CN110508291A - A kind of Au-ZnIn2S4The preparation method of nano-array electrode photocatalysis fixed nitrogen material - Google Patents
A kind of Au-ZnIn2S4The preparation method of nano-array electrode photocatalysis fixed nitrogen material Download PDFInfo
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims abstract description 100
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 50
- 239000000463 material Substances 0.000 title claims abstract description 36
- 238000007146 photocatalysis Methods 0.000 title claims abstract description 33
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 239000000243 solution Substances 0.000 claims abstract description 65
- 239000011521 glass Substances 0.000 claims abstract description 40
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 38
- 230000008021 deposition Effects 0.000 claims abstract description 37
- 238000006243 chemical reaction Methods 0.000 claims abstract description 25
- 229910052724 xenon Inorganic materials 0.000 claims abstract description 24
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000002245 particle Substances 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 18
- 239000007864 aqueous solution Substances 0.000 claims abstract description 14
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 14
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 12
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 7
- 238000003491 array Methods 0.000 claims abstract description 4
- 239000010931 gold Substances 0.000 claims description 43
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 40
- 238000000151 deposition Methods 0.000 claims description 37
- 238000003487 electrochemical reaction Methods 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- PSCMQHVBLHHWTO-UHFFFAOYSA-K indium(iii) chloride Chemical compound Cl[In](Cl)Cl PSCMQHVBLHHWTO-UHFFFAOYSA-K 0.000 claims description 12
- 239000002243 precursor Substances 0.000 claims description 12
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 11
- 229910052737 gold Inorganic materials 0.000 claims description 11
- 238000005286 illumination Methods 0.000 claims description 11
- 238000013019 agitation Methods 0.000 claims description 10
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 10
- 238000001291 vacuum drying Methods 0.000 claims description 10
- -1 polytetrafluoroethylene Polymers 0.000 claims description 9
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 9
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 9
- 239000010409 thin film Substances 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 8
- 235000019441 ethanol Nutrition 0.000 claims description 8
- 239000011701 zinc Substances 0.000 claims description 8
- 238000003760 magnetic stirring Methods 0.000 claims description 7
- 229910002651 NO3 Inorganic materials 0.000 claims description 6
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 6
- 239000003814 drug Substances 0.000 claims description 5
- 229910052697 platinum Inorganic materials 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- 229940079593 drug Drugs 0.000 claims description 4
- 239000010408 film Substances 0.000 claims description 4
- 238000004321 preservation Methods 0.000 claims description 4
- 238000007789 sealing Methods 0.000 claims description 4
- 238000004544 sputter deposition Methods 0.000 claims description 4
- 238000002604 ultrasonography Methods 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 3
- 239000004202 carbamide Substances 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 230000005611 electricity Effects 0.000 claims description 3
- 239000003792 electrolyte Substances 0.000 claims description 3
- 238000004088 simulation Methods 0.000 claims description 3
- 238000004073 vulcanization Methods 0.000 claims description 3
- 235000007164 Oryza sativa Nutrition 0.000 claims description 2
- 239000000908 ammonium hydroxide Substances 0.000 claims description 2
- 235000009566 rice Nutrition 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 240000007594 Oryza sativa Species 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 7
- 238000010521 absorption reaction Methods 0.000 abstract description 6
- 230000008901 benefit Effects 0.000 abstract description 5
- 230000005518 electrochemistry Effects 0.000 abstract description 3
- 231100000252 nontoxic Toxicity 0.000 abstract description 3
- 230000003000 nontoxic effect Effects 0.000 abstract description 3
- 230000003287 optical effect Effects 0.000 abstract description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 19
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 8
- 229910021529 ammonia Inorganic materials 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 238000002835 absorbance Methods 0.000 description 3
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N hydrogen peroxide Substances OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 238000007540 photo-reduction reaction Methods 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 241000446313 Lamella Species 0.000 description 1
- 241000209094 Oryza Species 0.000 description 1
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical class [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 1
- 229910004410 SrSnO3 Inorganic materials 0.000 description 1
- 230000032900 absorption of visible light Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- RCTYPNKXASFOBE-UHFFFAOYSA-M chloromercury Chemical compound [Hg]Cl RCTYPNKXASFOBE-UHFFFAOYSA-M 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 229940000406 drug candidate Drugs 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000003777 experimental drug Substances 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 238000007144 microwave assisted synthesis reaction Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002073 nanorod Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 230000005619 thermoelectricity Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- 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
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
-
- B01J35/23—
-
- B01J35/33—
-
- B01J35/39—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/14—Decomposition by irradiation, e.g. photolysis, particle radiation or by mixed irradiation sources
Abstract
A kind of Au-ZnIn2S4The preparation method of nano-array electrode photocatalysis fixed nitrogen material belongs to the preparation of optical electro-chemistry catalysis material and modified method.Preparation method: it is based on ZnIn2S4Nano-array electrode improves ZnIn in its surface light deposition nanometer Au particle2S4Photocatalysis fixed nitrogen performance；One layer of ZnIn is grown on FTO electro-conductive glass using hydro-thermal method first2S4Nano-chip arrays deposit Au particle on its surface by the method for light deposition and Au-ZnIn are made2S4Electrode；Au-ZnIn2S4Electrode slice fixation is put into methanol aqueous solution, high pure nitrogen is continually fed into, by N under Xenon light shining2It is converted into NH3, and then it is converted into NH4+；It takes reaction solution to mix colour developing with nessler reagent, determines NH in reaction solution4+Concentration, and then determine material light catalysis fixed nitrogen performance.Advantage: preparation is simple, and preparation condition is loose, nontoxic, is easily recycled, can recycle in material application process；With ZnIn2S4Forbidden bandwidth is relatively narrow, can absorb larger range of visible light, and Au can also have very strong absorption in visible-range, improves material to the comprehensive utilization ratio of visible light.
Description
Technical field
The present invention relates to a kind of preparations of optical electro-chemistry catalysis material and modified method, especially a kind of Au-ZnIn2S4It receives
The preparation method of rice array electrode photocatalysis fixed nitrogen material.
Background technique
Ammonia is the essential raw materials for production of chemical industry, medicine, agricultural etc..It remains unchanged currently, synthesizing ammonia in industrial production
It is traditional aber process, reaction temperature is anti-in ferrum-based catalyst catalytic process mostly at 300 DEG C or more, pressure 100atm or more
It answers.H needed for synthetic reaction2It is mainly converted and is generated by the evaporation of natural gas, entire reaction process is maintained to consume on the earth
The fossil energy of 1-2%, and cause a large amount of CO2Discharge.From the consumption and less greenhouse gases for reducing non-renewable energy resources
Discharge angle is seen, is to have very much scientific research value using luminous energy synthesis ammonia.
Photoelectrocatalysis process is to convert light energy into the process of chemical energy, is one of the thinking for solving energy crisis.There is light
The material of catalytic performance is numerous, but the material for being able to achieve photocatalysis fixed nitrogen is seldom, is primarily due to N2Molecule is highly stable, beats completely
It opens every mole of N ≡ N molecule and needs at least 941.69kJ energy, wherein the dissociation of first N-N key needs 410kJmol-1Energy, so
Energy needed for converting ammonia for nitrogen is very big.
Current research it is most be TiO2Catalysis material, TiO2It is solid that its photocatalysis can be improved by various modified methods
Nitrogen performance.Gong Jinlong team, University Of Tianjin is to TiO2Electrode fixed nitrogen carried out research, raw on FTO electro-conductive glass by hydro-thermal method
Long one layer of TiO2Nano rod, then to TiO2Electrode, which introduces Lacking oxygen and noble metal, realizes being increased to for fixed nitrogen performance
13.4nmol/cm2/ h (bibliography: Alammar, T.；Hamm,I.；Grasmik,V.；Wark,M.；Mudring,A.V.,
Microwave-Assisted Synthesis of Perovskite SrSnO3 Nanocrystals in Ionic
Liquids for Photocatalytic Applications.Inorg Chem 2017,56(12),6920-6932.).Base
In TiO2The modification of material also has very much, photocatalysis fixed nitrogen it is still not satisfactory.It is limited by TiO2Material itself forbidden bandwidth
For 3.2eV, band gap is wide, is only capable of absorbing the ultraviolet light for accounting for energy 4% in sunlight.It is mentioned by its modified photocatalysis performance of later period
Height improves, but matrix TiO2It is the key that restrict its photocatalysis fixed nitrogen performance not high that itself visible light utilization efficiency is not high.
Nanometer Zn In2S4Microcosmic appearance is sheet, has biggish photolytic activity area, forbidden bandwidth, can near 2.5eV
To absorb the visible light of wider range, while there is good photochemical stability.Using standard hydrogen electrode as under reference test
ZnIn2S4Conduction band positions near -0.74eV, valence band location is near+1.66eV, N2+6H++6e-→2NH3Reduction potential
For -0.15eV.Its reduction potential is in ZnIn2S4Within conduction band, theoretically it can be achieved on N2It is reduced to NH3's.Through remarkable
Noble metal nano particles are deposited on a kind of method that semiconductor surface is common raising semiconductor light electrical property to design.It is expensive
Metal absorption luminous energy generates hot carrier, the thermoelectricity when hot carrier energy is higher than Schottky barrier at metal-semiconductor interface
Son can be directly injected into semiconductor conduction band.The present invention passes through the ZnIn of nanometer Au modified2S4Visible light is utilized and has been obtained very
Big promotion has very big research space in photoelectric field, photocatalysis field.
Summary of the invention
The invention aims to provide a kind of Au-ZnIn2S4The preparation side of nano-array electrode photocatalysis fixed nitrogen material
Method, solves in current photocatalysis field that photolytic activity area is low in photocatalysis field, photoelectric properties are not high, catalytic performance is not high asks
Topic.
Realize the technical solution that the object of the invention uses: Au-ZnIn2S4The preparation method of nano-array is: being based on
ZnIn2S4Nano-array electrode improves ZnIn in its surface light deposition nanometer Au particle2S4Photocatalysis fixed nitrogen performance；It adopts first
One layer of ZnIn is grown on FTO electro-conductive glass with hydro-thermal method2S4Nano-chip arrays are deposited by the method for light deposition on its surface
Au particle；Au-ZnIn2S4Electrode slice fixation is put into methanol aqueous solution, high pure nitrogen is continually fed into, by N under Xenon light shining2
It is converted into NH3, and then it is converted into NH4+；It takes reaction solution to mix colour developing with nessler reagent, determines NH in reaction solution4+Concentration, into
And determine material light catalysis fixed nitrogen performance.
The Au-ZnIn2S4The preparation of nano-array, the specific steps are as follows:
Step 1. utilizes zinc nitrate Zn (NO3)2·6H2O, indium trichloride InCl3, vulcanization urea CH4N2S is with molar ratio for 1:
The proportional arrangement precursor solution of 2:4, being made by one step hydro thermal method has ZnIn2S4The FTO conductive glass electrode of nanometer layer,
That is ZnIn2S4Nano-array electrode；
Step 2. takes the HAuCl of 20-60 μ L 50mmol/L4Solution is diluted to 100mL with pure water, which is transferred to
In quartzy electrolytic cell, by ZnIn2S4Electrode slice polytetrafluoroethylene electrode folder is fixed in quartzy electrolytic cell, is simulated by xenon lamp
Sunlight irradiation makes the Au in solution3+The Au simple substance being reduced into is deposited on ZnIn2S4Electrode slice surface, prepares Au-ZnIn2S4
Nano-array electrode；
Step 3. is to Au-ZnIn2S4Nano-array electrode photocatalysis fixed nitrogen material property is tested, Au-ZnIn2S4Electricity
Extremely fixation is put into methanol aqueous solution, is continually fed into high pure nitrogen, and ventilate 20min in advance before simulated solar irradiation irradiation, with
Simulated solar irradiation is energy source, determines Au-ZnIn with platinum plate electrode is clamping2S4Electrode sets up light-catalyzed reaction pond；In xenon lamp
According to lower by N2It is converted into NH3, and then it is converted into NH4+；It takes reaction solution to mix colour developing with nessler reagent, determines NH in reaction solution4 +Concentration, and then determine material light catalysis fixed nitrogen performance.
In the step 1, ZnIn2S4It is prepared by the growth of nano-array, the specific steps are as follows:
Cleaning: sputtering is had SnO by step (1-1)2FTO electro-conductive glass be cut into the small pieces and number of 2 × 3cm, successively use
It is mixed with pure water solution, pure water, isopropanol, alcohol 95 wt%, the ethyl alcohol 99wt% ultrasound 30min of glass cleaner, is dried in the air naturally afterwards
It is dry, it is spare；
Step (1-2), it is modified: the FTO electro-conductive glass cleaned up in step (1-1) is put into the bis- Yang Shui ︰ ammonia of Chun Shui ︰
Water is to stand 10min, tweezers press from both sides out, and clean with a large amount of pure water rinsings, naturally dry is spare in the solution of 5 ︰, 1 ︰ 1；
Step (1-3) prepares precursor solution: the aqueous solution for being 1.8 with hydrochloric acid configuration pH, by 0.75mmol Zn
(NO3)2·6H2O、1.50mmol InCl3、3mmol CH4N2S is dissolved in the water of 30mL pH=1.8, and magnetic agitation 20min makes
Drug is completely dissolved, and precursor solution is made；
The FTO electro-conductive glass conducting surface of modified mistake is downwardly inclined and is put into 50ml hydrothermal reaction kettle by step (1-4)
Lining, precursor solution in step (1-3) is transferred in reaction kettle；
Step (1-5), reaction kettle sealing, is placed in baking oven, 180 DEG C of heat preservation 3h, cooled to room temperature obtains FTO and leads
Electric glass conducting surface uniformly covers with flaxen film, which is ZnIn2S4Nano thin-film；FTO electro-conductive glass warp
Slow water rinses, obtains ZnIn after vacuum drying 6h2S4Nano-array electrode.
In the step 2, in ZnIn2S4Nano-array electrode surface deposition gold；Specific step is as follows:
Step (2-1), by the AuHCl of 40 μ l 50mmol/L4It is diluted to 100mL with pure water, obtaining amount containing Au is
The solution of 0.394mg moves into solution in quartzy electrolytic cell；
Step (2-2), by ZnIn2S4Electrode polytetrafluoroethylene electrode is clamping fixed, is totally immersed into solution in step (2-1),
With ZnIn2S4Nano thin-film facing towards xenon source, the illumination 30min in magnetic agitation, to ZnIn2S4Electrode implements light
Deposition；
Step (2-3), the electrode that light deposition is crossed are rinsed 3 times with deionized water, and it is heavy that 60 DEG C of vacuum drying 6h obtain surface
The Au-ZnIn of product Au2S4Nano-array electrode.
In the step 2, the intensity of illumination of simulated solar irradiation irradiation is 100mW/cm2, 20- is irradiated at room temperature
40min。
In the step 3, the flow 20ml/min for the high pure nitrogen N2 being passed through, before simulated solar irradiation irradiation in advance
Ventilate 20min；In the methanol aqueous solution, the volume ratio of 99% methanol and water is 1:4.
In ZnIn2S4The dedicated unit of nano-array surface light deposition gold particle: including xenon lamp simulated solar irradiation, electrode holder,
ZnIn2S4Nano-array electrode, magnetic stirring apparatus, magneton and electrochemical reaction cell；Electrochemical reaction is disposed on magnetic stirring apparatus
There is magneton in pond in electrochemical reaction cell, has electrode holder in electrochemical reaction cell upper end, electrode holder clamps ZnIn2S4Nano-array
Electrode has xenon lamp simulated solar irradiation to irradiate ZnIn outside electrochemical reaction cell2S4Nano-array electrode 3, ZnIn2S4Nano-array
Electrode is placed in electrolyte.
Beneficial effect using one step hydro thermal method, grows ZnIn on FTO electro-conductive glass as the above scheme is adopted2S4
Nano-array；Then HAuCl is immersed in by light irradiation4ZnIn in aqueous solution2S4Nano-array electrode makes Au3+It is reduced generation
Gold particle, illumination 30min, cleans, is dried to obtain the ZnIn of surface deposition nanometer Au particle under stirring conditions2S4Nanometer battle array
Column electrode.
Au-ZnIn is prepared using the method for light deposition2S4Electrode slice, by Au-ZnIn2S4Electrode slice is used for photocatalysis fixed nitrogen
A kind of completely new photocatalysis fixed nitrogen material is developed in field.Au particles benefit is deposited in raising ZnIn2S4Absorption to light, light deposition
Method be conducive to Au selectivity be deposited on high activity face, ZnIn2S4Nano material is laminated structure, the seamed edge tool of lamella
There are higher photoelectric properties, and then promotes Au particle in ZnIn2S4Piece seamed edge is deposited by photo-reduction.Deposition Au particles benefit is in mentioning
High ZnIn2S4Absorption to light, the photoelectron that Au particle in seamed edge absorbs is to ZnIn2S4Transfer, and then promote to be adsorbed on
ZnIn2S4On N2Photocatalysis fixed nitrogen is realized in activation.
In ZnIn2S4Nano-array upper surface deposits gold particle, and golden surface plasma bulk effect effectively improves
ZnIn2S4Light absorption in visible light region, while nanogold particle absorbs luminous energy and generates thermoelectron, enhances ZnIn2S4Nanometer battle array
Column photo-reduction N2Generate NH3Ability.Experiment shows the ZnIn by simple light deposition nanogold particle2S4Nano-array pair
The absorption of visible light significantly improves, and photoelectric properties also increase.Meanwhile this material is array material, can simply recycle it
After reuse, preparation and treatment process it is nontoxic and relatively easy, have huge potentiality in terms of photocatalysis fixed nitrogen.
It solves the problems, such as that photolytic activity area is low in current photocatalysis field, photoelectric properties are not high, catalytic performance is not high, reaches
The purpose of the present invention is arrived.
The invention has the following advantages that
1. material preparation is simple, preparation condition is loose, nontoxic, is easily recycled in material application process, can recycle benefit
With.
2. with ZnIn2S4Forbidden bandwidth is relatively narrow, can absorb larger range of visible light, and Au can also have very in visible-range
Strong absorption, and then material is improved to the comprehensive utilization ratio of visible light.
Detailed description of the invention
Fig. 1 is the present invention in ZnIn2S4Nano-array surface light deposition gold particle apparatus structure schematic diagram.
Fig. 2 is to grow ZnIn on FTO electro-conductive glass in the embodiment of the present invention 12S4The typical XRD spectrum of nano-array.
Fig. 3-a is to grow ZnIn on FTO electro-conductive glass in the embodiment of the present invention 12S4The typical scan Electronic Speculum of nano-array
Shape appearance figure.
Fig. 3-b is to grow ZnIn on FTO electro-conductive glass in the embodiment of the present invention 22S4Nano-array surface light deposition gold
Scanning electron microscope (SEM) photograph.
Fig. 3-c is to grow ZnIn on FTO electro-conductive glass in the embodiment of the present invention 22S4Nano-array surface light deposition gold
Large area scanning electron microscope.
Fig. 4 is that the present invention grows ZnIn on FTO electro-conductive glass2S4Purple after nano-array and light deposition different quality Au
Outside-visible diffusing reflection abosrption spectrogram.
Fig. 5 is that the present invention grows ZnIn on FTO electro-conductive glass2S4Can after nano-array and light deposition different quality Au
Photoelectric current individual features figure under light-exposed irradiation.
Fig. 6 is that the present invention grows ZnIn on FTO electro-conductive glass2S4Can after nano-array and light deposition different quality Au
AC impedance Nyquist schemes under light-exposed irradiation.
Fig. 7 is that the present invention grows ZnIn on FTO electro-conductive glass2S4Light is urged after nano-array and light deposition different quality Au
Change fixed nitrogen performance map.
In Fig. 1,1. xenon lamp simulated solar irradiations；2. electrode holder；3.ZnIn2S4Nano-array electrode；4. magnetic stirring apparatus；5.
Magneton；6. electrochemical reaction cell.
Specific embodiment
Au-ZnIn2S4The preparation method of nano-array is: being based on ZnIn2S4Nano-array electrode is received in its surface light deposition
Rice Au particle, improves ZnIn2S4Photocatalysis fixed nitrogen performance；One layer is grown on FTO electro-conductive glass using hydro-thermal method first
ZnIn2S4Nano-chip arrays deposit Au particle on its surface by the method for light deposition；Au-ZnIn2S4Electrode slice fixation is put into
In methanol aqueous solution, it is continually fed into high pure nitrogen, by N under Xenon light shining2It is converted into NH3, and then it is converted into NH4+；It negates and answers
Solution mixes colour developing with nessler reagent, determines NH in reaction solution4+Concentration, and then determine material light catalysis fixed nitrogen performance.
The Au-ZnIn2S4The preparation of nano-array, the specific steps are as follows:
Step 1. utilizes zinc nitrate Zn (NO3)2·6H2O, indium trichloride InCl3, vulcanization urea CH4N2S is with molar ratio for 1:
The proportional arrangement precursor solution of 2:4, being made by one step hydro thermal method has ZnIn2S4The FTO conductive glass electrode of nanometer layer,
That is ZnIn2S4Electrode slice；
Step 2. takes the HAuCl of 20-60 μ L 50mmol/L4Solution is diluted to 100mL with pure water, which is transferred to
In quartzy electrolytic cell, by ZnIn2S4Electrode slice polytetrafluoroethylene electrode folder is fixed in quartzy electrolytic cell, is simulated by xenon lamp
Sunlight irradiation makes the Au in solution3+The Au simple substance being reduced into is deposited on ZnIn2S4Electrode slice surface, prepares Au-ZnIn2S4
Nano-array electrode；
Step 3.Au-ZnIn2S4Nano-array electrode fixation is put into methanol aqueous solution, high pure nitrogen is continually fed into, in xenon
Light is according to lower by N2It is converted into NH3, and then it is converted into NH4+；It takes reaction solution to mix colour developing with nessler reagent, determines reaction solution
Middle NH4+Concentration, and then determine material light catalysis fixed nitrogen performance.
In the step 1, ZnIn2S4It is prepared by the growth of nano-array, the specific steps are as follows:
Cleaning: sputtering is had SnO by step (1-1)2FTO electro-conductive glass be cut into the small pieces and number of 2 × 3cm, successively use
It is mixed with pure water solution, pure water, isopropanol, alcohol 95 wt%, the ethyl alcohol 99wt% ultrasound 30min of glass cleaner, is dried in the air naturally afterwards
It is dry, it is spare；
Step (1-2), it is modified: the FTO electro-conductive glass cleaned up in step (1-1) is put into the bis- Yang Shui ︰ ammonia of Chun Shui ︰
Water is to stand 10min, tweezers press from both sides out, and clean with a large amount of pure water rinsings, naturally dry is spare in the solution of 5 ︰, 1 ︰ 1；
Step (1-3) prepares precursor solution: the aqueous solution for being 1.8 with hydrochloric acid configuration pH, by 0.75mmol Zn
(NO3)2·6H2O、1.50mmol InCl3、3mmol CH4N2S is dissolved in the water of 30mL pH=1.8, and magnetic agitation 20min makes
Drug is completely dissolved, and precursor solution is made；
The FTO electro-conductive glass conducting surface of modified mistake is downwardly inclined and is put into 50ml hydrothermal reaction kettle by step (1-4)
Lining, precursor solution in step (1-3) is transferred in reaction kettle；
Step (1-5), reaction kettle sealing, is placed in baking oven, 180 DEG C of heat preservation 3h, cooled to room temperature obtains FTO and leads
Electric glass conducting surface uniformly covers with flaxen film, which is ZnIn2S4Nano thin-film；FTO electro-conductive glass warp
Slow water rinses, obtains ZnIn after vacuum drying 6h2S4Nano-array electrode.
In the step 2, in ZnIn2S4Nano-array electrode surface deposition gold；Specific step is as follows:
Step (2-1), by the AuHCl of 40 μ l 50mmol/L4It is diluted to 100mL with pure water, obtaining amount containing Au is
The solution of 0.394mg moves into solution in quartzy electrolytic cell；
Step (2-2), by ZnIn2S4Electrode polytetrafluoroethylene electrode is clamping fixed, is totally immersed into solution in step (2-1),
With ZnIn2S4Nano thin-film facing towards xenon source, the illumination 30min in magnetic agitation, to ZnIn2S4Nano-array electricity
Implement light deposition in pole；
Step (2-3), the electrode that light deposition is crossed are rinsed 3 times with deionized water, and it is heavy that 60 DEG C of vacuum drying 6h obtain surface
The Au-ZnIn of product Au2S4Electrode slice；
In the step 2, the intensity of illumination of simulated solar irradiation irradiation is 100mW/cm2, 20- is irradiated at room temperature
40min。
In ZnIn2S4The dedicated unit of nano-array surface light deposition gold particle: including xenon lamp simulated solar irradiation 1, electrode holder
2、ZnIn2S4Nano-array electrode 3, magnetic stirring apparatus 4, magneton 5 and electrochemical reaction cell 6；
Electrochemical reaction cell 6 is disposed on magnetic stirring apparatus 4, there is magneton 5 in electrochemical reaction cell 6, it is anti-in electrochemistry
6 upper end of pond is answered to have electrode holder 2, electrode holder 2 clamps ZnIn2S4Nano-array electrode 3 has xenon lamp simulation outside electrochemical reaction cell 6
Sunlight 1 irradiates ZnIn2S4Nano-array electrode 3, ZnIn2S4Nano-array electrode 3 is placed in electrolyte.
In conjunction with attached drawing experiment specific embodiment, invention is further described in detail.
1. the present invention prepares ZnIn using one step hydro thermal method2S4Nano-array is improved by surface light deposition nanometer Au particle
Its photoelectrochemical behaviour, while improving the ability of its photocatalysis fixed nitrogen.
2. various experimental drugs are that analysis is pure in following embodiment.
3. the ZnIn2S4Nano-array is mono-crystalline structures, hexagonal phase crystal form, with a thickness of 100nm or so
4. preparing ZnIn2S4Nano-array, the specific steps are as follows:
Sputtering is had SnO by (4-1)2FTO glass be cut into the small pieces of 2 × 3cm and numbered in nonconductive surface, successively with mixed
There are pure water solution, pure water, isopropanol, alcohol 95 wt%, the ethyl alcohol 99wt% ultrasound 30min of glass cleaner.Naturally dry afterwards,
It is spare；
Glass in (4-1) is put into V by (4-2)Pure water︰ VHydrogen peroxide︰ VAmmonium hydroxideIn solution for 5 ︰, 1 ︰ 1,10min, tweezers folder are stood
Out, clean with a large amount of pure water rinsings, naturally dry is spare；
(4-3) weighs 0.2231g Zn (NO with assay balance3)2·6H2O、0.2284g CH4N2S、0.3318gInCl3
In 50mL beaker, the aqueous hydrochloric acid solution of 30mLpH=1.8 is added to it, by the complete dissolution of drug under magnetic agitation effect；
The FTO electro-conductive glass conducting surface of modified mistake is downwardly inclined and is put into 50ml hydrothermal reaction kettle liner by (4-4), will
Solution is gone in liner in 4-3)；
The sealing of (4-5) reaction kettle, is placed in baking oven, 180 DEG C of heat preservation 3h, cooled to room temperature obtains FTO conducting surface
Flaxen film is uniformly covered with, FTO is delayed water and rinses, obtains ZnIn after vacuum drying2S4Nano-array electrode.
Embodiment 1: with 0.2mgAu in ZnIn2S4Nano-array surface deposition.
1. by the AuHCl of 20 μ l 50mmol/L4It is dissolved in 100mL pure water, obtains the solution containing Au0.2mg, solution is moved
Enter in quartzy electrolytic cell.
2. electrode slice polytetrafluoroethylene electrode is clamping fixed, it is totally immersed into middle solution, with ZnIn2S4Nano thin-film
Facing towards xenon source, the illumination 30min in magnetic agitation.
3. electrode slice is taken out, 3min is slowly rinsed with pure water, 60 DEG C of vacuum drying 6h obtain light deposition 0.2mg Au's
Au-ZnIn2S4 electrode slice.
Embodiment 2: with 0.4mgAu in ZnIn2S4Nano-array surface deposition.
1. by the AuHCl of 40 μ l 50mmol/L4It is dissolved in 100mL pure water, obtains the solution containing Au0.4mg, solution is moved
Enter in quartzy electrolytic cell.
2. electrode slice polytetrafluoroethylene electrode is clamping fixed, it is totally immersed into middle solution, with ZnIn2S4Nano thin-film
Facing towards xenon source, the illumination 30min in magnetic agitation.
3. electrode slice is taken out, 3min is slowly rinsed with pure water, 60 DEG C of vacuum drying 6h obtain light deposition 0.4mg Au's
Au-ZnIn2S4Electrode slice.
Embodiment 3: with 0.6mgAu in ZnIn2S4Nano-array surface deposition.
1. by the AuHCl of 60 μ l 50mmol/L4It is dissolved in 100mL pure water, obtains the solution containing Au0.6mg, solution is moved
Enter in quartzy electrolytic cell.
2. electrode slice polytetrafluoroethylene electrode is clamping fixed, it is totally immersed into solution, with ZnIn2S4The face of nano thin-film
Towards xenon source, the illumination 30min in magnetic agitation.
3. electrode slice is taken out, 3min is slowly rinsed with pure water, 60 DEG C of vacuum drying 6h obtain light deposition 0.6mg Au's
Au-ZnIn2S4Electrode slice.
Embodiment 4:ZnIn2S4Electrode slice and Au-ZnIn2S4The test of electrode slice photoelectrochemical behaviour.
1. matching the Na of 150mL0.1mol/L2SO4Solution, electrode slice platinum plate electrode is clamping fixed, and platinum plate electrode is to electricity
Pole, it is that reference electrode forms three-electrode system that Hg/HgCl, which is saturated potassium chloride electrode,.Electrode slice is tested by electrochemical workstation
Photoelectrochemical behaviour.
2. in Fig. 5, the photocurrent response feature of test Different electrodes piece is biased as 0V.
3. in Fig. 6, test Different electrodes piece carries out applying 0.2V bias when AC impedance under illumination condition, and high frequency is
50000Hz, low frequency 0.1Hz.
Embodiment 5:ZnIn2S4Electrode slice and Au-ZnIn2S4The photocatalysis fixed nitrogen performance test of electrode slice.
1. configuring 30mL methanol aqueous solution (VMethanol 95wt%: VPure water=1:4), electrode slice platinum plate electrode is clamping fixed, it is placed in
In special reactor, high pure nitrogen, Ventilation Rate 20mL/min are passed through from reactor bottom to it.
2. with the ZnIn in 300W xenon source irradiation reactor2S4Electrode slice collects 2mL reaction solution every 25min.
3. taking 1mL to collect solution to mix with 1mL Na Shi solution, 10min is reacted in the dark, is moved into 2ml cuvette, is used
The absorbance of test reaction liquid under ultraviolet-uisible spectrophotometer 420nm light.
4. the absorbance of test reaction liquid finds corresponding ammonia density in standard ammonia solution absorbance curve, unit is carried out
ZnIn before and after gold-supported is compared in conversion2S4The photoelectricity fixed nitrogen of nano-array, as shown in Figure 7.
Claims (7)
1. a kind of Au-ZnIn2S4The preparation method of nano-array electrode photocatalysis fixed nitrogen material, it is characterized in that: Au-ZnIn2S4It receives
The preparation method of rice array is: based on ZnIn2S4Nano-array electrode improves ZnIn in its surface light deposition nanometer Au particle2S4
Photocatalysis fixed nitrogen performance；One layer of ZnIn is grown on FTO electro-conductive glass using hydro-thermal method first2S4Nano-chip arrays pass through light
The method of deposition deposits Au particle on its surface；Au-ZnIn2S4Electrode slice fixation is put into methanol aqueous solution, is continually fed into high-purity
Nitrogen, by N under Xenon light shining2It is converted into NH3, and then it is converted into NH4+；Reaction solution is taken to mix colour developing with nessler reagent, really
Determine NH in reaction solution4+Concentration, and then determine material light catalysis fixed nitrogen performance.
2. a kind of Au-Znaccording to claim 12S4The preparation method of nano-array electrode photocatalysis fixed nitrogen material,
It is characterized in: the Au-ZnIn2S4The preparation of nano-array, the specific steps are as follows:
Step 1. utilizes zinc nitrate Zn (NO3)2·6H2O, indium trichloride InCl3, vulcanization urea CH4N2S is 1:2:4 with molar ratio
Proportional arrangement precursor solution, by one step hydro thermal method be made have ZnIn2S4The FTO conductive glass electrode of nanometer layer, i.e.,
ZnIn2S4Nano-array electrode；
Step 2. takes the HAuCl of 20-60 μ L 50mmol/L4Solution is diluted to 100mL with pure water, which is transferred to quartzy electricity
Xie Chizhong, by ZnIn2S4Electrode slice polytetrafluoroethylene electrode folder is fixed in quartzy electrolytic cell, passes through xenon lamp simulated solar irradiation
Irradiation makes the Au in solution3+The Au simple substance being reduced into is deposited on ZnIn2S4Electrode slice surface, prepares Au-ZnIn2S4Nanometer battle array
Column electrode；
Step 3. is to Au-ZnIn2S4Nano-array electrode photocatalysis fixed nitrogen material property is tested, Au-ZnIn2S4Electrode slice is solid
Surely it puts into methanol aqueous solution, is continually fed into high pure nitrogen, ventilate 20min in advance before simulated solar irradiation irradiation, with simulation
Sunlight is energy source, determines Au-ZnIn with platinum plate electrode is clamping2S4Nano-array electrode sets up light-catalyzed reaction pond；In xenon
Light is according to lower by N2It is converted into NH3, and then it is converted into NH4+；It takes reaction solution to mix colour developing with nessler reagent, determines reaction solution
Middle NH4+Concentration, and then determine material light catalysis fixed nitrogen performance.
3. a kind of Au-Znaccording to claim 22S4The preparation method of nano-array electrode photocatalysis fixed nitrogen material,
It is characterized in: in the step 1, ZnIn2S4It is prepared by the growth of nano-array, the specific steps are as follows:
Cleaning: sputtering is had SnO by step (1-1)2FTO electro-conductive glass be cut into the small pieces and number of 2 × 3cm, successively with being mixed with
Pure water solution, pure water, isopropanol, alcohol 95 wt%, the ethyl alcohol 99wt% ultrasound 30min of glass cleaner, rear naturally dry are standby
With；
Step (1-2), modified: the FTO electro-conductive glass cleaned up in step (1-1), which is put into the bis- Yang Shui ︰ ammonium hydroxide of Chun Shui ︰, is
In the solution of 5 ︰, 1 ︰ 1,10min is stood, tweezers press from both sides out, and clean with a large amount of pure water rinsings, naturally dry is spare；
Step (1-3) prepares precursor solution: the aqueous solution for being 1.8 with hydrochloric acid configuration pH, by 0.75mmol Zn (NO3)2·
6H2O、1.50mmolInCl3、3mmolCH4N2S is dissolved in the water of 30mL pH=1.8, and magnetic agitation 20min keeps drug completely molten
Precursor solution is made in solution；
The FTO electro-conductive glass conducting surface of modified mistake is downwardly inclined and is put into 50ml hydrothermal reaction kettle liner by step (1-4), will
Precursor solution is transferred in reaction kettle in step (1-3)；
Step (1-5), reaction kettle sealing, is placed in baking oven, 180 DEG C of heat preservation 3h, cooled to room temperature obtains FTO conduction glass
Glass conducting surface uniformly covers with flaxen film, which is ZnIn2S4Nano thin-film；FTO electro-conductive glass is through slow water
It rinses, obtain ZnIn after vacuum drying 6h2S4Nano-array electrode.
4. a kind of Au-Znaccording to claim 22S4The preparation method of nano-array electrode photocatalysis fixed nitrogen material,
It is characterized in: in the step 2, in ZnIn2S4Nano-array surface deposition gold；Specific step is as follows:
Step (2-1), by the AuHCl of 20-60 μ l 50mmol/L4It is diluted to 100mL with pure water, solution is moved into quartzy electrolytic cell
In；
Step (2-2), by ZnIn2S4Electrode polytetrafluoroethylene electrode is clamping fixed, is totally immersed into solution in step (2-1), with
ZnIn2S4Nano thin-film facing towards xenon source, the illumination 20-40min in magnetic agitation, to ZnIn2S4It is heavy that electrode implements light
Product；
Step (2-3), the electrode that light deposition is crossed are rinsed 3 times with deionized water, and 60 DEG C of vacuum drying 6h obtain surface deposition Au
Au-ZnIn2S4Nano-array electrode.
5. a kind of Au-Znaccording to claim 22S4The preparation method of nano-array electrode photocatalysis fixed nitrogen material,
Be characterized in: in the step 2, the intensity of illumination of simulated solar irradiation irradiation is 100mW/cm2, 20- is irradiated at room temperature
40min。
6. a kind of Au-Znaccording to claim 22S4The preparation method of nano-array electrode photocatalysis fixed nitrogen material,
It is characterized in: in the step 3, the high pure nitrogen N that is passed through2Flow 20ml/min, simulated solar irradiation irradiation before in advance
Ventilate 20min；In the methanol aqueous solution, the volume ratio of 99wt% methanol and water is 1:4.
7. a kind of Au-Znaccording to claim 1 or 22S4The preparation method of nano-array electrode photocatalysis fixed nitrogen material
Dedicated unit, it is characterized in that: in ZnIn2S4The dedicated unit of nano-array surface light deposition gold particle: too including xenon lamp simulation
Sunlight, electrode holder, ZnIn2S4Nano-array electrode, magnetic stirring apparatus, magneton and electrochemical reaction cell；Pacify on magnetic stirring apparatus
Electrochemical reaction cell is set, there is magneton in electrochemical reaction cell, has electrode holder, electrode holder clamping in electrochemical reaction cell upper end
ZnIn2S4Nano-array electrode has xenon lamp simulated solar irradiation to irradiate ZnIn outside electrochemical reaction cell2S4Nano-array electrode,
ZnIn2S4Nano-array electrode is placed in electrolyte.
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| CN112264049A (en) * | 2020-10-14 | 2021-01-26 | 盐城工学院 | Mo or Fe doped Zn for synthesizing ammonia by photocatalysis and nitrogen fixation1-xIn2S4Process for preparing catalyst |
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