CN109234761B - Co for producing hydrogen by photoelectrocatalysis3O4Preparation method of/Pt composite film - Google Patents
Co for producing hydrogen by photoelectrocatalysis3O4Preparation method of/Pt composite film Download PDFInfo
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- CN109234761B CN109234761B CN201811175729.7A CN201811175729A CN109234761B CN 109234761 B CN109234761 B CN 109234761B CN 201811175729 A CN201811175729 A CN 201811175729A CN 109234761 B CN109234761 B CN 109234761B
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
- C25B11/093—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds at least one noble metal or noble metal oxide and at least one non-noble metal oxide
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/50—Processes
- C25B1/55—Photoelectrolysis
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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
Abstract
The invention disclosesCo for producing hydrogen by photoelectrocatalysis3O4The preparation method of the/Pt composite film comprises the following steps: 1 adding cobalt nitrate into absolute ethyl alcohol, magnetically stirring at room temperature, adding thioacetamide, adjusting pH, continuously stirring, and standing for 3d to obtain Co3O4Precursor sol; 2 Co prepared from clean FTO conductive glass in step 13O4Dipping and lifting the precursor sol and drying; after repeated coating, drying the FTO conductive glass subjected to secondary coating; annealing the dried sample to obtain Co3O4A film; 3 configuration H2PtCl6Depositing the solution to obtain Pt depositing solution; 4, performing electrochemical deposition; 5 Co obtained in step 43O4/Pt is repeatedly washed by absolute ethyl alcohol and distilled water and dried to obtain final Co3O4a/Pt composite film. The photocurrent density of the invention is obviously improved, the preparation method is simple and feasible, and the cost of raw materials is low.
Description
Technical Field
The invention belongs to the technical field of photoelectrocatalysis materials, and particularly relates to Co for photoelectrocatalysis hydrogen production3O4A preparation method of a/Pt composite film.
Background
Environmental pollution and energy problems are significant problems related to human sustainable development. Hydrogen energy is favored by people as a clean and environment-friendly secondary energy, and the traditional hydrogen production technology mainly adopts a natural gas thermal cracking method. This method consumes limited fossil energy and also brings about serious environmental pollution. Photoelectrochemical water splitting based on semiconductor photoelectrodes is considered as a promising artificial photosynthesis method, and has the advantages of cleanness, low cost and environmental protection. The key of the photoelectrochemistry water splitting decomposition hydrogen production is to find the condition (1) meeting the hydrogen production; (2) the wide photoresponse and absorption range can fully utilize the good stability of the solar energy (3). Cobalt oxide (Co)3O4) Is a typical and environmentally friendly p-type metal oxide, and has been widely used for lithium batteries, supercapacitor catalysts, and photoelectrochemical devices due to its excellent physicochemical properties. And with a suitable band gap width of 2.07eV to capture a wide range of visible light, has been used as photocathodes in PEC programs to generate hydrogen. Indeed, Co is due to the low electron mobility and slow photoinduced electron-hole pair separation3O4The actual performance of (a) is far from expected. Therefore, effective strategies are urgently needed to overcome these bottlenecks. SelectingThe selective deposition of promoters, particularly noble metals (e.g., Pt, Pd), to significantly catalyze the Hydrogen Evolution Reaction (HER) is an important route to accelerate charge transfer and reduce interfacial recombination. It not only captures electrons, but also provides an efficient proton reduction site.
At present, Co3O4The application in the field of photoelectrocatalysis hydrolysis is less, and research on different functional layers for modification is relatively less, so that the Co is currently used3O4The photoelectrocatalytic hydrolysis of the/Pt binary functional layer system is a research subject which is worthy of research and has great potential.
Disclosure of Invention
Aiming at the technical problems in the prior art, the invention provides Co for photoelectrocatalysis hydrogen production3O4The preparation method of the Pt/Pt composite film can obviously improve the photocurrent density, and has the advantages of simple and feasible preparation method and low raw material cost.
In order to solve the technical problems, the invention adopts the technical scheme that: co for producing hydrogen by photoelectrocatalysis3O4The preparation method of the/Pt composite film comprises the following steps:
(1) adding cobalt nitrate into absolute ethyl alcohol, magnetically stirring at room temperature, adding thioacetamide, adjusting pH, continuously stirring, and standing for 3d to obtain Co3O4Precursor sol;
(2) clean FTO conductive glass is subjected to Co prepared in the step (1)3O4Dipping and lifting the precursor sol and drying; after repeated coating, drying the FTO conductive glass subjected to secondary coating; annealing the dried sample to obtain Co3O4A film;
(3) configuration H2PtCl6Depositing the solution to obtain Pt depositing solution;
(4) co prepared by the step (2)3O4Taking the film as a working electrode, the platinum sheet as a counter electrode, Ag/AgCl as a reference electrode and the electrolyte as the 10mmol.L-1Pt deposition solution prepared in the step (3), and carrying out electrochemical deposition to obtain Co3O4/Pt：
(5) The Co obtained in the step (4) is mixed3O4/Pt is repeatedly washed by absolute ethyl alcohol and distilled water and dried to obtain final Co3O4a/Pt composite film.
Preferably, in the step (1), the dosage of the cobalt nitrate is 1.46-4.37 g, the dosage of the absolute ethyl alcohol is 50mL, the magnetic stirring condition is 10-15 min, the dosage of the thioacetamide is 0.38-1.13 g, the pH is adjusted to 1, the stirring condition is continued for 1-2 h, the standing condition is 3d, and the obtained Co is obtained3O4The concentration of the precursor sol is 0.1-0.3 mol.L-1。
Preferably, in the step (2), the FTO conductive glass is dipped for 15s at the speed of 1-5 mm/s and then pulled; the drying condition is that the FTO conductive glass is placed in an oven at 80 ℃, wherein the FTO conductive glass subjected to secondary coating is dried for 1-4 hours; the annealing condition is that the furnace is placed in a muffle furnace at 500 ℃ for 2 h.
Preferably, in step (3), 1g H is added2PtCl6Dissolving in 200ml distilled water, stirring at room temperature for 1H to obtain uniform transparent yellow H2PtCl6Depositing the solution to obtain 10mmol.L-1Pt depositing solution.
Preferably, in step (4), the deposition current for electrochemical deposition is 1mA/cm2The deposition time is 10-50 s.
Preferably, in the step (5), the drying condition is that the container is placed in an oven at 60 ℃.
Compared with the prior art, the invention has the beneficial effects that:
(1) co obtained by the invention3O4The performance of the/Pt composite film is compared with that of pure Co after a photocurrent test3O4The photocurrent density under the simulated sunlight reaches-0.66 mA/cm2。
(2) The preparation method provided by the invention is simple and feasible, the cost of raw materials is low, and the prepared Co3O4The Pt/Pt composite film has no pollution and good performance of photoelectrocatalysis water decomposition.
Detailed Description
In order that those skilled in the art will better understand the technical solutions of the present invention, the following detailed description of the present invention is provided in connection with specific embodiments.
The first embodiment is as follows:
the embodiment of the invention discloses Co for producing hydrogen by photoelectrocatalysis3O4The preparation method of the/Pt composite film comprises the steps of adding 1.49g of cobalt nitrate into 50mL of absolute ethyl alcohol, magnetically stirring for 10min at room temperature, then adding 0.39g of thioacetamide, adjusting the pH value to be 1, continuously stirring for 1h to obtain a transparent solution, and standing for 3d to obtain Co composite film3O4Precursor sol; 0.1mol.L is obtained-1Co of (A)3O4A precursor;
cleaning FTO conductive glass, and placing the cleaned FTO conductive glass on the Co prepared in the above way at the speed of 1mm/s3O4Dipping the precursor sol for 15s, pulling, and drying in an oven at 80 ℃; then, repeatedly coating the film, and drying the FTO conductive glass subjected to secondary film coating in an oven at 80 ℃ for 1.5 h; putting the dried sample in a muffle furnace for annealing treatment at 500 ℃ for 2h to obtain Co3O4A film;
1gH is reacted with2PtCl6Dissolving in 200ml distilled water, stirring at room temperature for 1H to obtain uniform transparent yellow H2PtCl6Depositing liquid; obtaining 10mmol.L-1Pt deposition solution;
co obtained as described above3O4The film is a working electrode, the platinum sheet is a counter electrode, Ag/AgCl is a reference electrode, the electrolyte is the prepared 10mmol.L-1Pt deposition solution, and the deposition current is 1mA/cm2The deposition time is 18 s; then repeatedly washing the mixture with absolute ethyl alcohol and distilled water for a plurality of times, and placing the mixture in a 60 ℃ drying oven for drying to finally obtain Co3O4a/Pt composite film.
Example two:
the embodiment of the invention discloses Co for producing hydrogen by photoelectrocatalysis3O4The preparation method of the/Pt composite film comprises the steps of adding 2.18g of cobalt nitrate into 50mL of absolute ethyl alcohol, magnetically stirring for 12min at room temperature, then adding 0.56g of thioacetamide, adjusting the pH value to be 1, continuously stirring for 1.3h to obtain a transparent solution, and standing for 3d to obtain Co3O4Precursor sol; to obtain0.15mol.L-1Co of (A)3O4A precursor;
cleaning FTO conductive glass, and placing the cleaned FTO conductive glass on the prepared Co at the speed of 2mm/s3O4Dipping the precursor sol for 15s, pulling, and drying in an oven at 80 ℃; then repeatedly coating the film, and drying the FTO conductive glass subjected to secondary film coating in an oven at 80 ℃ for 2 hours; putting the dried sample in a muffle furnace for annealing treatment at 500 ℃ for 2h to obtain Co3O4A film;
1gH is reacted with2PtCl6Dissolving in 200ml distilled water, stirring at room temperature for 1H to obtain uniform transparent yellow H2PtCl6Depositing liquid; obtaining 10mmol.L-1Pt deposition solution;
co obtained as described above3O4The film is a working electrode, the platinum sheet is a counter electrode, Ag/AgCl is a reference electrode, the electrolyte is the prepared 10mmol.L-1Pt deposition solution, and the deposition current is 1mA/cm2The deposition time is 35 s; then repeatedly washing the mixture with absolute ethyl alcohol and distilled water for a plurality of times, and placing the mixture in a 60 ℃ drying oven for drying to finally obtain Co3O4a/Pt composite film.
Example three:
the embodiment of the invention discloses Co for producing hydrogen by photoelectrocatalysis3O4The preparation method of the/Pt composite film comprises the steps of adding 4.17g of cobalt nitrate into 50mL of absolute ethyl alcohol, magnetically stirring for 14min at room temperature, then adding 1.07g of thioacetamide, adjusting the pH value to be 1, continuously stirring for 2h to obtain a transparent solution, and standing for 3d to obtain Co composite film3O4Precursor sol; 0.3 mol. L is obtained-1Co of (A)3O4A precursor;
cleaning FTO conductive glass, and placing the cleaned FTO conductive glass on the Co prepared at the speed of 5mm/s3O4Dipping the precursor sol for 15s, pulling, and drying in an oven at 80 ℃; then, repeatedly coating the film, and drying the FTO conductive glass subjected to secondary film coating in an oven at 80 ℃ for 3.5 hours; putting the dried sample in a muffle furnace for annealing treatment at 500 ℃ for 2h to obtain Co3O4A film;
1gH is reacted with2PtCl6Dissolving in 200ml distilled water, stirring at room temperature for 1H to obtain uniform transparent yellow H2PtCl6Depositing liquid; obtaining 10mmol.L-1Pt deposition solution;
co obtained as described above3O4The film is a working electrode, the platinum sheet is a counter electrode, Ag/AgCl is a reference electrode, the electrolyte is the prepared 10mmol.L-1Pt deposition solution, and the deposition current is 1mA/cm2The deposition time is 48 s; then repeatedly washing the mixture with absolute ethyl alcohol and distilled water for a plurality of times, and placing the mixture in a 60 ℃ drying oven for drying to finally obtain Co3O4a/Pt composite film.
The present invention has been described in detail with reference to the embodiments, but the description is only illustrative of the present invention and should not be construed as limiting the scope of the present invention. The scope of the invention is defined by the claims. The technical solutions of the present invention or those skilled in the art, based on the teaching of the technical solutions of the present invention, should be considered to be within the scope of the present invention, and all equivalent changes and modifications made within the scope of the present invention or equivalent technical solutions designed to achieve the above technical effects are also within the scope of the present invention. It should be noted that for the sake of clarity, parts of the description of the invention have been omitted where there is no direct explicit connection with the scope of protection of the invention, but where components and processes are known to those skilled in the art.
Claims (6)
1. Co for producing hydrogen by photoelectrocatalysis3O4The preparation method of the/Pt composite film is characterized by comprising the following steps:
(1) adding cobalt nitrate into absolute ethyl alcohol, magnetically stirring at room temperature, adding thioacetamide, adjusting pH, continuously stirring, and standing for 3d to obtain Co3O4Precursor sol;
(2) clean FTO conductive glass is subjected to Co prepared in the step (1)3O4Dipping and lifting the precursor sol and drying; after repeated coating, drying the FTO conductive glass subjected to secondary coating(ii) a Annealing the dried sample to obtain Co3O4A film;
(3) configuration H2PtCl6Depositing the solution to obtain Pt depositing solution;
(4) co prepared by the step (2)3O4The film is a working electrode, the platinum sheet is a counter electrode, Ag/AgCl is a reference electrode, and the electrolyte is 10mmol.L prepared in the step (3)-1Performing electrochemical deposition on Pt deposition solution to obtain Co3O4/Pt；
(5) The Co obtained in the step (4) is mixed3O4/Pt is repeatedly washed by absolute ethyl alcohol and distilled water and dried to obtain final Co3O4a/Pt composite film.
2. Co for photoelectrocatalytic hydrogen production according to claim 13O4The preparation method of the/Pt composite film is characterized in that in the step (1), the dosage of cobalt nitrate is 1.46-4.37 g, the dosage of absolute ethyl alcohol is 50mL, the magnetic stirring condition is 10-15 min, the dosage of thioacetamide is 0.38-1.13 g, the pH is adjusted to 1, the continuous stirring condition is 1-2 h, and the standing condition is 3d, so that the obtained Co composite film3O4The concentration of the precursor sol is 0.1-0.3 mol.L-1。
3. Co for photoelectrocatalytic hydrogen production according to claim 13O4The preparation method of the/Pt composite film is characterized in that in the step (2), the FTO conductive glass is dipped for 15s at the speed of 1-5 mm/s and then pulled; the drying condition is that the FTO conductive glass is placed in an oven at 80 ℃, wherein the FTO conductive glass subjected to secondary coating is dried for 1-4 hours; the annealing condition is that the furnace is placed in a muffle furnace at 500 ℃ for 2 h.
4. Co for photoelectrocatalytic hydrogen production according to claim 13O4The preparation method of the/Pt composite film is characterized in that in the step (3), 1gH is added2PtCl6Dissolving in 200ml distilled water, stirring at room temperature for 1H to obtain uniform transparent yellow H2PtCl6Depositing to obtain 10mmol·L-1And (4) depositing Pt.
5. Co for photoelectrocatalytic hydrogen production according to claim 13O4The preparation method of the/Pt composite film is characterized in that in the step (4), the deposition current of electrochemical deposition is 1mA/cm2The deposition time is 10-50 s.
6. Co for photoelectrocatalytic hydrogen production according to claim 13O4The preparation method of the/Pt composite film is characterized in that in the step (5), the drying condition is that the film is placed in a 60 ℃ drying oven.
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