CN110508291B - Au-ZnIn2S4Preparation method of nano array electrode photocatalytic nitrogen fixation material - Google Patents

Au-ZnIn2S4Preparation method of nano array electrode photocatalytic nitrogen fixation material Download PDF

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CN110508291B
CN110508291B CN201910823580.7A CN201910823580A CN110508291B CN 110508291 B CN110508291 B CN 110508291B CN 201910823580 A CN201910823580 A CN 201910823580A CN 110508291 B CN110508291 B CN 110508291B
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毛梁
李坤
顾修全
蔡晓燕
杨鼎
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China University of Mining and Technology CUMT
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Abstract

Au-ZnIn2S4A preparation method of a nano array electrode photocatalysis nitrogen fixation material belongs to a method for preparing and modifying photoelectrochemistry catalysis materials. The preparation method comprises the following steps: based on ZnIn2S4The nano-array electrode photo-deposits nano Au particles on the surface of the nano-array electrode to improve ZnIn2S4The photocatalytic nitrogen fixation performance; firstly, a layer of ZnIn is grown on FTO conductive glass by adopting a hydrothermal method2S4The nanosheet array is prepared by depositing Au particles on the surface of the nanosheet array by a photo-deposition method to obtain Au-ZnIn2S4An electrode; Au-ZnIn2S4Fixing the electrode plate in methanol water solution, continuously introducing high-purity nitrogen, and irradiating N under xenon lamp2Conversion to NH3And then converted into NH4+(ii) a Mixing the reaction solution with a Nashi reagent for color development, and determining NH in the reaction solution4+And the concentration further determines the photocatalytic nitrogen fixation performance of the material. The advantages are that: the preparation is simple, the preparation conditions are loose, the materials are nontoxic, and the materials are easy to recover in the application process and can be recycled; ZnIn is added2S4The forbidden band width is narrower, the material can absorb visible light in a wider range, Au can also absorb the visible light strongly in the visible light range, and the comprehensive utilization rate of the material to the visible light is improved.

Description

Au-ZnIn2S4Preparation method of nano array electrode photocatalytic nitrogen fixation material
Technical Field
The present invention relates to a photoelectrochemical catalytic materialPreparation and modification method, in particular to Au-ZnIn2S4A preparation method of a nano array electrode photocatalysis nitrogen fixation material.
Background
Ammonia is an essential production raw material in the aspects of chemical industry, medicine, agriculture and the like. At present, the synthetic ammonia in industrial production is still the traditional haber method, the reaction temperature is more than 300 ℃, the pressure is more than 100atm, and the synthetic ammonia reacts in the catalytic process of the iron-based catalyst. H required in the synthesis reaction2Mainly produced by the evaporative conversion of natural gas, the maintenance of the whole reaction process consumes 1-2% of fossil energy on earth and causes a large amount of CO2And (4) discharging. From the viewpoint of reducing the consumption of non-renewable energy sources and the emission of less greenhouse gases, the synthesis of ammonia by utilizing light energy is very valuable for scientific research.
The photoelectrocatalysis process is a process for converting light energy into chemical energy and is one of ideas for solving energy crisis. Many materials with photocatalytic properties are available, but few materials capable of achieving photocatalytic nitrogen fixation are available, mainly because of N2The molecule is very stable and requires at least 941.69kJ of energy per mole of N.ident.N molecule to be fully opened, wherein 410kJmol are required for the first N-N bond to be dissociated-1The energy required to convert nitrogen to ammonia is very large.
TiO is most studied at present2Photocatalytic material, TiO2The photocatalytic nitrogen fixation performance can be improved by various modification means. Gongjin dragon team of Tianjin university TiO2The research of fixing nitrogen by electrodes is carried out, and a layer of TiO grows on the FTO conductive glass by a hydrothermal method2Nanorod followed by TiO2The introduction of oxygen vacancy and noble metal into the electrode realizes the improvement of nitrogen fixation performance to 13.4nmol/cm2[ solution ] h (reference: Alammar, T.; Hamm, I.; Grasmik, V.; Wark, M.; Mudring, A.V., Microwave-Assisted Synthesis of Perovskite SrSnO3 Nanocrystals in Ionic liquids for Photocaltic applications, Inorg Chem 2017,56(12), 6920-6932.). Based on TiO2The modification of the material is also many, and the photocatalysis nitrogen fixation is still not ideal. Is subject to TiO2The material has the forbidden band width of 3.2eV and the band gap is too wide, and can only absorb and occupy the sunUltraviolet light of 4% of the energy in the light. The photocatalytic performance is improved to a certain extent by later-stage modification, but the matrix TiO2The low utilization rate of the visible light is the key for limiting the low photocatalytic nitrogen fixation performance.
Nano ZnIn2S4The microscopic appearance is sheet-shaped, has a larger optical activity area, has a forbidden band width of about 2.5eV, can absorb a wider range of visible light, and has good photochemical stability. ZnIn under standard hydrogen electrode as reference test2S4Has a conduction band position of about-0.74 eV, a valence band position of about +1.66eV, and N2+6H++6e-→2NH3The reduction potential of (a) is-0.15 eV. Its reduction potential is ZnIn2S4Within the conduction band, it can theoretically be realized that N is2Reduction to NH3In (1). The precious metal nano particles are deposited on the surface of the semiconductor through artificial design, which is a common method for improving the photoelectric property of the semiconductor. The noble metal absorbs the light energy to generate hot carriers, and hot electrons are directly injected into the semiconductor conduction band when the hot carrier energy is higher than the schottky barrier at the metal-semiconductor interface. The invention relates to ZnIn modified by nano Au2S4The utilization of visible light is greatly improved, and the method has great research space in the photoelectric field and the photocatalysis field.
Disclosure of Invention
The invention aims to provide Au-ZnIn2S4The preparation method of the nano array electrode photocatalytic nitrogen fixation material solves the problems of low light activity area, low photoelectric property and low catalytic property in the photocatalytic field in the current photocatalytic field.
The technical scheme adopted for realizing the purpose of the invention is as follows: Au-ZnIn2S4The preparation method of the nano array comprises the following steps: based on ZnIn2S4The nano-array electrode photo-deposits nano Au particles on the surface of the nano-array electrode to improve ZnIn2S4The photocatalytic nitrogen fixation performance; firstly, a layer of ZnIn is grown on FTO conductive glass by adopting a hydrothermal method2S4The nano sheet array is used for depositing Au particles on the surface of the nano sheet array by a photo-deposition method; Au-ZnIn2S4Fixing the electrode plate in methanol water solution, continuously introducing high-purity nitrogen, and irradiating N under xenon lamp2Conversion to NH3And then converted into NH4+(ii) a Mixing the reaction solution with a Nashi reagent for color development, and determining NH in the reaction solution4+And the concentration further determines the photocatalytic nitrogen fixation performance of the material.
The Au-ZnIn2S4The preparation of the nano array comprises the following specific steps:
step 1, zinc nitrate Zn (NO) is utilized3)2·6H2O, indium trichloride InCl3Urea sulfide CH4N2S is prepared into a precursor solution according to the molar ratio of 1:2:4, and ZnIn is prepared by a one-step hydrothermal method2S4Nano-layered FTO conductive glass electrodes, i.e. ZnIn2S4A nano-array electrode;
step 2, 20-60 mu L of 50mmol/L HAuCl is taken4The solution was diluted to 100mL with pure water, transferred to a quartz electrolytic cell, and ZnIn was added2S4The electrode plate is fixed in a quartz electrolytic cell by a polytetrafluoroethylene electrode clamp, and the irradiation of sunlight is simulated by a xenon lamp to lead Au in the solution to be3+The reduced Au simple substance is deposited on ZnIn2S4Preparing Au-ZnIn on the surface of the electrode slice2S4A nano-array electrode;
step 3, for Au-ZnIn2S4The performance of the nano array electrode photocatalytic nitrogen fixation material is tested, namely Au-ZnIn2S4Fixing the electrode in methanol water solution, introducing high-purity nitrogen gas continuously, introducing gas for 20min before irradiation of simulated sunlight, fixing Au-ZnIn with platinum sheet electrode clamp by using the simulated sunlight as energy source2S4The electrode is used for constructing a photocatalytic reaction tank; under the illumination of xenon lamp, N2Conversion to NH3And then converted into NH4+(ii) a Mixing the reaction solution with a Nashi reagent for color development, and determining NH in the reaction solution4 +And the concentration further determines the photocatalytic nitrogen fixation performance of the material.
In the step 1, ZnIn2S4The growth preparation of the nano array comprises the following specific stepsThe method comprises the following steps:
step (1-1), cleaning: will be sputtered with SnO2Cutting the FTO conductive glass into 2 × 3cm pieces, numbering, sequentially performing ultrasonic treatment on the pieces for 30min by using pure water solution mixed with a glass cleaning agent, pure water, isopropanol, 95 wt% of ethanol and 99 wt% of ethanol, and naturally airing for later use;
step (1-2), modification: putting the cleaned FTO conductive glass in the step (1-1) into a solution of pure water: hydrogen peroxide: ammonia water at a ratio of 5: 1, standing for 10min, taking out the FTO conductive glass, washing the FTO conductive glass with a large amount of pure water, and naturally drying for later use;
step (1-3), preparing a precursor solution: preparing aqueous solution with pH of 1.8 with hydrochloric acid, adding 0.75mmol Zn (NO)3)2·6H2O、1.50mmol InCl3、3mmol CH4N2Dissolving S in 30mL of water with pH of 1.8, and magnetically stirring for 20min to completely dissolve the medicine to obtain a precursor solution;
step (1-4), placing the modified FTO conductive glass with the conductive surface inclined downwards into a 50ml hydrothermal reaction kettle lining, and transferring the precursor solution in the step (1-3) into the reaction kettle;
step (1-5), sealing the reaction kettle, placing the reaction kettle in an oven, preserving heat for 3 hours at 180 ℃, naturally cooling to room temperature to obtain a flaxen film with the FTO conductive glass conductive surface uniformly growing over, wherein the flaxen film is ZnIn2S4A nano-film; the ZnIn is obtained after the FTO conductive glass is washed by slow water and dried for 6h in vacuum2S4And (4) a nano array electrode.
In the step 2, in ZnIn2S4Depositing gold on the surface of the nano array electrode; the method comprises the following specific steps:
step (2-1), 40. mu.l of 50mmol/L AuHCl4Diluting to 100mL by pure water to obtain a solution with the Au content of 0.394mg, and transferring the solution into a quartz electrolytic cell;
step (2-2) of reacting ZnIn2S4The electrode is fixed by a polytetrafluoroethylene electrode clamp and is completely immersed into the solution in the step (2-1) and ZnIn grows on the electrode2S4The surface of the nano film faces to a xenon lamp light source, and is irradiated for 30min in magnetic stirring to irradiate ZnIn2S4Carrying out light deposition on the electrode;
step (2-3), washing the electrode subjected to the photo-deposition with deionized water for 3 times, and performing vacuum drying at 60 ℃ for 6 hours to obtain Au-ZnIn with Au deposited on the surface2S4And (4) a nano array electrode.
In the step 2, the illumination intensity of the simulated sunlight illumination is 100mW/cm2Irradiating at room temperature for 20-40 min.
In the step 3, the flow rate of the introduced high-purity nitrogen N2 is 20ml/min, and the high-purity nitrogen N2 is introduced for 20min before the irradiation of the simulated sunlight; in the methanol aqueous solution, the volume ratio of 99 percent methanol to water is 1: 4.
In ZnIn2S4The special device for depositing gold particles on the surface of the nano array comprises: comprises a xenon lamp simulating sunlight, an electrode clamp and ZnIn2S4The device comprises a nano array electrode, a magnetic stirrer, magnetons and an electrochemical reaction tank; an electrochemical reaction tank is arranged on the magnetic stirrer, magnetons are arranged in the electrochemical reaction tank, an electrode clamp is arranged at the upper end of the electrochemical reaction tank, and ZnIn is clamped by the electrode clamp2S4A nano array electrode, a xenon lamp outside the electrochemical reaction tank for simulating the ZnIn irradiated by sunlight2S4 Nano array electrode 3, ZnIn2S4The nano-array electrode is placed in the electrolyte.
The method has the beneficial effects that due to the adoption of the scheme, the ZnIn is grown on the FTO conductive glass by adopting a one-step hydrothermal method2S4A nano-array; then immersed in HAuCl by light irradiation4ZnIn in aqueous solution2S4Nano array electrode of Au3+Reduced to generate gold particles, irradiated for 30min under the condition of stirring, cleaned and dried to obtain ZnIn with nano Au particles deposited on the surface2S4And (4) a nano array electrode.
Preparation of Au-ZnIn by photo-deposition2S4Electrode pad of Au-ZnIn2S4The electrode slice is used in the field of photocatalytic nitrogen fixation, and develops a brand new photocatalytic nitrogen fixation material. The deposition of Au particles is beneficial to improving ZnIn2S4The method of light absorption and light deposition is favorable for Au selective depositionOn the high active side, ZnIn2S4The nano material is of a sheet structure, and edges of the sheet layer have higher photoelectric property, so that Au particles are promoted to be ZnIn2S4The sheet edges are photoreductively deposited. The deposition of Au particles is beneficial to improving ZnIn2S4Absorption of light, photoelectrons absorbed by Au particles at edges to ZnIn2S4Transfer to promote adsorption of ZnIn2S4N of (A) to2And activating to realize photocatalytic nitrogen fixation.
In ZnIn2S4Gold particles are deposited on the upper surface of the nano array, and the surface plasma effect of gold effectively improves ZnIn2S4Light absorption in a visible light region, and the nano gold particles absorb light energy to generate hot electrons, so that ZnIn is enhanced2S4Nanoarray photoreduction N2Generation of NH3The ability of the cell to perform. Experiments show that ZnIn of gold nanoparticles is simply photo-deposited2S4The absorption of the nano array to visible light is obviously improved, and the photoelectric property is also improved. Meanwhile, the material is an array material, can be recycled simply, is nontoxic and relatively simple in preparation and treatment processes, and has great potential in the aspect of photocatalytic nitrogen fixation.
The problems of low optical activity area, low photoelectric performance and low catalytic performance in the current photocatalysis field are solved, and the purpose of the invention is achieved.
The invention has the following advantages:
1. the material is simple to prepare, loose in preparation conditions, non-toxic, easy to recover in the application process of the material and capable of being recycled.
2. ZnIn is added2S4The forbidden band width is narrower, the material can absorb visible light in a wider range, and Au can also have strong absorption in the visible light range, so that the comprehensive utilization rate of the material to the visible light is improved.
Drawings
FIG. 1 shows the structure of ZnIn of the present invention2S4The surface of the nano array is provided with a schematic structure of a gold particle deposition device.
FIG. 2 shows an FTO conductive glass in embodiment 1 of the present inventionZnIn growth on glass2S4Typical XRD patterns of nanoarrays.
FIG. 3-a shows ZnIn grown on FTO conductive glass in example 1 of the present invention2S4Typical scanning electron microscope topography of the nanoarray.
FIG. 3-b shows ZnIn grown on FTO conductive glass in example 2 of the present invention2S4Scanning electron microscope image of gold on the surface of the nano array.
FIG. 3-c shows ZnIn grown on FTO conductive glass in example 2 of the present invention2S4Large-scale scanning electron microscope images of gold on the surface of the nano array.
FIG. 4 shows ZnIn grown on FTO conductive glass according to the present invention2S4And (3) ultraviolet-visible diffuse reflection absorption spectrograms of the nano array and Au with different qualities after photo-deposition.
FIG. 5 shows the growth of ZnIn on FTO conductive glass according to the present invention2S4And (3) corresponding characteristic graphs of photocurrent under visible light irradiation after the nano-array and the Au with different qualities are subjected to photo-deposition.
FIG. 6 shows ZnIn grown on FTO conductive glass according to the present invention2S4And (3) carrying out Nyquist graph of alternating current impedance under visible light irradiation after the nano-array and the photo-deposition of Au with different masses.
FIG. 7 shows ZnIn grown on FTO conductive glass according to the present invention2S4And (4) a nano array and a photo-deposition photocatalytic nitrogen fixation performance graph of Au with different masses.
In fig. 1, 1. a xenon lamp simulates sunlight; 2. an electrode holder; ZnIn2S4A nano-array electrode; 4. a magnetic stirrer; 5. a magneton; 6. an electrochemical reaction cell.
Detailed Description
Au-ZnIn2S4The preparation method of the nano array comprises the following steps: based on ZnIn2S4The nano-array electrode photo-deposits nano Au particles on the surface of the nano-array electrode to improve ZnIn2S4The photocatalytic nitrogen fixation performance; firstly, a layer of ZnIn is grown on FTO conductive glass by adopting a hydrothermal method2S4The nano sheet array is used for depositing Au particles on the surface of the nano sheet array by a photo-deposition method; Au-ZnIn2S4Fixing the electrode plate in methanol water solution, continuously introducing high-purity nitrogen, and irradiating N under xenon lamp2Conversion to NH3And then converted into NH4+(ii) a Mixing the reaction solution with a Nashi reagent for color development, and determining NH in the reaction solution4+And the concentration further determines the photocatalytic nitrogen fixation performance of the material.
The Au-ZnIn2S4The preparation of the nano array comprises the following specific steps:
step 1, zinc nitrate Zn (NO) is utilized3)2·6H2O, indium trichloride InCl3Urea sulfide CH4N2S is prepared into a precursor solution according to the molar ratio of 1:2:4, and ZnIn is prepared by a one-step hydrothermal method2S4Nano-layered FTO conductive glass electrodes, i.e. ZnIn2S4An electrode sheet;
step 2, 20-60 mu L of 50mmol/L HAuCl is taken4The solution was diluted to 100mL with pure water, transferred to a quartz electrolytic cell, and ZnIn was added2S4The electrode plate is fixed in a quartz electrolytic cell by a polytetrafluoroethylene electrode clamp, and the irradiation of sunlight is simulated by a xenon lamp to lead Au in the solution to be3+The reduced Au simple substance is deposited on ZnIn2S4Preparing Au-ZnIn on the surface of the electrode slice2S4A nano-array electrode;
step 3.Au-ZnIn2S4The nano array electrode is fixedly placed in methanol water solution, high-purity nitrogen is continuously introduced, and N is obtained under the illumination of a xenon lamp2Conversion to NH3And then converted into NH4+(ii) a Mixing the reaction solution with a Nashi reagent for color development, and determining NH in the reaction solution4+And the concentration further determines the photocatalytic nitrogen fixation performance of the material.
In the step 1, ZnIn2S4The growth preparation of the nano array comprises the following specific steps:
step (1-1), cleaning: will be sputtered with SnO2Cutting the FTO conductive glass into 2 × 3cm pieces, numbering, sequentially performing ultrasonic treatment on the pieces for 30min by using pure water solution mixed with a glass cleaning agent, pure water, isopropanol, 95 wt% of ethanol and 99 wt% of ethanol, and naturally airing for later use;
step (1-2), modification: putting the cleaned FTO conductive glass in the step (1-1) into a solution of pure water: hydrogen peroxide: ammonia water at a ratio of 5: 1, standing for 10min, taking out the FTO conductive glass, washing the FTO conductive glass with a large amount of pure water, and naturally drying for later use;
step (1-3), preparing a precursor solution: preparing aqueous solution with pH of 1.8 with hydrochloric acid, adding 0.75mmol Zn (NO)3)2·6H2O、1.50mmol InCl3、3mmol CH4N2Dissolving S in 30mL of water with pH of 1.8, and magnetically stirring for 20min to completely dissolve the medicine to obtain a precursor solution;
step (1-4), placing the modified FTO conductive glass with the conductive surface inclined downwards into a 50ml hydrothermal reaction kettle lining, and transferring the precursor solution in the step (1-3) into the reaction kettle;
step (1-5), sealing the reaction kettle, placing the reaction kettle in an oven, preserving heat for 3 hours at 180 ℃, naturally cooling to room temperature to obtain a flaxen film with the FTO conductive glass conductive surface uniformly growing over, wherein the flaxen film is ZnIn2S4A nano-film; the ZnIn is obtained after the FTO conductive glass is washed by slow water and dried for 6h in vacuum2S4And (4) a nano array electrode.
In the step 2, in ZnIn2S4Depositing gold on the surface of the nano array electrode; the method comprises the following specific steps:
step (2-1), 40. mu.l of 50mmol/L AuHCl4Diluting to 100mL by pure water to obtain a solution with the Au content of 0.394mg, and transferring the solution into a quartz electrolytic cell;
step (2-2) of reacting ZnIn2S4The electrode is fixed by a polytetrafluoroethylene electrode clamp and is completely immersed into the solution in the step (2-1) and ZnIn grows on the electrode2S4The surface of the nano film faces to a xenon lamp light source, and is irradiated for 30min in magnetic stirring to irradiate ZnIn2S4Performing photo-deposition on the nano-array electrode;
step (2-3), washing the electrode subjected to the photo-deposition with deionized water for 3 times, and performing vacuum drying at 60 ℃ for 6 hours to obtain Au-ZnIn with Au deposited on the surface2S4An electrode sheet;
the steps are2, the illumination intensity of the simulated sunlight irradiation is 100mW/cm2Irradiating at room temperature for 20-40 min.
In ZnIn2S4The special device for depositing gold particles on the surface of the nano array comprises: comprises a xenon lamp simulating sunlight 1, an electrode clamp 2 and ZnIn2S4The device comprises a nano array electrode 3, a magnetic stirrer 4, magnetons 5 and an electrochemical reaction tank 6;
an electrochemical reaction tank 6 is arranged on the magnetic stirrer 4, magnetons 5 are arranged in the electrochemical reaction tank 6, an electrode clamp 2 is arranged at the upper end of the electrochemical reaction tank 6, and ZnIn is clamped by the electrode clamp 22S4A nano array electrode 3, a xenon lamp outside the electrochemical reaction tank 6 for simulating the irradiation of the sunlight 1 to ZnIn2S4 Nano array electrode 3, ZnIn2S4The nano-array electrode 3 is placed in the electrolyte.
The invention is further explained in detail by combining experimental concrete embodiments with the attached drawings.
1. The invention adopts a one-step hydrothermal method to prepare ZnIn2S4The nano array improves the photoelectrochemical property of the nano Au particles through surface photo-deposition, and simultaneously improves the photocatalysis nitrogen fixation capability of the nano Au particles.
2. In the following examples, the experimental drugs were all analytically pure.
3. The ZnIn2S4The nano-array has a single crystal structure and a hexagonal crystal form, and the thickness of the nano-array is about 100 nm.
4. Preparation of ZnIn2S4The nano array comprises the following specific steps:
(4-1) sputtering with SnO2Cutting the FTO glass into 2 × 3cm pieces, numbering on a non-conductive surface, sequentially performing ultrasonic treatment on the pieces for 30min by using a pure water solution mixed with a glass cleaning agent, pure water, isopropanol, 95 wt% of ethanol and 99 wt% of ethanol, and naturally drying for later use;
(4-2) putting the glass in the step (4-1) into the VPure water︰VHydrogen peroxide solution︰VAqueous ammoniaStanding in solution at ratio of 5: 1 for 10min, taking out with forceps, washing with large amount of pure water, and naturally drying;
(4-3) 0.2231g of Zn (NO) were weighed out with an analytical balance3)2·6H2O、0.2284g CH4N2S、0.3318gInCl3Adding 30mL of hydrochloric acid aqueous solution with the pH value of 1.8 into a 50mL beaker, and completely dissolving the medicine under the action of magnetic stirring;
(4-4) placing the modified FTO conductive glass into a 50ml hydrothermal reaction kettle lining in an inclined manner with the conductive surface facing downwards, and transferring the solution in the step 4-3) into the lining;
(4-5) sealing the reaction kettle, placing the reaction kettle in an oven, preserving heat for 3 hours at 180 ℃, naturally cooling to room temperature to obtain a flaxen thin film with the FTO conductive surface uniformly growing, and flushing the FTO with slow water and drying in vacuum to obtain ZnIn2S4And (4) a nano array electrode.
Example 1: 0.2mgAu in ZnIn2S4And (4) depositing the surface of the nano array.
1. Mu.l of 50mmol/L AuHCl4Dissolved in 100mL of pure water to obtain a solution containing Au0.2mg, and the solution was transferred into a quartz electrolytic cell.
2. Fixing the electrode plate with polytetrafluoroethylene electrode clamp, immersing the electrode plate into the medium solution completely, and growing ZnIn2S4The surface of the nano film faces to a xenon lamp light source, and the light is irradiated for 30min in magnetic stirring.
3. And taking out the electrode plate, slowly washing the electrode plate for 3min by using pure water, and carrying out vacuum drying at 60 ℃ for 6h to obtain the Au-ZnIn2S4 electrode plate with 0.2mg of Au deposited by light.
Example 2: 0.4mgAu in ZnIn2S4And (4) depositing the surface of the nano array.
1. 40. mu.l of 50mmol/L AuHCl4Dissolved in 100mL of pure water to obtain a solution containing Au0.4mg, and the solution was transferred into a quartz electrolytic cell.
2. Fixing the electrode plate with polytetrafluoroethylene electrode clamp, immersing the electrode plate into the medium solution completely, and growing ZnIn2S4The surface of the nano film faces to a xenon lamp light source, and the light is irradiated for 30min in magnetic stirring.
3. Taking out the electrode slice, slowly washing with pure water for 3min, vacuum drying at 60 deg.C for 6h to obtain Au-ZnIn with 0.4mg Au photo-deposition2S4An electrode sheet.
Example 3: 0.6mgAu in ZnIn2S4And (4) depositing the surface of the nano array.
1. 60. mu.l of 50mmol/L AuHCl4Dissolved in 100mL of pure water to obtain a solution containing Au0.6mg, and the solution was transferred into a quartz electrolytic cell.
2. Fixing the electrode plate with polytetrafluoroethylene electrode clamp, immersing all the electrode plates in the solution, and growing ZnIn2S4The surface of the nano film faces to a xenon lamp light source, and the light is irradiated for 30min in magnetic stirring.
3. Taking out the electrode slice, slowly washing with pure water for 3min, vacuum drying at 60 deg.C for 6h to obtain Au-ZnIn with 0.6mg Au photo-deposition2S4An electrode sheet.
Example 4: ZnIn2S4Electrode sheet and Au-ZnIn2S4And testing the photoelectrochemical property of the electrode plate.
1. Prepared with 150mL0.1mol/L of Na2SO4And (3) fixing the electrode slice by using a platinum slice electrode clamp, wherein the platinum slice electrode is a counter electrode, and the Hg/HgCl saturated potassium chloride electrode is a reference electrode to form a three-electrode system. And testing the photoelectrochemical property of the electrode plate through an electrochemical workstation.
2. In fig. 5, photocurrent response characteristics of different electrode sheets were tested with an applied bias voltage of 0V.
3. In fig. 6, when the ac impedance of different electrode sheets was tested under the illumination condition, a bias of 0.2V was applied, with a high frequency of 50000Hz and a low frequency of 0.1 Hz.
Example 5: ZnIn2S4Electrode sheet and Au-ZnIn2S4And testing the photocatalytic nitrogen fixation performance of the electrode plate.
1. 30mL of an aqueous methanol solution (V) was preparedMethanol 95 wt%：VPure water1:4), fixing the electrode slice by a platinum slice electrode clamp, placing the electrode slice in a special reactor, and introducing high-purity nitrogen gas from the bottom of the reactor at the aeration rate of 20 mL/min.
2. Irradiating ZnIn in the reactor by a 300W xenon lamp light source2S4Electrode slice, 2mL reaction solution was collected every 25 min.
3. Mixing 1mL of the collected solution with 1mL of the Nashi solution, reacting for 10min in the dark, transferring into a 2mL cuvette, and testing the absorbance of the reaction solution under the light of 420nm of an ultraviolet-visible spectrophotometer.
4. Testing the absorbance of the reaction solution, finding out the corresponding ammonia concentration in the absorbance curve of the standard ammonia solution, performing unit conversion, and comparing ZnIn before and after loading gold2S4Photo-electric nitrogen fixation of nano-arrays as shown in fig. 7.

Claims (2)

1. Au-ZnIn2S4The preparation method of the nano array electrode photocatalysis nitrogen fixation material is characterized by comprising the following steps: Au-ZnIn2S4The preparation method of the nano array comprises the following steps: based on ZnIn2S4The nano-array electrode photo-deposits nano Au particles on the surface of the nano-array electrode to improve ZnIn2S4The photocatalytic nitrogen fixation performance; firstly, a layer of ZnIn is grown on FTO conductive glass by adopting a hydrothermal method2S4The nano sheet array is used for depositing Au particles on the surface of the nano sheet array by a photo-deposition method; Au-ZnIn2S4Fixing the electrode plate in methanol water solution, continuously introducing high-purity nitrogen, and irradiating N under xenon lamp2Conversion to NH3And then converted into NH4 +(ii) a Mixing the reaction solution with a Nashi reagent for color development, and determining NH in the reaction solution4 +Concentration, and further determining the photocatalytic nitrogen fixation performance of the material;
the Au-ZnIn2S4The preparation method of the nano array comprises the following specific steps:
step 1, zinc nitrate Zn (NO) is utilized3)2·6H2O, indium trichloride InCl3Urea sulfide CH4N2S is prepared into a precursor solution according to the molar ratio of 1:2:4, and ZnIn is prepared by a one-step hydrothermal method2S4Nano-layered FTO conductive glass electrodes, i.e. ZnIn2S4A nano-array electrode;
step 2, 20-60 mu L of 50mmol/L HAuCl is taken4The solution was diluted to 100mL with pure water, transferred to a quartz electrolytic cell, and ZnIn was added2S4The electrode plate is fixed in a quartz electrolytic cell by a polytetrafluoroethylene electrode clamp, and the irradiation of sunlight is simulated by a xenon lamp to lead Au in the solution to be3+The reduced Au simple substance is deposited on ZnIn2S4Preparing Au-ZnIn on the surface of the electrode slice2S4A nano-array electrode;
step 3, for Au-ZnIn2S4The performance of the nano array electrode photocatalytic nitrogen fixation material is tested, namely Au-ZnIn2S4Fixing electrode plate in methanol water solution, introducing high purity nitrogen gas continuously, introducing gas for 20min before irradiation of simulated sunlight, fixing Au-ZnIn with platinum sheet electrode clamp by using simulated sunlight as energy source2S4The nano array electrode is used for constructing a photocatalytic reaction tank; under the illumination of xenon lamp, N2Conversion to NH3And then converted into NH4 +(ii) a Mixing the reaction solution with a Nashi reagent for color development, and determining NH in the reaction solution4 +Concentration, and further determining the photocatalytic nitrogen fixation performance of the material;
in the step 2, the illumination intensity of the simulated sunlight illumination is 100mW/cm2Irradiating at room temperature for 20-40 min;
in the step 3, high-purity nitrogen N is introduced2The flow rate of (2) is 20mL/min, and ventilation is carried out for 20min before irradiation of simulated sunlight; in the methanol aqueous solution, the volume ratio of 99 wt% methanol to water is 1: 4;
in the step 1, ZnIn2S4The growth preparation of the nano array comprises the following specific steps:
step (1-1), cleaning: will be sputtered with SnO2Cutting the FTO conductive glass into 2 × 3cm pieces, numbering, sequentially performing ultrasonic treatment on the pieces for 30min by using pure water solution mixed with a glass cleaning agent, pure water, isopropanol, 95 wt% of ethanol and 99 wt% of ethanol, and naturally airing for later use;
step (1-2), modification: putting the cleaned FTO conductive glass in the step (1-1) into a solution of pure water: hydrogen peroxide: ammonia water at a ratio of 5: 1, standing for 10min, taking out the FTO conductive glass, washing the FTO conductive glass with a large amount of pure water, and naturally drying for later use;
step (1-3), preparing a precursor solution: preparing pH 1.8 aqueous solution with hydrochloric acid, adding 0.75mmol Zn (NO)3)2·6H2O、1.50mmolInCl3、3mmolCH4N2Dissolving S in 30mL of water with pH of 1.8, and magnetically stirring for 20min to completely dissolve the medicine to obtain a precursor solution;
step (1-4), placing the modified FTO conductive glass with the conductive surface inclined downwards into a 50mL hydrothermal reaction kettle lining, and transferring the precursor solution in the step (1-3) into the reaction kettle;
step (1-5), sealing the reaction kettle, placing the reaction kettle in an oven, preserving heat for 3 hours at 180 ℃, naturally cooling to room temperature to obtain a flaxen film with the FTO conductive glass conductive surface uniformly growing over, wherein the flaxen film is ZnIn2S4A nano-film; the ZnIn is obtained after the FTO conductive glass is washed by slow water and dried for 6h in vacuum2S4A nano-array electrode;
in the step 2, in ZnIn2S4Depositing gold on the surface of the nano array; the method comprises the following specific steps:
step (2-1), 20-60. mu.L of 50mmol/L HAuCl4Diluting to 100mL by pure water, and transferring the solution into a quartz electrolytic cell;
step (2-2) of reacting ZnIn2S4The electrode is fixed by a polytetrafluoroethylene electrode clamp and is completely immersed into the solution in the step (2-1) and ZnIn grows on the electrode2S4The surface of the nano film faces to a xenon lamp light source, and is irradiated for 20-40min in magnetic stirring to ZnIn2S4Carrying out light deposition on the electrode;
step (2-3), washing the electrode subjected to the photo-deposition with deionized water for 3 times, and performing vacuum drying at 60 ℃ for 6 hours to obtain Au-ZnIn with Au deposited on the surface2S4And (4) a nano array electrode.
2. An Au-ZnIn as claimed in claim 12S4The special device for the preparation method of the nano array electrode photocatalytic nitrogen fixation material is characterized in that: in ZnIn2S4The special device for depositing gold particles on the surface of the nano array comprises: comprises a xenon lamp simulating sunlight, an electrode clamp and ZnIn2S4The device comprises a nano array electrode, a magnetic stirrer, magnetons and an electrochemical reaction tank; an electrochemical reaction pool with magnetons is arranged on the magnetic stirrer for electrochemical reactionThe upper end of the chemical reaction tank is provided with an electrode clamp which clamps ZnIn2S4A nano array electrode, a xenon lamp outside the electrochemical reaction tank for simulating the ZnIn irradiated by sunlight2S4Nanoarray electrodes, ZnIn2S4The nano-array electrode is placed in the electrolyte.
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