematite at 1.23V (vs. RHE) was 12.6mA/cm 2 A high solar-hydrogen conversion efficiency of 15.5% can be achieved. Although various doping and nanocrystallization methods have been explored to overcome the problems of long sunlight absorption depth and extremely short carrier lifetime of hematite, the practical photoelectric conversion performance of hematite still does not reach the expected level far, mainly due to the limitation (10-12 s) caused by the short lifetime of excited carriers, the short hole diffusion length (2-4 nm), the abundant surface states, and especially the low conductivity of the surface. It is therefore highly desirable to develop a versatile method to solve the above problems simultaneously. The report of Environmental Applied Catalysis B reports Ti-Fe 2 O 3 Nanowire arrays and In 2 O 3 The Z-shaped photo-anode system formed by the layers improves the photoelectrochemical water splitting performance; the report Nature Communications reports the collectionThe core-shell structure of the tantalum doped hematite homojunction nanorod is prepared by a method combining hydrothermal regrowth and mixed microwave annealing, so that the photocurrent density is improved, and meanwhile, the starting voltage is reduced; the two-step hydrothermal method is reported in Fe in Chemical Engineering Journal 2 O 3 Intrinsic (oxygen vacancies, V) o ) And extrinsic (Cu) 2+ ) Dopant, then annealing treatment, at Fe 2 O 3 The homogeneous p-n junction is prepared, and the result shows that the composite membrane photo-anode has good PEC photocatalytic water splitting performance.
In recent years, metal selenides have attracted considerable attention in terms of water splitting due to their good electrical conductivity and high catalytic activity. Furthermore, since the Se 4p orbitals form a valence band shallower than the O2 p and S3 p orbitals, their band gap is narrower than the corresponding metal (oxy) sulfides, allowing for wider solar wavelength absorption. Wherein cobalt diselenide (CoSe) 2 ) Is a typical p-type semiconductor and exhibits excellent catalytic performance as a catalyst for photocatalytic/electrocatalytic decomposition of water. Fe (Fe) 2 O 3 As an n-type semiconductor, coSe 2 With Fe 2 O 3 The heterojunction is formed, the separation of electrons and holes can be improved, and the diffusion of carriers under an internal electric field is accelerated, so that the water decomposition performance is more efficient. Thus, ti-Fe 2 O 3 /CoSe 2 The photo-anode film is a material for photoelectrochemical decomposition of water, which has a great development prospect.
Disclosure of Invention
In view of the defects in the prior art, the invention provides a high-performance heterojunction Ti-Fe 2 O 3 /CoSe 2 A preparation method and application of a photoelectrode film. The method has the advantages of simple preparation method, convenient operation, easy control of experimental conditions and the like.
In order to achieve the above purpose, the present invention adopts the following technical scheme: high-performance heterojunction Ti-Fe 2 O 3 /CoSe 2 The preparation method of the photoelectrode film comprises the following steps:
1) Dissolving ferric salt and urea in deionized water, and adding TiCl 4 Stirring to obtain precursorA bulk solution; placing the precursor solution and the FTO conductive glass in a hydrothermal kettle, and growing a precursor Ti-FeOOH on the conductive glass FTO through hydrothermal reaction to obtain a Ti-FeOOH photoelectrode film; calcining the Ti-FeOOH photoelectrode film under the air condition to obtain Ti-Fe 2 O 3 A photoelectrode thin film;
2) Dissolving selenium powder in strong alkali solution, adding cobalt salt and disodium ethylenediamine tetraacetate, performing hydrothermal reaction at 180deg.C for 16 hr, centrifuging and oven drying precipitate to obtain CoSe 2 Powder;
3) CoSe is to 2 And polyethylene glycol are dissolved in ethanol, and CoSe is prepared by ultrasonic treatment 2 An impregnating solution; the Ti-Fe obtained in the step 1) is processed 2 O 3 Photoelectrode thin film in CoSe 2 After the dipping treatment in the dipping liquid, calcining in inert gas to obtain Ti-Fe 2 O 3 /CoSe 2 A photoelectrode thin film.
Further, in the above preparation method, in step 1), the iron salt is ferric trichloride hexahydrate or ferric sulfate.
Further, in the preparation method, the molar ratio of the ferric salt to the urea is 1-2:1.
Further, in the preparation method and the step 1), the hydrothermal reaction is carried out for 8-12 hours at the temperature of 90-120 ℃.
Further, in the preparation method, in the step 1), the calcination is carried out at 400-600 ℃ for 1-3 hours, and the temperature rising speed is 1-10 ℃/min.
Further, in the above preparation method, in step 2), the cobalt salt is cobalt nitrate hexahydrate or cobalt chloride hexahydrate.
Further, according to the preparation method, the molar ratio of the cobalt salt to the selenium powder is 0.5:1-2.
Further, in the preparation method, in the step 2), the strong alkali solution is a sodium hydroxide solution or a potassium hydroxide solution with a concentration of 20 mol/L.
Further, in the preparation method and the step 2), the drying is performed at 50-100 ℃ for 10-24 hours.
Further, in the preparation method and the step 3), the dipping treatment is performed at a dipping rate of 1cm/min for 0.5-5min.
Further, in the above preparation method, in step 3), the calcination is performed at 300 to 500 ℃ for 1 to 2 hours.
Further, in the preparation method, the inert gas is nitrogen.
The high-performance heterojunction Ti-Fe provided by the invention 2 O 3 /CoSe 2 The photoelectrode film is applied to photoelectrochemical water splitting hydrogen production.
The beneficial effects of the invention are as follows:
1. the Ti-Fe provided by the invention 2 O 3 /CoSe 2 The photoelectrode film is of a p-n heterojunction structure, the heterojunction structure can more easily effectively separate photo-generated electrons and holes, the recombination rate is reduced, and the photoelectrochemistry performance and the hydrogen production capacity by decomposing water can be effectively improved.
2. The Ti-Fe provided by the invention 2 O 3 /CoSe 2 The preparation method of the photoelectrode film has the advantages of low cost and easy obtainment of raw materials, simple and convenient operation, provides a new catalytic material for water splitting, relieves the situation of current energy shortage and has good application prospect.
3. The Ti-Fe provided by the invention 2 O 3 /CoSe 2 Photoelectrode thin film, hydrogen production rate under visible light is Ti-Fe 2 O 3 About 2 times as large as the above.
Drawings
FIG. 1 shows Ti-Fe prepared in example 1 2 O 3 /CoSe 2 Photoelectrode thin film, ti-Fe 2 O 3 Film and CoSe 2 Comparison plot of powder XRD.
FIG. 2 is a diagram of Ti-Fe prepared in example 1 2 O 3 /CoSe 2 Photoelectrode thin film, ti-Fe 2 O 3 Film and pure CoSe 2 Comparison of photocurrent of thin films prepared from powders.
FIG. 3 is a diagram of Ti-Fe prepared in example 1 2 O 3 /CoSe 2 Photoelectrode thin film and Ti-Fe 2 O 3 Comparison of open circuit voltage of thin films.
FIG. 4 shows the Ti-doped steel prepared in example 1Fe 2 O 3 /CoSe 2 Photoelectrode thin film and Ti-Fe 2 O 3 Water splitting hydrogen production rate graph of the film.
Detailed Description
Example 1 high Performance heterojunction Ti-Fe 2 O 3 /CoSe 2 Photoelectrode film
Process for the preparation of (I)
1、CoSe 2 Is prepared from the powder
0.1580g (0.002 mol) of selenium powder is dissolved in 5mL of KOH solution with concentration of 20mol/L, and after 30min of magnetic stirring, 0.291g (0.001 mol) of Co (NO) is added 3 ) 2 ·6H 2 O and 0.5952g (0.0016 mol) EDTA-2Na, continuing magnetic stirring for 1h, transferring to a 50mL reaction kettle, performing hydrothermal reaction at 180deg.C for 16h, centrifuging, washing, and drying at 60deg.C for 24h to obtain CoSe 2 Is a powder of (a) a powder of (b).
2. n-type Ti-Fe 2 O 3 Preparation of photoelectrode thin film
0.81g (0.003 mol) of ferric trichloride hexahydrate and 0.18g (0.003 mol) of urea were dissolved in 20mL of deionized water, and 150. Mu.L of 5% TiCl was added dropwise 4 Ethanol solution, and fully stirring to prepare precursor solution.
And (3) placing the precursor solution and the cleaned FTO conductive glass in a 100mL hydrothermal kettle, and performing hydrothermal reaction for 12 hours at the temperature of 100 ℃ to obtain the Ti-FeOOH photoelectrode film.
Calcining the Ti-FeOOH photoelectrode film for 2 hours at 550 ℃ to obtain a high-performance n-type photoelectrode material Ti-Fe 2 O 3 A photoelectrode thin film.
3. High performance heterojunction Ti-Fe 2 O 3 /CoSe 2 Preparation of photoelectrode thin film
60mg CoSe 2 Dissolving the powder and 0.5mL of polyethylene glycol in 50mL of ethanol solution, and performing ultrasonic treatment for 60min to obtain CoSe 2 And (5) impregnating liquid.
Ti-Fe 2 O 3 Photoelectrode thin film impregnated with CoSe 2 In the dipping solution, the dipping time is 2min, and the dipping speed is 1cm/min. Calcining for 2 hours at 300 ℃ under the protection of nitrogen to obtain high-performance heterojunction Ti-Fe 2 O 3 /CoSe 2 A photoelectrode thin film.
(II) detection
FIG. 1 shows the prepared Ti-Fe 2 O 3 /CoSe 2 Photoelectrode thin film, ti-Fe 2 O 3 Film and CoSe 2 Comparison plot of powder XRD. As can be seen from FIG. 1, ti-Fe 2 O 3 /CoSe 2 Diffraction peaks correspond to SnO, respectively 2 (FTO)、Fe 2 O 3 (PDF#73-0603) and CoSe 2 Diffraction peaks of (PDF # 053-0449). Demonstration of CoSe 2 At Fe 2 O 3 Successful loading of the surface.
Example 2 application
The prepared CoSe 2 、Ti-Fe 2 O 3 、Ti-Fe 2 O 3 /CoSe 2 The photoelectrode thin film was subjected to performance tests such as photocurrent, open circuit voltage (OCP), and water decomposition.
All electrochemical experimental testing procedures were performed in the electrochemical workstation (Princeton Applied Research 2273) of the three-electrode system. The sample film is used as a working electrode, the platinum sheet is used as a counter electrode, ag/AgCl is used as a reference electrode, the electrolyte is 1M potassium hydroxide, and the light irradiation area of the sample is 1cm 2 The split water test uses GC-1690 to detect the hydrogen production per time period.
Photocurrent testing: the light source is a 300W xenon lamp, the bias voltage is 1.23V vs. RHE, the measured result is shown in figure 2, and the result shows that the heterojunction Ti-Fe 2 O 3 /CoSe 2 The photocurrent density of the film is far higher than that of Ti-Fe 2 O 3 Description of CoSe loading 2 The post photoelectrochemical properties are improved.
Open circuit voltage (OCP) test: the light source was a 300W xenon lamp with a bias voltage of 1.23V vs. RHE, and the results were shown in FIG. 3 by loading CoSe 2 With Ti-Fe 2 O 3 After formation of heterojunction, ti-Fe 2 O 3 /CoSe 2 OCP (OCV) of photoelectrode thin film dark -OCV light ) A value greater than Ti-Fe 2 O 3 Is described by loading CoSe 2 With Ti-Fe 2 O 3 After heterojunction is formed, ti-Fe is effectively improved 2 O 3 Separation efficiency of carriers in vivo.
And (3) hydrogen production test by decomposing water: the light source was a 300W xenon lamp with a bias voltage of 1.23V vs. RHE, and the results were shown in FIG. 4 by loading CoSe 2 With Ti-Fe 2 O 3 After formation of heterojunction, ti-Fe 2 O 3 /CoSe 2 The hydrogen production rate value of the photoelectrode film is larger than that of Ti-Fe 2 O 3 Is illustrated by the CoSe loading of hydrogen production rate values 2 With Ti-Fe 2 O 3 After heterojunction is formed, ti-Fe is effectively improved 2 O 3 The hydrogen production efficiency of (2) and Faraday efficiency also reach 98%, which proves that Ti-Fe 2 O 3 /CoSe 2 Has more effective water oxidation driving force.
Claims (10)
1. High-performance heterojunction Ti-Fe 2 O 3 /CoSe 2 The preparation method of the photoelectrode film is characterized by comprising the following steps:
1) Dissolving ferric salt and urea in deionized water, and adding TiCl 4 Stirring to obtain a precursor solution; placing the precursor solution and the FTO conductive glass in a hydrothermal kettle, and growing a precursor Ti-FeOOH on the conductive glass FTO through hydrothermal reaction to obtain a precursor Ti-FeOOH photoelectrode film; calcining the precursor Ti-FeOOH photoelectrode film under the air condition to obtain Ti-Fe 2 O 3 A photoelectrode thin film;
2) Dissolving selenium powder in strong alkali solution, adding cobalt salt and disodium ethylenediamine tetraacetate, performing hydrothermal reaction at 180deg.C for 16 hr, centrifuging and oven drying precipitate to obtain CoSe 2 Powder;
3) CoSe is to 2 And polyethylene glycol are dissolved in ethanol, and CoSe is prepared by ultrasonic treatment 2 An impregnating solution; the Ti-Fe obtained in the step 1) is processed 2 O 3 Photoelectrode thin film in CoSe 2 After the dipping treatment in the dipping liquid, calcining in inert gas to obtain Ti-Fe 2 O 3 /CoSe 2 A photoelectrode thin film.
2. The method of claim 1, wherein in step 1), the iron salt is ferric trichloride hexahydrate or ferric sulfate.
3. The process according to claim 2, wherein the molar ratio of iron salt to urea is 1-2:1.
4. The method according to claim 1, wherein in step 1), the hydrothermal reaction is carried out at 90 to 120 ℃ for 8 to 12 hours; the calcination is carried out at 400-600 ℃ for 1-3h, and the temperature rising speed is 1-10 ℃/min.
5. The method of claim 1, wherein in step 2), the cobalt salt is cobalt nitrate hexahydrate or cobalt chloride hexahydrate; the molar ratio of the cobalt salt to the selenium powder is 0.5:1-2.
6. The method according to claim 1, wherein in the step 2), the strong alkali solution is a 20mol/L sodium hydroxide solution or potassium hydroxide solution.
7. The method according to claim 1, wherein in step 2), the drying is performed at 50 to 100℃for 10 to 24 hours.
8. The method according to claim 1, wherein in the step 3), the dipping treatment is a dipping treatment for 0.5 to 5 minutes.
9. The method of claim 1, wherein in step 3), the calcination is performed at 300 to 500 ℃ for 1 to 2 hours; the inert gas is nitrogen.
10. High performance heterojunction Ti-Fe prepared according to the method of any one of claims 1-9 2 O 3 /CoSe 2 The photoelectrode film is applied to photoelectrochemical water splitting hydrogen production.
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| CN202211682794.5A CN115992367A (en) | 2022-12-27 | 2022-12-27 | High-performance heterojunction Ti-Fe 2 O 3 /CoSe 2 Preparation method and application of photoelectrode film |
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