CN113293404B - Heterojunction photo-anode material and preparation method and application thereof - Google Patents
Heterojunction photo-anode material and preparation method and application thereof Download PDFInfo
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- 239000010405 anode material Substances 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 229910006167 NiWO4 Inorganic materials 0.000 claims abstract description 37
- 238000001354 calcination Methods 0.000 claims abstract description 29
- 150000001879 copper Chemical class 0.000 claims abstract description 15
- 150000002815 nickel Chemical class 0.000 claims abstract description 15
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 30
- 239000010408 film Substances 0.000 claims description 26
- 239000000243 solution Substances 0.000 claims description 24
- 229910052751 metal Inorganic materials 0.000 claims description 16
- 239000002184 metal Substances 0.000 claims description 16
- 239000000463 material Substances 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- 239000011521 glass Substances 0.000 claims description 11
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 8
- 229910017604 nitric acid Inorganic materials 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- 238000002791 soaking Methods 0.000 claims description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 5
- 239000010409 thin film Substances 0.000 claims description 5
- 238000001548 drop coating Methods 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 3
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 3
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical group [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 3
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 3
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 3
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical group [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 3
- 239000004065 semiconductor Substances 0.000 abstract description 18
- 238000006243 chemical reaction Methods 0.000 abstract description 14
- 238000000926 separation method Methods 0.000 abstract description 12
- 230000000694 effects Effects 0.000 abstract description 8
- 239000000969 carrier Substances 0.000 abstract description 6
- 230000031700 light absorption Effects 0.000 abstract description 4
- 150000001875 compounds Chemical class 0.000 abstract description 2
- 239000007772 electrode material Substances 0.000 abstract 1
- 239000012528 membrane Substances 0.000 description 29
- 239000000725 suspension Substances 0.000 description 15
- 238000001035 drying Methods 0.000 description 14
- 238000010438 heat treatment Methods 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- 229910021642 ultra pure water Inorganic materials 0.000 description 10
- 239000012498 ultrapure water Substances 0.000 description 10
- 238000000354 decomposition reaction Methods 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 238000004140 cleaning Methods 0.000 description 5
- 238000001027 hydrothermal synthesis Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000000527 sonication Methods 0.000 description 4
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 238000005286 illumination Methods 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 229910021607 Silver chloride Inorganic materials 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 230000001788 irregular Effects 0.000 description 2
- 238000004502 linear sweep voltammetry Methods 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 239000013307 optical fiber Substances 0.000 description 2
- 230000001699 photocatalysis Effects 0.000 description 2
- 229910000160 potassium phosphate Inorganic materials 0.000 description 2
- 235000011009 potassium phosphates Nutrition 0.000 description 2
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- 229910021592 Copper(II) chloride Inorganic materials 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- 241000080590 Niso Species 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229910000366 copper(II) sulfate Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
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- 238000006722 reduction reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
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- 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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- 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 provides a heterojunction photo-anode material and a preparation method and application thereof, belonging to the technical field of photo-electrode materials. CuWO of the invention4/NiWO4With WO3Inorganic copper salt and inorganic nickel salt are generated in one step through calcination reaction, and the inorganic copper salt and the inorganic nickel salt share WO3As a template for the reaction, CuWO4And NiWO4The problem of lattice mismatching does not exist between interfaces, so that the efficient separation of photo-generated charges can be realized, and the separation efficiency and the photocurrent density of photo-generated carriers are greatly improved. In the present invention, CuWO4Being an n-type semiconductor, NiWO4The p-type semiconductor is a p-type semiconductor, and the two energy bands are matched to form an effective pn junction, so that the charge separation of photo-generated charges between heterojunction interfaces is promoted, and the photocurrent density is obviously improved. And constructed CuWO4/NiWO4The nano heterojunction can widen the light absorption range, further increase the light absorption efficiency and improve the CuWO4The photoelectrocatalysis activity of the compound is obvious.
Description
Technical Field
The invention relates to the technical field of photoelectrode materials, in particular to a heterojunction photoanode material and a preparation method and application thereof.
Background
Solar energy is clean and pollution-free energy, and water is decomposed into hydrogen and oxygen by utilizing the solar energy, so that an effective way is provided for solving the energy crisis of human beings. In this context, semiconductor photocatalytic and photoelectrocatalytic technologies have been developed. Semiconductor photocatalysis technology can utilize a semiconductor to absorb sunlight, generate photoproduction electrons and holes, and then drive water reduction and oxidation reactions. However, because the photogenerated charges have short life and are quickly recombined, the technology is difficult to realize full water decomposition, and the hydrogen production is accompanied by the consumption of a sacrificial agent. The semiconductor photoelectrocatalysis technology can realize the separation of photon-generated carriers under the assistance of a small amount of external bias voltage, thereby effectively avoiding the use of a sacrificial agent, and has better application prospect than the photoelectrocatalysis technology, and the development of semiconductor photoelectrode materials is the key for realizing the application of the photoelectrocatalysis technology.
CuWO4Is an n-type semiconductor and is used as a photo-anode material in the field of photoelectrocatalysis water decomposition. CuWO4The band gap is narrow, can absorb more visible light, and the valence band potential is positive, can drive water oxidation in thermodynamics. Furthermore, CuWO4The photo-anode has excellent light stability in neutral or weak alkaline, which is beneficial to the application of the photo-anode in the field of photoelectrocatalysis. CuWO4The maximum theoretical photocurrent of the photoelectrode can reach 10.7mA/cm at most2And the theoretical photoelectric hydrogen production rate of solar energy can reach 13%. However, in practical applications CuWO4The unsatisfactory water oxidation capability of the photoanode can be attributed to the low electron-hole separation efficiency and slow water oxidation kinetics of the material. Therefore, research is being conducted on CuWO4The modification is carried out, so that the photoelectrocatalysis performance of the material is improved. The heterojunction is an effective way for promoting charge transfer of a semiconductor interface by combining two semiconductors, but the quality of the two semiconductor interfaces has great influence on the separation of photogenerated carriers, the photoelectrocatalysis activity of the semiconductors can be improved without combining the two semiconductors, the two semiconductors are simply combined, gaps, defects or lattice mismatching conditions possibly exist between the two interfaces, the separation of the carriers is prevented, and the photoelectrocatalysis water decomposition activity is limited finally.
Disclosure of Invention
In view of the above, the present invention provides a heterojunction photo-anode material, and a preparation method and an application thereof. The heterojunction photo-anode material prepared by the invention has the advantages that the interface lattice matching is realized, the efficient separation of photo-generated charges can be realized, and the separation efficiency and the photocurrent density of photo-generated carriers are greatly improved.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of a heterojunction photo-anode material, which comprises the following steps of;
growing WO on the surface of FTO glass3A film;
mixing inorganic copper salt, inorganic nickel salt and acetic acid to obtain metal mixed solution;
drop coating the metal mixture to the WO3And calcining the thin film to obtain the heterojunction photo-anode material.
Preferably, the molar ratio of the copper element in the inorganic copper salt to the nickel element in the inorganic nickel salt is 10: 1-1: 1.
Preferably, the inorganic copper salt is copper nitrate, copper chloride or copper sulfate.
Preferably, the inorganic nickel salt is nickel nitrate, nickel chloride, and nickel sulfate.
Preferably, the area is 1X 1.5cm2Of (2) the WO3The volume of the metal mixed liquid dripped on the film is 100-200 mu L.
Preferably, the calcining temperature is 500-700 ℃ and the calcining time is 2-5 h.
Preferably, the heating rate of heating to the calcining temperature is 1-5 ℃/min.
Preferably, the method further comprises the step of soaking the obtained film electrode in a nitric acid solution for 10-30 min after the calcination is finished.
The invention also provides the heterojunction photo-anode material prepared by the preparation method in the technical scheme.
The invention also provides the application of the heterojunction photo-anode material in the technical scheme in a photoelectric material.
The invention provides a preparation method of a heterojunction photo-anode material, which comprises the following steps: growing WO on the surface of FTO glass3A film; mixing inorganic copper salt, inorganic nickel salt and acetic acid to obtain metal mixed solution; drop coating the metal mixture to the WO3And calcining the thin film to obtain the heterojunction photo-anode material. Heterojunction photoanode material (CuWO) of the invention4/NiWO4) With WO3Inorganic copper salt and inorganic nickel salt are generated in one step through calcination reaction, and the inorganic copper salt and the inorganic nickel salt share WO3As a template for the reaction, CuWO4And NiWO4The problem of lattice mismatching does not exist between interfaces, so that the efficient separation of photo-generated charges can be realized, and the separation efficiency and the photocurrent density of photo-generated carriers are greatly improved.
The invention also provides a heterojunction photo-anode material prepared by the preparation method of the technical scheme, and in the invention, CuWO4Being an n-type semiconductor, NiWO4The p-type semiconductor is a p-type semiconductor, and the two energy bands are matched to form an effective pn junction, so that the charge separation of photo-generated charges between heterojunction interfaces is promoted, and the photocurrent density is obviously improved. And constructed CuWO4/NiWO4The nano heterojunction can widen the light absorption range, further increase the light absorption efficiency and improve the CuWO4The photoelectrocatalysis activity of the compound is obvious. The data of the examples show that when CuWO is used4And NiWO4The photocurrent density after the combination to form the heterojunction is obviously increased, and the photocurrent density under the bias voltage of 0.8V is changed from CuWO40.03mA · cm-2Increase to CuWO4/NiWO40.11mA · cm of-2The increase is 2.67 times, which shows that CuWO4/NiWO4The photocurrent density of the CuWO is more single4The electrode is greatly improved, and the construction of CuWO is shown4/NiWO4Nano-heterojunction pair improved CuWO4The photoelectrocatalysis water decomposition activity has great promotion effect.
Drawings
FIG. 1 is a CuWO prepared in example 14And CuWO4/NiWO4A current-potential curve graph of the photoelectric electrode film under the irradiation of simulated sunlight;
FIG. 2 is a CuWO prepared in example 24/NiWO4Photoelectrode under 0.6V bias voltage and simulated sunlight irradiationA flow-time plot;
FIG. 3 is CuWO prepared in example 34/NiWO4An X-ray diffraction pattern of the photoelectrode;
FIG. 4 is CuWO prepared in example 44/NiWO4Scanning electron microscope images of photoelectrodes.
Detailed Description
The invention provides a preparation method of a heterojunction photo-anode material, which comprises the following steps of;
growing WO on the surface of FTO glass3A film;
mixing inorganic copper salt, inorganic nickel salt and acetic acid to obtain metal mixed solution;
drop coating the metal mixture to the WO3And calcining the thin film to obtain the heterojunction photo-anode material.
The invention grows WO on the surface of FTO glass3A film. The present invention is directed to said WO3The thickness and the production method of the film are not particularly limited, and a method known to those skilled in the art may be used. In a specific embodiment of the invention, the WO is prepared3The process of the film preferably comprises the steps of: weigh 0.124gNa2WO4·2H2Dissolving O in 15mL of ultrapure water, dropwise adding 3mol/L hydrochloric acid, stirring at room temperature to obtain a white suspension, and adding dissolved (NH)4)2C2O4·2H2And 15mL of O solution, transferring the suspension into a 50mL reaction kettle after the suspension is clarified, inserting FTO glass, and carrying out hydrothermal reaction for 4h in an oven at 150 ℃. After the reaction is finished, taking out the membrane, cleaning the membrane by ultrapure water, drying the membrane, calcining the membrane in a muffle furnace at 500 ℃ for 2.5h at the heating rate of 3 ℃/min to obtain WO3A film.
The invention mixes inorganic copper salt, inorganic nickel salt and acetic acid to obtain metal mixed liquid.
In the present invention, the molar ratio of the copper element in the inorganic copper salt to the nickel element in the inorganic nickel salt is preferably 10:1 to 1:1, and more preferably 5:1 to 2: 1.
In the present invention, the inorganic copper salt is preferably copper nitrate, copper chloride or copper sulfate.
In the present invention, the inorganic nickel salt is preferably nickel nitrate, nickel chloride and nickel sulfate.
The amount of the acetic acid used and the specific manner of mixing are not particularly limited in the present invention, and the inorganic metal salt can be completely dissolved.
Obtaining the metal mixed solution and WO3A film formed by applying the metal mixture to the WO3And calcining the thin film to obtain the heterojunction photo-anode material.
In the present invention, the area is 1X 1.5cm2Of (2) the WO3The volume of the metal mixture solution to be dropped on the film is preferably 100 to 200. mu.L, and more preferably 150. mu.L.
In the invention, the dripping is preferably performed repeatedly, the number of times of the repeating is preferably 1-2, and the dripping is preferably performed for the first time, and then the second time after the first time is dried. The present invention is not particularly limited to the specific operation of the drying. In the present invention, the area is 1X 1.5cm in the repeated process2Of (2) the WO3The volume of the metal mixture solution to be dropped on the film is preferably 100 to 200. mu.L, and more preferably 150. mu.L.
In the invention, the calcination temperature is preferably 500-700 ℃, more preferably 550-600 ℃, and the time is preferably 2-5 h. In the present invention, the calcination is preferably carried out in a muffle furnace.
In the present invention, the heating rate for heating to the calcination temperature is preferably 1 to 5 ℃/min, and more preferably 2 to 3 ℃/min.
In the invention, after the calcination is finished, the obtained membrane electrode is soaked in a nitric acid solution for 10-30 min, the concentration of the nitric acid solution is preferably 1mo/L, and the soaking can remove the excessive CuO and NiO.
The invention also provides the heterojunction photo-anode material prepared by the preparation method in the technical scheme.
The invention also provides the application of the heterojunction photo-anode material in the technical scheme in a photoelectric material.
In order to further illustrate the present invention, the heterojunction photoanode material provided by the present invention, the preparation method and the application thereof are described in detail below with reference to examples, but they should not be construed as limiting the scope of the present invention.
Example 1
Preparation of WO3Film formation: weigh 0.124gNa2WO4·2H2Dissolving O in 15mL of ultrapure water, dropwise adding 3mol/L hydrochloric acid, stirring at room temperature to obtain a white suspension, and adding dissolved (NH)4)2C2O4·2H2And 15mL of O solution, transferring the suspension into a 50mL reaction kettle after the suspension is clarified, inserting FTO glass, and carrying out hydrothermal reaction for 4h in an oven at 150 ℃. After the reaction is finished, taking out the membrane, cleaning the membrane by ultrapure water, drying the membrane, calcining the membrane in a muffle furnace at 500 ℃ for 2.5h at the heating rate of 3 ℃/min to obtain WO3A film.
0.121gCu (NO)3)2Dissolved in 5mL of acetic acid and 0.145gNi (NO) was added3)2Solid, dissolved by sonication. 100. mu.L of the solution was pipetted onto a 1X 1.5cm thick tube2WO3On the membrane, dropwise adding for the second time after drying, placing in a muffle furnace at 550 ℃ for calcining for 2h at the heating rate of 2 ℃/min after drying, soaking the obtained membrane electrode in a nitric acid solution of 1mo/L for 15min after cooling, removing excessive CuO and NiO, and obtaining CuWO4/NiWO4And a photoelectrode.
FIG. 1 is a schematic representation of CuWO prepared in example 14And CuWO4/NiWO4The current-potential curve diagram of the photoelectrode film under the simulated sunlight irradiation adopts an electrochemical workstation to test the water decomposition performance of the photoelectrode, and concretely adopts CuWO4Or CuWO4/NiWO4Is a working electrode, Ag/AgCl is a reference electrode, a Pt sheet is a counter electrode, simulated sunlight is introduced to the surface of the electrode through an optical fiber, and CuWO is measured through a linear sweep voltammetry method4Or CuWO4/NiWO4The photoelectrode has the current density under illumination, the electrolyte is 0.1mol/L potassium phosphate solution, and the pH value of the solution is 7. Under simulated sunlight irradiation, with the increase of the potential, CuWO4The photocurrent density of the light source is gradually increased, and the polarization potential is about 0.2V.When CuWO is used4And NiWO4The photocurrent density after combination to form a heterojunction is significantly increased, e.g., from CuWO at a bias of 0.8V40.03mA · cm-2Increase to CuWO4/NiWO40.11mA · cm of-2The increase is 2.67 times. The results of this test illustrate CuWO4/NiWO4The photocurrent density of the CuWO is more single4The electrode is greatly improved, and the surface is constructed with CuWO4/NiWO4Nano-heterojunction pair improved CuWO4The photoelectrocatalysis water decomposition activity has great promotion effect.
Example 2
Preparation of WO3Film formation: weigh 0.124gNa2WO4·2H2Dissolving O in 15mL of ultrapure water, dropwise adding 3mol/L hydrochloric acid, stirring at room temperature to obtain a white suspension, and adding dissolved (NH)4)2C2O4·2H2And 15mL of O solution, transferring the suspension into a 50mL reaction kettle after the suspension is clarified, inserting FTO glass, and carrying out hydrothermal reaction for 4h in an oven at 150 ℃. After the reaction is finished, taking out the membrane, cleaning the membrane by ultrapure water, drying the membrane, calcining the membrane in a muffle furnace at 500 ℃ for 2.5h at the heating rate of 3 ℃/min to obtain WO3A film.
0.121gCu (NO)3)2Dissolved in 5mL of acetic acid and 0.083gNi (NO) was added3)2Solid, dissolved by sonication. 150. mu.L of the solution was pipetted onto a 1X 1.5cm thick tube2WO3On the membrane, dropwise adding for the second time after drying, calcining for 3h in a 600 ℃ muffle furnace after drying at the heating rate of 1 ℃/min, soaking the obtained membrane electrode in 1mo/L nitric acid solution for 30min after cooling, removing excessive CuO and NiO, and obtaining CuWO4/NiWO4And a photoelectrode.
FIG. 2 is a CuWO prepared in example 24/NiWO4Current-time curve diagram of photoelectrode under 0.6V bias and simulated sunlight irradiation with CuWO4/NiWO4Is a working electrode, Ag/AgCl is a reference electrode, a Pt sheet is a counter electrode, simulated sunlight is introduced to the surface of the electrode through an optical fiber, and CuWO is measured through a linear sweep voltammetry method4/NiWO4The current density of the photoelectrode under illumination, the electrolyte of the potassium phosphate solution of 0.1mol/L and the pH value of the solution are 7, and the graph shows that the photocurrent is only attenuated by 12.5 percent under the illumination time of 4.2 hours, which indicates that the CuWO prepared by the invention4/NiWO4The photoelectrode has better light stability, which is for CuWO4/NiWO4The practical application of the photoelectrode is of great importance.
Example 3
Preparation of WO3Film formation: weigh 0.124gNa2WO4·2H2Dissolving O in 15mL of ultrapure water, dropwise adding 3mol/L hydrochloric acid, stirring at room temperature to obtain a white suspension, and adding dissolved (NH)4)2C2O4·2H2And 15mL of O solution, transferring the suspension into a 50mL reaction kettle after the suspension is clarified, inserting FTO glass, and carrying out hydrothermal reaction for 4h in an oven at 150 ℃. After the reaction is finished, taking out the membrane, cleaning the membrane by ultrapure water, drying the membrane, calcining the membrane in a muffle furnace at 500 ℃ for 2.5h at the heating rate of 3 ℃/min to obtain WO3A film.
0.264g of CuCl2Dissolved in 5mL of acetic acid, and 0.129g of NiCl was added2Solid, dissolved by sonication. 180. mu.L of the solution was pipetted onto a 1X 1.5cm thick tube2WO3On the membrane, dropwise adding for the second time after drying, calcining for 3h in a 600 ℃ muffle furnace after drying, heating at the rate of 3 ℃/min, cooling, soaking the obtained membrane electrode in 1mo/L nitric acid solution for 20min, removing excessive CuO and NiO, and obtaining CuWO4/NiWO4And a photoelectrode.
FIG. 3 is CuWO prepared in example 34/NiWO4The photoelectrode X-ray diffraction pattern can be found through retrieval, and the X-ray peak in the pattern can be well retrieved as CuWO4、NiWO4And SnO2(SnO is present on the surface of FTO glass2So that SnO has appeared2Signal) proves that the process can realize CuWO4/NiWO4And (3) preparing the composite photoelectrode film.
Example 4
Preparation of WO3Film formation: weigh 0.124gNa2WO4·2H2Dissolving O in 15mL of ultrapure water, dropwise adding 3mol/L hydrochloric acid, stirring at room temperature to obtain a white suspension, and adding dissolved (NH)4)2C2O4·2H2And 15mL of O solution, transferring the suspension into a 50mL reaction kettle after the suspension is clarified, inserting FTO glass, and carrying out hydrothermal reaction for 4h in an oven at 150 ℃. After the reaction is finished, taking out the membrane, cleaning the membrane by ultrapure water, drying the membrane, calcining the membrane in a muffle furnace at 500 ℃ for 2.5h at the heating rate of 3 ℃/min to obtain WO3A film.
Mixing 0.70g of CuSO4Dissolved in 5mL of acetic acid, 0.262g of NiSO was added4Solid, dissolved by sonication. 100. mu.L of the solution was pipetted onto a 1X 1.5cm thick tube2WO3On the membrane, dropwise adding for the second time after drying, calcining for 3h in a muffle furnace at 550 ℃ after drying, heating at the rate of 2 ℃/min, cooling, soaking the obtained membrane electrode in a 1mo/L nitric acid solution for 30min, removing excessive CuO and NiO, and obtaining CuWO4/NiWO4And a photoelectrode.
FIG. 4 is CuWO prepared in example 44/NiWO4The scanning electron microscope image of the photoelectrode shows that the prepared electrode is irregular in appearance mainly due to solid-phase reaction in the calcining process, the electrode is composed of a plurality of irregular nano particles, and the particles are stacked mutually.
The foregoing is merely a preferred embodiment of the invention and is not intended to limit the invention in any manner. It should be noted that, for those skilled in the art, without departing from the principle of the present invention, several improvements and modifications can be made, and these improvements and modifications should also be construed as the protection scope of the present invention.
Claims (10)
1. A preparation method of a heterojunction photo-anode material is characterized by comprising the following steps;
growing WO on the surface of FTO glass3A film;
mixing inorganic copper salt, inorganic nickel salt and acetic acid to obtain metal mixed solution;
drop coating the metal mixture to the WO3Calcining the film to obtain the heterojunction photo-anode material which is CuWO4/NiWO4A nano-heterojunction.
2. The method according to claim 1, wherein the molar ratio of the copper element in the inorganic copper salt to the nickel element in the inorganic nickel salt is 10:1 to 1: 1.
3. The method according to claim 1 or 2, wherein the inorganic copper salt is copper nitrate, copper chloride or copper sulfate.
4. The production method according to claim 1 or 2, wherein the inorganic nickel salt is nickel nitrate, nickel chloride, and nickel sulfate.
5. The method of claim 1, wherein the area is 1 x 1.5cm2Of (2) the WO3The volume of the metal mixed liquid dripped on the film is 100-200 mu L.
6. The preparation method according to claim 1, wherein the calcining temperature is 500-700 ℃ and the calcining time is 2-5 h.
7. The method according to claim 6, wherein the rate of temperature increase to the calcination temperature is 1 to 5 ℃/min.
8. The preparation method of claim 1, 6 or 7, further comprising soaking the obtained thin film electrode in a nitric acid solution for 10-30 min after the calcination is completed.
9. The heterojunction photoanode material prepared by the preparation method of any one of claims 1 to 8.
10. Use of the heterojunction photoanode material of claim 9 in a photovoltaic material.
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| CN105568314A (en) * | 2015-12-21 | 2016-05-11 | 河南师范大学 | Preparation method of CuWO4/WO3 heterostructured nanosheet array film |
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