CN110639584A - Black silicon/(GaN)1-x(ZnO)xNano-rod composite photo-anode and preparation method thereof - Google Patents
Black silicon/(GaN)1-x(ZnO)xNano-rod composite photo-anode and preparation method thereof Download PDFInfo
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- 229910021418 black silicon Inorganic materials 0.000 title claims abstract description 65
- 239000002131 composite material Substances 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000002073 nanorod Substances 0.000 claims abstract description 52
- 229910007486 ZnGa2O4 Inorganic materials 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 13
- 238000005121 nitriding Methods 0.000 claims abstract description 11
- 239000002159 nanocrystal Substances 0.000 claims abstract description 3
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- 238000010438 heat treatment Methods 0.000 claims description 12
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 239000012286 potassium permanganate Substances 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- 239000006185 dispersion Substances 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 8
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 7
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- 238000001035 drying Methods 0.000 claims description 7
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- CHPZKNULDCNCBW-UHFFFAOYSA-N gallium nitrate Chemical compound [Ga+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O CHPZKNULDCNCBW-UHFFFAOYSA-N 0.000 description 10
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- 229910021607 Silver chloride Inorganic materials 0.000 description 1
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- 229910052733 gallium Inorganic materials 0.000 description 1
- QZQVBEXLDFYHSR-UHFFFAOYSA-N gallium(III) oxide Inorganic materials O=[Ga]O[Ga]=O QZQVBEXLDFYHSR-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
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- 238000007747 plating Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
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- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B01J35/33—
-
- B01J35/39—
-
- 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
- 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
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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
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- 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
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Abstract
The invention relates to black silicon/(GaN)1‑x(ZnO)xA nano-rod composite photo-anode and a preparation method thereof. The method comprises the following steps: preparation of black silicon/ZnO nano-rod, black silicon/ZnO nano-rod-ZnGa2O4Preparation of nanocrystals, black silicon/(GaN)1‑x(ZnO)xAnd (4) preparing the nanorod composite photo-anode. The method has the advantages of low nitriding temperature, short nitriding time and black silicon/(GaN) obtained1‑x(ZnO)xThe nano rod has a large x value and has high photocurrent density.
Description
Technical Field
The invention belongs to the field of photoelectrocatalysis anodes and preparation thereof, and particularly relates to black silicon/(GaN)1-x(ZnO)xA nano-rod composite photo-anode and a preparation method thereof.
Background
In recent years, environmental and energy problems have been increased, and the photoelectrocatalysis technology has received great attention because it can decompose water into hydrogen and oxygen using sunlight and can degrade pollutants. The most widely and deeply studied photocatalytic material in the past half century was TiO2The wide band gap semiconductor can only absorb ultraviolet light, and the utilization rate of sunlight is extremely low, so that the development and utilization of the photocatalytic material responding to visible light are very important.
(GaN)1-x(ZnO)xIs a stable solid solution formed by ZnO and GaN, and is a new visible light catalytic material in recent years. (GaN)1-x(ZnO)xThe solid solution has a narrow forbidden band width (2.4-2.8 eV), has strong absorption in a visible light region, is stable in chemical property, and has a good application prospect in the field of photocatalysis. Preparation at present (GaN)1-x(ZnO)xThe method of (1) is mainly Ga2O3And ZnO micropowder as a raw material, by nitriding at high temperature in an ammonia atmosphere, but obtained by this method (GaN)1-x(ZnO)xMicron-sized, and heavily agglomerated, with a very low specific surface area, a long photoproduction load transfer time to the surface, and a low charge separation efficiency, thus producing nano-sized (GaN)1-x(ZnO)xSolid solutions are of critical importance. Furthermore, (GaN)1-x(ZnO)xThe band gap of the solid solution decreases with increasing ZnO content and thus increases (GaN)1-x(ZnO)xThe content of ZnO in the film (i.e. x value) can effectively absorb visible light, increase photocurrent and enhance quantum efficiency, but (GaN)1-x(ZnO)xThe control of the components and the adjustment of the band gap still have great challenges, and the main problem is that Zn is reduced into simple substances and volatilized under high-temperature conditions and a reducing atmosphere.
To solve the above problems, it is important to develop a new synthesis strategy to prepare nanoscale (GaN)1-x(ZnO)xSolid solution, and as low as possible synthesis (GaN)1-x(ZnO)xIs nitrided inTemperature, increase (GaN)1-x(ZnO)xThe content of ZnO in the product. Literature [ Jing Li, et al, organic Chemistry,2018,9,5240-]Successfully synthesize (GaN) on a silicon wafer substrate1-x(ZnO)xThe photocurrent of the nano-wire can reach 30 mu A/cm under the irradiation of visible light2However, the method is to plate a layer of Au on the silicon chip and then obtain (GaN) by VLS mechanism1-x(ZnO)xThe method uses Au, so that the cost is high, the nitriding temperature is high (850 ℃), the value of x is between 0.10 and 0.47, and the range is narrow and not high enough.
Disclosure of Invention
The technical problem to be solved by the invention is to provide black silicon/(GaN)1-x(ZnO)xNano-rod composite photoanode and its preparation method, which overcomes the disadvantages of existing synthesis (GaN)1-x(ZnO)xThe required nitridation reaction temperature is too high, the x value is small and the range is narrow.
The invention provides a black silicon/(GaN)1-x(ZnO)xThe nano-rod composite photo-anode is characterized in that ZnO nano-rods grow on a black silicon substrate, and then are self-assembled and loaded with ZnGa on the ZnO nano-rods2O4Nanocrystalline and then nitriding treatment.
The (GaN)1-x(ZnO)xThe length of the nano-rod is 3-5 μm, the diameter is 200-500 nm, and the value of x is 0.12-0.94.
The ZnGa compound2O4The size of the nanocrystalline grains is 30-80 nm.
The invention also provides black silicon/(GaN)1-x(ZnO)xThe preparation method of the nanorod composite photoanode comprises the following steps:
(1) vertically putting the cleaned black silicon substrate into a mixed solution of zinc nitrate hexahydrate aqueous solution, ammonia water and ethanolamine for water bath reaction, washing with water and drying in the air to obtain a black silicon/ZnO nanorod;
(2) putting nano ZnGa on a hot bench2O4Dropwise adding the dispersion liquid onto the black silicon/ZnO nano-rod in the step (1), evaporating to dryness, and loading ZnGa on the ZnO nano-rod through self-assembly2O4Obtaining black silicon/ZnO nano-rod by using nano-crystal-ZnGa2O4A nanocrystal;
(3) the black silicon/ZnO nano rod-ZnGa obtained in the step (2)2O4The nanocrystalline is nitridized in ammonia gas and cooled to obtain black silicon/(GaN)1-x(ZnO)xThe nanorod composite photo-anode is characterized in that nitridation is carried out: heating to 600-750 ℃ and preserving the heat for 1-4 h.
The cleaning of the black silicon substrate in the step (1) comprises the following steps: the black silicon substrate is ultrasonically washed in acetone, ethanol and deionized water respectively, and then treated by potassium permanganate solution and washed by water.
The concentration of the zinc nitrate hexahydrate aqueous solution in the step (1) is 0.03-0.07 mol/L; the volume ratio of the zinc nitrate hexahydrate aqueous solution to the ammonia water (25-28%) to the ethanolamine is 18:1: 0.5-18: 1: 2.
The water bath reaction temperature in the step (1) is 70-95 ℃, and the water bath reaction time is 1-5 h.
The nano ZnGa in the step (2)2O4The preparation method of the dispersion comprises the following steps: carrying out hydrothermal reaction on a uniformly mixed aqueous solution of zinc nitrate hexahydrate, gallium nitrate hydrate and urea, centrifugally washing and drying to obtain ZnGa2O4Powder; ZnGa is reacted with2O4Adding the powder into deionized water, stirring, and performing ultrasonic treatment.
The concentration of zinc nitrate hexahydrate and gallium nitrate hydrate in the mixed water solution is 0.02-0.03 mol/L, and the concentration of urea is 0.1-0.3 mol/L.
The hydrothermal reaction temperature is 150-200 ℃, and the hydrothermal reaction time is 10-15 h.
The drying is carried out for 10-20 h at 50-90 ℃.
The nano ZnGa in the step (2)2O4The concentration of the dispersion is 10-20 mg/mL.
ZnGa in the step (2)2O4High activity of nanocrystalline enables black silicon/ZnO nanorod-ZnGa2O4The nanocrystalline reacts with NH at a relatively low temperature3The reaction produces a nitriding effect which cannot be obtained by the fine powder.
The temperature of the hot stage in the step (2) is 150-200 ℃.
The ammonia gas flow in the step (3) is 100-300 mL/min; the nitridation heating rate is 2-7 ℃/min.
The invention also provides black silicon/(GaN)1-x(ZnO)xThe application of the nanorod composite photo-anode in photoelectrocatalysis.
The invention introduces high-activity ZnGa2O4The nanocrystalline has the advantages of low nitriding temperature, short nitriding time, large x value and high photocurrent density.
Advantageous effects
(1) The invention can prepare black silicon/(GaN) with different ZnO contents (namely x value)1-x(ZnO)xThe nano-rod composite photo-anode has large x value and wide adjustable range.
(2) The invention can obviously reduce synthesis (GaN)1-x(ZnO)xThe required nitriding temperature, the nitriding time and the energy consumption are greatly reduced.
(3) Prepared by the present invention (GaN)1-x(ZnO)xThe nano-rod has nano-scale diameter and uniform distribution, and the nitridation temperature is 600 ℃ to obtain black silicon/(GaN)1-x(ZnO)xThe nanorods have a higher photocurrent density.
(4) The preparation method is simple, the raw materials are cheap and easy to obtain, and the operation is easy.
Drawings
FIG. 1 shows black silicon/(GaN) prepared in example 11-x(ZnO)xFESEM photographs of (a) surface and (b) cross section of the nanorods;
FIG. 2 shows black silicon/(GaN) prepared in example 11-x(ZnO)xThe X-ray diffraction pattern of the nano-rods;
FIG. 3 shows black silicon/(GaN) prepared in examples 1, 2 and 31-x(ZnO)xEDS energy spectrum of the nano-rod;
FIG. 4 shows black silicon/(GaN) prepared in example 21-x(ZnO)xUltraviolet-visible diffuse reflection absorption spectrum of the nanorods;
FIG. 5 shows black silicon/(GaN) prepared in example 11-x(ZnO)xPhotocurrent of nanorod under intermittent illumination conditionDensity map.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
The zinc nitrate hexahydrate, ammonia, ethanolamine, gallium nitrate hydrate, urea and potassium permanganate reagents used in the experiment are from national medicine group chemical reagent company Limited. All reagents were used without further treatment.
Example 1
(1) The black silicon substrate is sequentially ultrasonically washed in acetone, ethanol and deionized water for 20min, then 0.05mol/L potassium permanganate solution is prepared, and the cleaned black silicon is vertically placed in the potassium permanganate solution to be soaked for 30min, then washed with water and dried. 1.3387g of zinc nitrate hexahydrate was added to 90ml of water to form a 0.05mol/L homogeneous solution, and 5ml of ammonia water and 5ml of ethanolamine were added thereto and stirred to form a homogeneous mixed solution. Vertically putting the cleaned black silicon into the mixed solution, carrying out water bath reaction at 85 ℃ for 2h, washing with water, and airing to obtain a black silicon/ZnO nanorod;
(2) adding 0.60g of zinc nitrate hexahydrate, 0.51g of gallium nitrate hydrate and 0.60g of urea into 100ml of water to prepare a uniformly mixed aqueous solution, carrying out hydrothermal reaction for 15h at 150 ℃, carrying out centrifugal washing, and drying in an oven at 50 ℃ for 20h to obtain ZnGa2O4And (3) powder. 0.075g of ZnGa2O4The powder was added to 5mL water, stirred for 20min and sonicated for 20min to give a 15mg/mL homogeneous dispersion. Dropwise adding the dispersion liquid on the black silicon/ZnO nano rod obtained in the step (1) on a heating table at 150 ℃, and evaporating to dryness to load ZnGa on the ZnO nano rod2O4Particles;
(3) placing the sample obtained in the step (2) in a tubular furnace, introducing flowing ammonia gas, controlling the flow of the ammonia gas to be 200mL/min, heating from room temperature to 600 ℃, controlling the heating speed to be 4 ℃/min, and preserving the heat at 600 DEG CAfter 2h, naturally cooling to room temperature to obtain black silicon/(GaN)1-x(ZnO)xAnd (x is 0.94).
FIG. 1 shows the black silicon/(GaN) obtained in this example1-x(ZnO)xFESEM photograph of the nanorods, from which (GaN)1-x(ZnO)xThe nano-rods have a diameter of about 200-500 nm, a length of about 3-5 μm, and are uniformly distributed.
FIG. 2 shows the black silicon/(GaN) obtained in this example1-x(ZnO)xAs seen from the X-ray diffraction pattern of the nanorods, the diffraction peak of the sample obtained in this example is between the characteristic peaks of ZnO (JCPDS NO.36-1451) and GaN (JCPDS NO.50-0792), indicating that a solid solution of ZnO and GaN is formed.
FIG. 3(a) shows black silicon/(GaN) obtained in the present example1-x(ZnO)xThe EDS spectrum of the nanorods can be calculated to obtain that the Zn atom content in the sample prepared in this example is 94%, i.e. x is 0.94.
The sample of this example was used as a working electrode, a Pt sheet as a counter electrode, an Ag/AgCl electrode as a reference electrode, and 0.5mol/L Na2SO4The solution is an electrolyte. The 300W xenon lamp with filter (lambda is more than or equal to 420nm) is used as visible light source, and the photocurrent density is tested under the condition of applied bias voltage of 1V, and the result is shown in figure 5, wherein the photocurrent is about 55 muA/cm2And the literature [ Jing Li, et al, organic Chemistry,2018,9,5240-](see comparative example 1) the photocurrent density was increased by about 25. mu.A/cm2。
Example 2
(1) The black silicon substrate is sequentially ultrasonically washed in acetone, ethanol and deionized water for 20min, then 0.05mol/L potassium permanganate solution is prepared, and the cleaned black silicon is vertically placed in the potassium permanganate solution to be soaked for 30min, then washed with water and dried. 0.8032g of zinc nitrate hexahydrate was added to 90ml of water to form a uniform solution of 0.03mol/L, and 5ml of ammonia water and 2.5ml of ethanolamine were added thereto and stirred to form a uniform mixed solution. Vertically putting the cleaned black silicon into the mixed solution, carrying out water bath reaction at 95 ℃ for 1h, washing with water, and airing to obtain a black silicon/ZnO nanorod;
(2) 0.74g of zinc nitrate hexahydrate and 0.64g of nitre hydrateAdding gallium acid and 1.20g of urea into 100ml of water to prepare a uniformly mixed aqueous solution, carrying out hydrothermal reaction at 180 ℃ for 12h, carrying out centrifugal washing, and drying in a 70 ℃ oven for 15h to obtain ZnGa2O4And (3) powder. 0.05g of ZnGa2O4The powder was added to 5mL water, stirred for 20min and sonicated for 20min to give a 10mg/mL homogeneous dispersion. Dropwise adding the dispersion liquid on the black silicon/ZnO nano rod obtained in the step (1) on a heating table at 170 ℃, and evaporating to dryness to load ZnGa on the ZnO nano rod2O4Particles;
(3) placing the sample obtained in the step (2) in a tubular furnace, introducing flowing ammonia gas, controlling the flow of the ammonia gas at 100mL/min, heating from room temperature to 650 ℃, heating at the speed of 2 ℃/min, keeping the temperature at 650 ℃ for 1h, and then naturally cooling to room temperature to obtain black silicon/(GaN)1-x(ZnO)xAnd (4) a nanorod composite photoanode (x is 0.70).
FIG. 3(b) shows black silicon/(GaN) obtained in the present example1-x(ZnO)xThe EDS spectrum of the nanorods can be calculated to obtain that the Zn atom content in the sample prepared in this example is 70%, i.e. x is 0.70.
FIG. 4 shows the black silicon/(GaN) obtained in this example1-x(ZnO)xAs for the ultraviolet-visible diffuse reflection absorption spectrum of the nanorod, the absorption edge position of the sample in the embodiment is about 480nm, which indicates that the nanorod has an absorption effect on visible light.
As in example 1, the magnitude of the photocurrent measured was about 23. mu.A/cm2。
Example 3
(1) The black silicon substrate is sequentially ultrasonically washed in acetone, ethanol and deionized water for 20min, then 0.05mol/L potassium permanganate solution is prepared, and the cleaned black silicon is vertically placed in the potassium permanganate solution to be soaked for 30min, then washed with water and dried. 1.8742g of zinc nitrate hexahydrate was added to 90ml of water to form a uniform solution of 0.07mol/L, and 5ml of ammonia water and 10ml of ethanolamine were added thereto and stirred to form a uniform mixed solution. Vertically putting the cleaned black silicon into the mixed solution, carrying out water bath reaction at 70 ℃ for 5 hours, washing with water, and airing to obtain a black silicon/ZnO nanorod;
(2) 0.89g of zinc nitrate hexahydrate, 0.77g of gallium nitrate hydrate andadding 1.80g of urea into 100ml of water to prepare a uniformly mixed aqueous solution, carrying out hydrothermal reaction for 10h at 200 ℃, carrying out centrifugal washing, and drying for 10h in a 90 ℃ oven to obtain ZnGa2O4And (3) powder. 0.10g of ZnGa2O4The powder was added to 5mL water, stirred for 20min and sonicated for 20min to give a uniform dispersion of 20 mg/mL. Dropwise adding the dispersion liquid on the black silicon/ZnO nano rod obtained in the step (1) on a hot table at 200 ℃, and evaporating to dryness to load ZnGa on the ZnO nano rod2O4Particles;
(3) placing the sample obtained in the step (2) in a tubular furnace, introducing flowing ammonia gas, controlling the flow of the ammonia gas at 300mL/min, heating from room temperature to 750 ℃, keeping the temperature at the heating speed of 7 ℃/min at 750 ℃ for 4h, and then naturally cooling to room temperature to obtain black silicon/(GaN)1-x(ZnO)xAnd (x is 0.12).
FIG. 3(c) shows black silicon/(GaN) obtained in the present example1-x(ZnO)xThe EDS spectrum of the nanorods can be calculated to obtain that the Zn atom content in the sample prepared in this example is 12%, i.e. x is 0.12.
As in example 1, the magnitude of the photocurrent measured was about 2. mu.A/cm2。
Comparative example 1
Literature [ Jing Li, et al, organic Chemistry,2018,9,5240-]Preparing Si/(GaN)1-x(ZnO)xThe nanowire is used as a photo-anode, and the specific preparation method comprises the following steps: firstly plating an Au layer with the thickness of 5nm on a silicon wafer substrate, then preparing a Zn-Ga-O powder precursor, and then preparing the (GaN) on the surface of the silicon wafer by utilizing a VLS mechanism in a tube furnace under the atmosphere of ammonia gas1-x(ZnO)xA nanowire. Si/(GaN) prepared by the method1-x(ZnO)xUnder the condition that the external bias voltage is 1V, the measured photocurrent density of the nanowire composite photo-anode reaches 30 mu A/cm2. Black silicon/(GaN) prepared by the invention1-x(ZnO)xThe photocurrent density of the nano-rod composite photo-anode can reach 55 muA/cm under the condition that the external bias voltage is 1V2Compared with the prior art, the photoelectric performance is obviously improved.
Claims (10)
1. Black silicon/(GaN)1-x(ZnO)xThe nano-rod composite photoanode is characterized in that ZnO nano-rods grow on a black silicon substrate, and then ZnGa is loaded on the ZnO nano-rods in a self-assembly manner2O4Nanocrystalline and then nitriding treatment.
2. The photoanode of claim 1, wherein the (GaN)1-x(ZnO)xThe length of the nano-rod is 3-5 μm, the diameter is 200-500 nm, and the value of x is 0.12-0.94; ZnGa2O4The size of the nanocrystalline grains is 30-80 nm.
3. Black silicon/(GaN)1-x(ZnO)xThe preparation method of the nanorod composite photoanode comprises the following steps:
(1) vertically putting the cleaned black silicon substrate into a mixed solution of zinc nitrate hexahydrate aqueous solution, ammonia water and ethanolamine for water bath reaction, washing with water and drying in the air to obtain a black silicon/ZnO nanorod;
(2) putting nano ZnGa on a hot bench2O4Dropwise adding the dispersed liquid onto the black silicon/ZnO nano rod in the step (1), and evaporating to dryness to obtain black silicon/ZnO nano rod-ZnGa2O4A nanocrystal;
(3) the black silicon/ZnO nano rod-ZnGa obtained in the step (2)2O4The nanocrystalline is nitridized in ammonia gas and cooled to obtain black silicon/(GaN)1-x(ZnO)xThe nanorod composite photo-anode is characterized in that nitridation is carried out: heating to 600-750 ℃ and preserving the heat for 1-4 h.
4. The method as claimed in claim 3, wherein the cleaning of the black silicon substrate in the step (1) is: the black silicon substrate is ultrasonically washed in acetone, ethanol and deionized water respectively, and then treated by potassium permanganate solution and washed by water.
5. The method as claimed in claim 3, wherein the concentration of the zinc nitrate hexahydrate aqueous solution in the step (1) is 0.03-0.07 mol/L; the volume ratio of the zinc nitrate hexahydrate aqueous solution to the ammonia water to the ethanolamine is 18:1: 0.5-18: 1: 2.
6. The method as claimed in claim 3, wherein the water bath reaction temperature in the step (1) is 70-95 ℃ and the water bath reaction time is 1-5 h.
7. The method of claim 3, wherein the step (2) is performed by using nano ZnGa2O4The concentration of the dispersion is 10-20 mg/mL.
8. The method according to claim 3, wherein the hot stage temperature in the step (2) is 150 to 200 ℃.
9. The method according to claim 3, wherein the ammonia gas flow rate in the step (3) is 100-300 mL/min; the nitridation heating rate is 2-7 ℃/min.
10. Use of the anode of claim 1 in photoelectrocatalysis.
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