CN115487830B - Method for inhibiting photo-corrosiveness of zinc indium sulfide by utilizing in-situ photochemical reaction - Google Patents
Method for inhibiting photo-corrosiveness of zinc indium sulfide by utilizing in-situ photochemical reaction Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 52
- 238000006552 photochemical reaction Methods 0.000 title claims abstract description 50
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 46
- YYKKIWDAYRDHBY-UHFFFAOYSA-N [In]=S.[Zn] Chemical compound [In]=S.[Zn] YYKKIWDAYRDHBY-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 230000002401 inhibitory effect Effects 0.000 title claims abstract description 34
- 229910006119 NiIn Inorganic materials 0.000 claims abstract description 111
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 82
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 59
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 59
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 53
- 239000000463 material Substances 0.000 claims abstract description 47
- 238000001035 drying Methods 0.000 claims abstract description 40
- 238000006243 chemical reaction Methods 0.000 claims abstract description 30
- 238000003756 stirring Methods 0.000 claims abstract description 29
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 26
- 239000011593 sulfur Substances 0.000 claims abstract description 26
- 229910052738 indium Inorganic materials 0.000 claims abstract description 25
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 20
- 238000004140 cleaning Methods 0.000 claims abstract description 16
- 230000001699 photocatalysis Effects 0.000 claims abstract description 15
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 14
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims abstract description 12
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims abstract description 9
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000010952 in-situ formation Methods 0.000 claims abstract description 8
- 239000011592 zinc chloride Substances 0.000 claims abstract description 6
- 235000005074 zinc chloride Nutrition 0.000 claims abstract description 6
- 239000012046 mixed solvent Substances 0.000 claims abstract description 3
- 239000000047 product Substances 0.000 claims description 33
- 239000008367 deionised water Substances 0.000 claims description 31
- 229910021641 deionized water Inorganic materials 0.000 claims description 31
- 239000011701 zinc Substances 0.000 claims description 25
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 23
- 229910052725 zinc Inorganic materials 0.000 claims description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- 238000005406 washing Methods 0.000 claims description 18
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- 238000005286 illumination Methods 0.000 claims description 10
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- XURCIPRUUASYLR-UHFFFAOYSA-N Omeprazole sulfide Chemical compound N=1C2=CC(OC)=CC=C2NC=1SCC1=NC=C(C)C(OC)=C1C XURCIPRUUASYLR-UHFFFAOYSA-N 0.000 claims description 8
- 238000007146 photocatalysis Methods 0.000 claims description 8
- 230000002829 reductive effect Effects 0.000 claims description 8
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 7
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- 230000000694 effects Effects 0.000 claims description 6
- PSCMQHVBLHHWTO-UHFFFAOYSA-K indium(iii) chloride Chemical group Cl[In](Cl)Cl PSCMQHVBLHHWTO-UHFFFAOYSA-K 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- 229910052724 xenon Inorganic materials 0.000 claims description 5
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 230000003647 oxidation Effects 0.000 claims description 4
- 238000007254 oxidation reaction Methods 0.000 claims description 4
- 238000009210 therapy by ultrasound Methods 0.000 claims description 4
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 3
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical group [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 3
- 239000007795 chemical reaction product Substances 0.000 claims description 3
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 3
- 230000036961 partial effect Effects 0.000 claims description 3
- 238000007789 sealing Methods 0.000 claims description 3
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 3
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims description 3
- 239000004246 zinc acetate Substances 0.000 claims description 3
- SHWZFQPXYGHRKT-FDGPNNRMSA-N (z)-4-hydroxypent-3-en-2-one;nickel Chemical group [Ni].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O SHWZFQPXYGHRKT-FDGPNNRMSA-N 0.000 claims 1
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 19
- 229910052739 hydrogen Inorganic materials 0.000 description 19
- 239000001257 hydrogen Substances 0.000 description 19
- 238000010586 diagram Methods 0.000 description 8
- 238000001259 photo etching Methods 0.000 description 7
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- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 6
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- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 4
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910021617 Indium monochloride Inorganic materials 0.000 description 2
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- APHGZSBLRQFRCA-UHFFFAOYSA-M indium(1+);chloride Chemical compound [In]Cl APHGZSBLRQFRCA-UHFFFAOYSA-M 0.000 description 2
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- -1 CdS Chemical class 0.000 description 1
- 229920001661 Chitosan Polymers 0.000 description 1
- 229910002441 CoNi Inorganic materials 0.000 description 1
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- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 241000949477 Toona ciliata Species 0.000 description 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
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- 230000033228 biological regulation Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- UBAZGMLMVVQSCD-UHFFFAOYSA-N carbon dioxide;molecular oxygen Chemical compound O=O.O=C=O UBAZGMLMVVQSCD-UHFFFAOYSA-N 0.000 description 1
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- 150000004763 sulfides Chemical class 0.000 description 1
- YVTHLONGBIQYBO-UHFFFAOYSA-N zinc indium(3+) oxygen(2-) Chemical compound [O--].[Zn++].[In+3] YVTHLONGBIQYBO-UHFFFAOYSA-N 0.000 description 1
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- 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
- B01J27/043—Sulfides with iron group metals or platinum group metals
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Abstract
The invention discloses a method for inhibiting the photo-corrosiveness of zinc indium sulfide by utilizing an in-situ photochemical reaction, and belongs to the technical field of photocatalytic materials and photochemistry. Adding a nickel source, an indium source and a sulfur source into a mixed solvent of ethylene glycol and N, N-dimethylformamide, stirring uniformly, transferring the solution into a reaction kettle for hydrothermal reaction, and centrifugally separating, cleaning and drying the product after the reaction is finished; dispersing the dried product in water, ultrasonic treating for a period of time, adding zinc chloride and nitric acidStirring and dissolving indium and thioacetamide, then carrying out water bath reaction, centrifuging, cleaning and drying the product after the reaction is finished to obtain type II NiIn 2 S 4 /ZnIn 2 S 4 A heterojunction material; for type II NiIn 2 S 4 /ZnIn 2 S 4 Carrying out photochemical treatment on the heterojunction to enable part of n-type NiIn 2 S 4 In situ formation of p-type Ni (OH) 2 The material finally obtains the p-n-n type Ni (OH) 2 /NiIn 2 S 4 /ZnIn 2 S 4 And a heterojunction. The preparation method is simple, has simple operation conditions, carrier directional transmission characteristics, higher catalytic efficiency and excellent photo-chemical corrosion resistance.
Description
Technical Field
The invention relates to the technical field of photocatalysis materials and photochemistry, in particular to a method for inhibiting the photo-corrosiveness of zinc indium sulfide by utilizing in-situ photochemical reaction.
Background
The photocatalysis technology is an ideal new energy development means, is an effective way for realizing the aim of carbon neutralization and solving the current greenhouse effect and environmental pollution, and is widely applied to the fields of pollutant degradation, photolysis of water to produce hydrogen and oxygen, carbon dioxide photoreduction, photoswitch, photochemistry nitrogen fixation and the like. However, conventional TiO 2 The problems of large band gap, narrow spectral response range, high photon-generated carrier recombination rate and the like of the photocatalysis material limit the practical application thereof.
Hexagonal phase ZnIn frequently used in the prior art 2 S 4 Is a novel ternary semiconductor sulfide, which has unique photoelectric property and photocatalysis property, special lamellar structure, moderate band gap width (2.2-2.5 eV), more negative conduction band position (-0.79 eV), good visible light absorption (absorption edge about 540 nm), however, znIn 2 S 4 The problems of high photon-generated carrier recombination rate, low quantum efficiency and serious photo-corrosion remain to be solved, especially the photo-corrosion affects the realityThe key of the application. In the prior art, the separation of photo-generated carriers is promoted by methods of protective layer coating, cocatalyst loading, heterojunction construction and the like, so that the photo-catalytic activity of the catalyst is improved; however, the current study of photo-corrosion resistance is mainly focused on binary sulfides such as CdS, znS and the like, and on ternary ZnIn 2 S 4 Little research is done on photo-corrosiveness. Recently, the spectral absorption performance of sulfide can be remarkably improved by utilizing the rearrangement of the energy band structures of the heterojunction, the directional migration of photo-generated electrons or holes can be realized by utilizing the built-in electric field of the heterojunction interface, and the photo-corrosiveness of sulfide materials can be effectively inhibited while the catalytic efficiency and the spectral absorption are rapidly improved, so that the sulfide material becomes a front research hot spot in recent years.
Document 1 (N.Jiang, chem.Eng.J.,2021,412,128627) discloses a hydrothermal method for coating a layer of reduced graphene oxide on the surface of CdS to prevent direct contact between photogenerated holes and CdS and suppress S 2- Ion diffusion, and after 60 minutes of illumination, cd 2- The ion erosion concentration was reduced from 3.32% to 0.96%. The method can significantly suppress the photo-corrosiveness of sulfide, but inevitably deteriorates the photo-absorption and photo-catalytic efficiency of sulfide material.
Document 2 (Y.Zhang, appl.Catal.B: environ.,2020,277,119152) involves grafting a layer of chitosan onto the CdS surface, using chitosan-NH 2 And the fast transfer of the-OH groups to the photo-generated holes, thereby significantly reducing the erosion of the photo-generated holes to CdS, and as a result, the photo-corrosion resistance of CdS is significantly improved. The method can inhibit the photo-corrosiveness of CdS, however, the grafted organic protective layer also obviously reduces the activity of CdS boundary sulfur.
Document 3 (Q.Gai, catal.Sci.Technol.,2021,11,5579-5589) prepares a CoNi-supported type II C 3 N 4 The photo-generated carrier separation efficiency is obviously improved by the CdS heterojunction material, and photo-generated holes on a CdS valence band are rapidly transferred to C under the action of a space charge field 3 N 4 And the Co-S bond formed between CdS and CoNi can further transfer the CdS photo-generated electrons rapidly, so that the erosion of photo-generated holes to CdS is greatly inhibited. The method can obviously inhibit the photo-corrosiveness of CdS, and after the built-in electric field of the II-type heterojunction is stable, the photo-generated hole transfer is receivedIt is difficult to further prevent the photo-etching.
Document 4 (M.R.Shariati, J.Mater.Chem.A,2018,6,20433-20443) prepares an Ag-PdS/ZnS/CdS composite photocatalyst, and uses a core-shell structure of I-type ZnS/CdS to rapidly transfer photo-generated electrons and photo-generated holes from a ZnS core to a CdS shell, and simultaneously uses a double promoter to rapidly transfer photo-generated electrons to an Ag promoter and rapidly transfer photo-generated holes to a PdS promoter, so that ZnS photo-generated carriers are separated efficiently, photo-corrosion of the photo-generated holes to ZnS materials is effectively inhibited, and as a result, the catalytic activity of the system is still maintained for 95% after 30 days. However, the construction of the system is difficult, noble metals increase the cost, and noble metal cocatalysts loaded with photoreaction are easy to run off, resulting in performance and photo-corrosion degradation.
Document 5 (Z.Wang, int.J.Hydrogen energy., 2020,45,4113-4121) discloses a hydrothermal method for LaNiO 3 Growing a layer of ZnIn on the surface of the nano cage 2 S 4 The nanosheets have good transmission channels for photo-generated charges due to the formation of Z-shaped heterogeneous interfaces, and as a result, the separation efficiency of photo-generated carriers and hydrogen evolution performance are remarkably improved, and due to ZnIn 2 S 4 Photoproduction of holes and LaNiO on valence band 3 The photo-generated electrons on the guide belt are annihilated rapidly, so that ZnIn 2 S 4 The photo-etching resistance is significantly improved. The method can effectively inhibit the photo-corrosion, but is limited by the second phase LaNiO 3 The properties, photocatalytic performance, are to be further improved.
Disclosure of Invention
Aiming at the defects of the prior art, the method for inhibiting the photo-corrosiveness of the zinc indium sulfide by utilizing the in-situ photochemical reaction is provided, and the photo-corrosiveness problem of the zinc indium sulfide is effectively solved on the premise of considering high photocatalytic efficiency; the p-n-n type Ni (OH) produced by the method 2 /NiIn 2 S 4 /ZnIn 2 S 4 The heterojunction has excellent hydrogen evolution performance and good visible light response under the photocatalysis condition, and realizes n-type NiIn under the photochemical action 2 S 4 Transformation of semiconductor to form p-type Ni (OH) in situ 2 Finally obtain the p-n-n NiIn 2 S 4 /ZnIn 2 S 4 Heterojunction of up toOn the premise of promoting the efficient separation of photo-generated carriers, the directional continuous transfer of photo-generated holes can be realized, and finally the ZnIn is prevented 2 S 4 The purpose of photo-etching is to give it excellent long-term stability and reproducibility.
In order to achieve the above purpose, the invention adopts the following technical scheme:
adding a nickel source, an indium source and a sulfur source into a mixed solvent of ethylene glycol and N, N-dimethylformamide, stirring uniformly, transferring the solution into a reaction kettle for hydrothermal reaction, and centrifuging, cleaning and drying the product after the reaction is finished; dispersing the dried product in water, ultrasonically treating for a period of time, adding zinc chloride, indium nitrate and thioacetamide, stirring for dissolving, then carrying out water bath reaction, centrifuging the product after the reaction is finished, cleaning and drying to obtain type II NiIn 2 S 4 /ZnIn 2 S 4 A heterojunction material; for type II NiIn 2 S 4 /ZnIn 2 S 4 Carrying out photochemical treatment on the heterojunction to enable part of n-type NiIn 2 S 4 In situ formation of p-type Ni (OH) 2 The material finally obtains the p-n-n type Ni (OH) 2 /NiIn 2 S 4 /ZnIn 2 S 4 And a heterojunction.
The p-n-n type Ni (OH) with good photo-activity and photo-corrosion resistance is constructed in situ by adopting a simple hydrothermal/water bath/photochemical three-step method 2 /NiIn 2 S 4 /ZnIn 2 S 4 Heterojunction materials.
The method comprises the following specific steps:
step 1, stirring and mixing ethylene glycol and N, N-dimethylformamide according to the volume ratio of (0.5-2): 1, and sequentially adding the mixture into a mixed solution of the ethylene glycol and the N, N-dimethylformamide according to the molar ratio of a nickel source to an indium source to a sulfur source of (4-6) of 1:2 by taking the concentration of the nickel source of 0.01-0.05 mol/L as a standard, and continuously stirring until the mixture is completely dissolved;
step 8, weighing the II-type NiIn 2 S 4 /ZnIn 2 S 4 Heterojunction, dispersed to H in the proportion of 500-800 mg/L 2 Transferring into O solvent, transferring into photochemical reactor, continuously stirring, vacuumizing, washing with nitrogen, turning on light source to make photochemical reaction, and making type II NiIn 2 S 4 /ZnIn 2 S 4 Partial n-type NiIn in heterojunction 2 S 4 In situ formation of p-type Ni (OH) 2 A material;
Further, in the step 1, the nickel source is nickel acetylacetonate or nickel chloride, the soluble indium source is indium chloride or indium nitrate, and the sulfur source is thioacetamide or thiourea; the stirring and mixing time of the mixed solution of the glycol and the N, N-dimethylformamide is 0.5-1 h.
Further, in the step 2, the hydrothermal reaction conditions are as follows: the hydrothermal temperature is 180-220 ℃, and the hydrothermal time is 12-24 hours.
Further, in the steps 3, 7 and 9, the washing times of the deionized water are 3 to 4 times, and the washing times of the absolute ethyl alcohol are 1 to 2 times; the drying conditions are as follows: the drying temperature is 70-80 ℃ and the drying time is 6-10 h.
Further, in step 4, the precursor NiIn 2 S 4 The ultrasonic time of the dispersion liquid of the product is 1 to 4 hours.
In step 5, the soluble zinc source is zinc acetate or zinc chloride, the soluble indium source is indium chloride or indium nitrate, and the sulfur source is thioacetamide or sodium sulfide; the stirring time for sequentially adding the zinc source, the indium source and the sulfur source into the dispersion liquid is 0.5-1 h.
In step 6, the temperature of the constant-temperature water bath is 70-100 ℃, and the time of the constant-temperature water bath is 2-6 h.
Further, in step 8, niIn type II 2 S 4 /ZnIn 2 S 4 Heterojunction addition to H 2 Stirring time in the O solvent is 30min, and vacuumizing time is 15-30 min after transferring to the photochemical reactor; the light source in the photocatalysis reaction process is a 300W xenon lamp; the light source, illumination time and light intensity of the photocatalytic reaction determine p-type Ni (OH) 2 The light source in the invention has the wavelength of 420-1100 nm, the illumination time of 2-30 h and the light intensity of 200-400 mW/cm 2 。
The beneficial effects are that: the invention adopts simple hydrothermal/water bath/photochemical method to successfully prepare p-n-n type Ni (OH) by reasonably selecting raw materials and utilizing in-situ transformation of phase 2 /NiIn 2 S 4 /ZnIn 2 S 4 Heterojunction materials, products with excellent photo-catalysisChemical property and good light corrosion resistance. The key problems to be solved by the invention are as follows: 1) The II type NiIn with good interface is successfully prepared by accurately controlling the types and the dosage of raw materials, the hydrothermal/water bath temperature, the hydrothermal/water bath time and other technological parameters 2 S 4 /ZnIn 2 S 4 A heterojunction; 2) In the photochemical reaction process, n-type NiIn is realized by accurately controlling photochemical reaction parameters such as light source interval, irradiation time, light intensity and the like and utilizing in-situ conversion of phases 2 S 4 In situ formation of p-type Ni (OH) 2 Realize type II NiIn 2 S 4 /ZnIn 2 S 4 Structural p-n-n type Ni (OH) 2 /NiIn 2 S 4 /ZnIn 2 S 4 A transition of structure;
3) Perfect heterogeneous interface control, thereby realizing directional migration of photo-generated holes and reaching ZnIn 2 S 4 Excellent photo-corrosiveness and can effectively improve the photo-catalytic performance in a short period; 4) P-type Ni (OH) 2 The p-n type Ni (OH) is realized mainly by precisely controlling the irradiation time, irradiation distance, light intensity and the like 2 /NiIn 2 S 4 The regulation and control of components and the continuous extraction of photo-generated holes finally achieve the inhibition of photo-corrosiveness.
By adopting the scheme, compared with the prior art, the invention has the following advantages:
1) The invention is characterized in that NiIn 2 S 4 In the preparation process, the reducing solvent glycol is added, so that the oxidation of the product under the high-temperature solvothermal condition is reduced; the ethylene glycol and DMF organic solvent moderately reduce the influence of polarity on molecular bonding, and NiIn with smaller size is obtained 2 S 4 Nano sheet for increasing NiIn 2 S 4 With ZnIn 2 S 4 Is beneficial to improving the contact area of type II NiIn 2 S 4 /ZnIn 2 S 4 The interface contact of the heterojunction improves the carrier mobility.
2) The invention is based on ZnIn 2 S 4 The problem of photo-etching of materials is that NiIn is utilized for the first time 2 S 4 Is realized from the photochemical reaction ofII NiIn 2 S 4 /ZnIn 2 S 4 Heterojunction to p-n-n type Ni (OH) 2 /NiIn 2 S 4 /ZnIn 2 S 4 The transition of the heterojunction can achieve the continuous extraction of the photo-generated holes and reduce the ZnIn of the photo-generated holes 2 S 4 Is finally improved by the erosion of ZnIn 2 S 4 Resistance to photo-etching.
3) In n-type NiIn due to in-situ photochemical reaction 2 S 4 In-situ generation of p-type Ni (OH) on material surface 2 Materials such that NiIn type II 2 S 4 /ZnIn 2 S 4 A good interface is formed between the heterojunctions, which is very beneficial for carrier transport.
4) The photo-generated holes have a much slower migration rate than photo-generated electrons, so that the difficulty of photo-generated hole extraction is high, the current catalysis technology mainly focuses on the extraction of photo-generated electrons, and the continuous directional extraction of photo-generated holes can be realized by utilizing double heterojunctions.
5) Due to the p-n-n type Ni (OH) 2 /NiIn 2 S 4 /ZnIn 2 S 4 The heterojunction can continuously drive the photo-generated electrons and photo-generated holes to directionally migrate by utilizing the II type heterojunction and the p-n type heterojunction, thereby effectively improving the ZnIn 2 S 4 The resulting photo-generated carrier separation efficiency results in a catalytic system having higher photo-catalytic activity.
Drawings
FIG. 1 is an XRD pattern of different samples of a method of inhibiting the photo-corrosiveness of zinc indium sulfide using an in situ photochemical reaction in accordance with the present invention.
FIG. 2 shows a p-n-n type Ni (OH) of the present invention for inhibiting the photo-corrosiveness of zinc indium sulfide by in situ photochemical reaction 2 /NiIn 2 S 4 /ZnIn 2 S 4 Ni element narrow sweep of heterojunction material.
FIG. 3 shows a p-n-n type Ni (OH) of the present invention for inhibiting the photo-corrosiveness of zinc indium sulfide by in situ photochemical reaction 2 /NiIn 2 S 4 /ZnIn 2 S 4 An O-element narrow sweep of heterojunction material.
FIG. 4 is a Raman diagram of various samples of a method of inhibiting the photo-corrosiveness of zinc indium sulfide using an in situ photochemical reaction in accordance with the present invention.
FIG. 5 shows NiIn type II in a method of inhibiting the photo-corrosiveness of zinc indium sulfide by in situ photochemical reaction 2 S 4 /ZnIn 2 S 4 HRTEM diagram of heterojunction intermediate.
FIG. 6 shows a p-n-n type Ni (OH) of the present invention using in situ photochemical reaction to inhibit the photo-corrosiveness of zinc indium sulfide 2 /NiIn 2 S 4 /ZnIn 2 S 4 HRTEM diagram of heterojunction material.
FIG. 7 shows NiIn type II in a method of inhibiting the photo-corrosiveness of zinc indium sulfide by in situ photochemical reaction 2 S 4 /ZnIn 2 S 4 Heterojunction material hydrogen evolution rate graph.
FIG. 8 shows a p-n-n type Ni (OH) of the present invention for inhibiting the photo-corrosiveness of zinc indium sulfide by in situ photochemical reaction 2 /NiIn 2 S 4 /ZnIn 2 S 4 Heterojunction material hydrogen evolution rate graph.
FIG. 9 shows a p-n-n type Ni (OH) of the present invention for inhibiting the photo-corrosiveness of zinc indium sulfide by in situ photochemical reaction 2 /NiIn 2 S 4 /ZnIn 2 S 4 Heterojunction material hydrogen evolution repeatability graph.
FIG. 10 shows pure phase ZnIn of a method of inhibiting the photo-corrosiveness of zinc indium sulfide by in situ photochemical reaction according to the invention 2 S 4 And NiIn type II 2 S 4 /ZnIn 2 S 4 And a zinc ion precipitation curve chart after the photochemical reaction of the heterojunction material.
Detailed Description
The invention will be further described with reference to specific examples.
The invention discloses a method for inhibiting the photo-corrosiveness of zinc indium sulfide by utilizing in-situ photochemical reaction, which comprises the following steps: the p-n-n type Ni (OH) with good photo-activity and photo-corrosion resistance is constructed in situ by adopting a simple hydrothermal/water bath/photochemical three-step method 2 /NiIn 2 S 4 /ZnIn 2 S 4 A heterojunction material; in a method in which the photocrosivity of zinc indium sulfide is inhibited by an in-situ photochemical reaction: first, using type II NiIn 2 S 4 /ZnIn 2 S 4 The energy band rearrangement of the heterojunction, the built-in electric field drives the photo-generated electrons from NiIn 2 S 4 Conduction band direction ZnIn 2 S 4 Conduction band transport, photo-generated holes from ZnIn 2 S 4 Valence band direction NiIn 2 S 4 Valence band migration, thereby promoting ZnIn 2 S 4 Separation efficiency of photo-generated carriers, and reduction of photo-generated hole pair ZnIn 2 S 4 Erosion of (a); then, the n-type NiIn is allowed to react by in situ photochemistry 2 S 4 Surface in situ formation of p-type Ni (OH) 2 By means of p-n type Ni (OH) 2 /NiIn 2 S 4 Built-in electric field will NiIn 2 S 4 The photo-generated holes on the valence band are further extracted into Ni (OH) 2 On the material, the photo-generated hole pair NiIn is reduced 2 S 4 Effectively stabilizing p-n-n type Ni (OH) 2 /NiIn 2 S 4 /ZnIn 2 S 4 Heterojunction with continuous directional extraction of ZnIn 2 S 4 Photo-generated holes on valence band (ZnIn) 2 S 4 →NiIn 2 S 4 →Ni(OH) 2 ) Thereby effectively preventing the photo-generated hole pair ZnIn 2 S 4 Is finally to promote ZnIn 2 S 4 Is resistant to photo-etching and has long-term stability.
The preparation process comprises the following steps:
(1) Mixing ethylene glycol and N, N-dimethylformamide according to a certain volume ratio, and then sequentially adding a nickel source, an indium source and a sulfur source into a mixed solution of the ethylene glycol and the N, N-dimethylformamide according to a certain proportion, and continuously stirring until all the materials are dissolved;
(2) Pouring the uniformly mixed solution into a reactor with a Teflon lining, sealing, and then placing into a baking oven for hydrothermal reaction, wherein the oxidation of reaction products is reduced through glycol in the solution in the hydrothermal reaction process;
(3) After the hydrothermal reaction is finished, by separationSeparating the precipitate from the core, cleaning the precipitate with deionized water and absolute ethyl alcohol in sequence, and then drying in an oven to obtain a precursor NiIn 2 S 4 A product;
(4) Weighing the NiIn 2 S 4 Adding the precursor product into deionized water, and performing ultrasonic treatment to obtain uniform dispersion;
(5) Sequentially adding a zinc source, an indium source and a sulfur source into the dispersion liquid according to a certain proportion, and fully stirring until the zinc source, the indium source and the sulfur source are completely dissolved;
(6) Transferring the solution into a constant-temperature water bath kettle for water bath reaction;
(7) After the water bath reaction is finished, separating out a precipitate by centrifugation, cleaning the precipitate by deionized water and absolute ethyl alcohol in sequence, and then putting the precipitate into a drying oven for drying, wherein the dried product is the II type NiIn 2 S 4 /ZnIn 2 S 4 A heterojunction;
(8) Weighing the type II NiIn 2 S 4 /ZnIn 2 S 4 Heterojunction, dispersed to H 2 Transferring into O solvent, transferring into photochemical reactor, continuously stirring, vacuumizing, washing with nitrogen, turning on light source to make photochemical reaction, and making type II NiIn 2 S 4 /ZnIn 2 S 4 Partial n-type NiIn in heterojunction 2 S 4 In situ formation of p-type Ni (OH) 2 A material;
(9) Centrifugally separating the product after photochemical reaction, cleaning the product sequentially by deionized water and absolute ethyl alcohol, and then drying in a drying oven to obtain p-n-n type Ni (OH) 2 /NiIn 2 S 4 /ZnIn 2 S 4 And a heterojunction.
In the step (1), the volume ratio of the ethylene glycol to the N, N-dimethylformamide is (0.5-2) 1; the nickel source is nickel acetylacetonate or nickel chloride, the soluble indium source is indium chloride or indium nitrate, and the sulfur source is thioacetamide or thiourea; the molar ratio of the nickel source to the indium source to the sulfur source is 1:2 (4-6); the concentration of the nickel source is 0.01-0.05 mol/L; the stirring and mixing time of the mixed solution of the glycol and the N, N-dimethylformamide is 0.5-1 h.
In the step (2), the hydrothermal reaction conditions are as follows: the hydrothermal temperature is 180-220 ℃, and the hydrothermal time is 12-24 hours.
In the step (3), the washing times by using deionized water are 3-4 times, and the washing times by using absolute ethyl alcohol are 1-2 times; the drying conditions are as follows: the drying temperature is 70-80 ℃ and the drying time is 6-10 h.
In the step (4), the precursor NiIn 2 S 4 The amount of product added determines the type II NiIn 2 S 4 /ZnIn 2 S 4 Material proportion of heterojunction, precursor NiIn in the invention 2 S 4 The addition amount of the product is calculated by taking a zinc source as a standard, and the molar ratio is NiIn 2 S 4 Zinc source=0.05 to 0.3; the precursor NiIn 2 S 4 The ultrasonic treatment time of the product dispersion liquid is 1-4 h.
In the step (5), the soluble zinc source is zinc acetate or zinc chloride, the soluble indium source is indium chloride or indium nitrate, and the sulfur source is thioacetamide or sodium sulfide; the mol ratio of the zinc source to the indium source to the sulfur source is 1:2 (4-6); the concentration of the zinc source is 0.03-0.1 mol/L, and the concentration of the indium source and the concentration of the sulfur source are converted according to the concentration of the zinc source; the stirring time for sequentially adding the zinc source, the indium source and the sulfur source into the dispersion liquid is 0.5-1 h.
In the step (6), the temperature of the constant-temperature water bath is 70-100 ℃, and the time of the constant-temperature water bath is 2-6 h.
In the step (7), the washing times by using deionized water are 3-4 times, and the washing times by using absolute ethyl alcohol are 1-2 times; the drying conditions are as follows: the drying temperature is 70-80 ℃ and the drying time is 6-10 h.
In the step (8), the II type NiIn 2 S 4 /ZnIn 2 S 4 The heterojunction additive amount is as follows: 500-800 mg/L; the stirring time is 30min, and the vacuumizing time is 15-30 min; the light source in the photocatalysis reaction process is a 300W xenon lamp; the light source, illumination time and light intensity of the photocatalytic reaction are determinedP-type Ni (OH) 2 The light source in the invention has the wavelength of 420-1100 nm, the illumination time of 2-30 h and the light intensity of 200-400 mW/cm 2 。
In the step (9), the washing times by using deionized water are 3-4 times, and the washing times by using absolute ethyl alcohol are 1-2 times; the drying conditions are as follows: the drying temperature is 70-80 ℃ and the drying time is 6-10 h.
Example 1:
first, 118.8mg of NiCl was weighed out 2 ·6H 2 O，293.2mg InCl 3 ·4H 2 O and 300.5mg of TAA were added sequentially to a 40mL mixed solution of ethylene glycol and N, N-dimethylformamide (V N, N-dimethylformamide :V Ethylene glycol =1:1), stirring at room temperature for 1h to obtain a transparent uniform solution; the solution was poured into 50mL of teflon liner, and the teflon liner was transferred to the reaction kettle, sealed and placed in an oven for hydrothermal reaction, hydrothermal conditions: the hydrothermal reaction time is 24 hours at the hydrothermal temperature of 200 ℃; after the reaction was completed, the reaction mixture was washed 3 times with deionized water, 2 times with absolute ethanol, and dried at 70℃for 10 hours.
Subsequently, 7.5mg of the dried product obtained in the step (1) is weighed and dispersed in 80mL of deionized water for standby; 0.4089g ZnCl 2 ，0.9812g In(NO 3 ) 3 ·6H 2 O and 0.4508g of TAA were added sequentially to 20mL of deionized water and stirred at room temperature for 1 hour to obtain a transparent and uniform solution. Mixing the obtained solution with the standby suspension, and stirring for 30min at room temperature; the resulting suspension was placed in a chemical bath at 80℃for 6h. After the reaction is finished, washing with deionized water for 3 times and absolute ethyl alcohol for 2 times; drying at 70deg.C for 10 hr to obtain NiIn II 2 S 4 /ZnIn 2 S 4 Heterojunction materials.
Finally, 100mg of NiIn type II above was weighed 2 S 4 /ZnIn 2 S 4 Heterojunction, added to 100mL triethanolamine and deionized water (V Deionized water :V Triethanolamine salt Mixed solution of =9:1); vacuumizing the reactor, and collecting 300W xenon lamp light source with 420nm cut-off filterThe mixture was placed 7cm above the reactor and irradiated for 9 hours. In the illumination process, circulating cooling water is utilized to keep the reaction temperature of the reactor at 10 ℃; after the reaction was completed, the sample was separated by centrifugation and washed with deionized water 3 times and absolute ethanol 2 times. Drying at 70deg.C for 10 hr to obtain p-n-n type Ni (OH) 2 /NiIn 2 S 4 /ZnIn 2 S 4 Heterojunction materials.
Example 2:
first, 118.8mg of NiCl was weighed out 2 ·6H 2 O，293.2mg InCl 3 ·4H 2 O and 300.5mg of TAA were added sequentially to a 40mL mixed solution of ethylene glycol and N, N-dimethylformamide (V N, N-dimethylformamide :V Ethylene glycol =2:1), stirring at room temperature for 1h, to obtain a transparent uniform solution; the solution was poured into 50mL teflon liner and transferred to the reactor, sealed and put into an oven for hydrothermal reaction, hydrothermal conditions: the hydrothermal temperature is 180 ℃ and the hydrothermal time is 24 hours; after the reaction is finished, washing with deionized water for 4 times and absolute ethyl alcohol for 1 time; and subsequently dried at 80℃for 6h.
Then, 37.5mg of the dried product obtained in the step (1) was weighed and ultrasonically dispersed in 80mL of deionized water for later use, followed by 0.4089g of ZnCl 2 ，0.9812g In(NO 3 ) 3 ·6H 2 O and 0.6762g of TAA were added sequentially to 20mL of deionized water and stirred at room temperature for 1h, followed by stirring to give a clear and homogeneous solution. The resulting solution was combined with additional NiIn 2 S 4 The suspension was mixed and stirred at room temperature for 30min. The resulting suspension was placed in a chemical bath at 80℃for 6h. After the reaction is finished, the deionized water is used for cleaning for 4 times; washing with absolute ethanol for 1 time. Drying at 80℃for 6h. Obtain type II NiIn 2 S 4 /ZnIn 2 S 4 Heterojunction materials.
Finally, niIn 2 S 4 /Ni(OH) 2 /ZnIn 2 S 4 n-p-n heterojunction material preparation: weighing 100mgNiIn 2 S 4 /ZnIn 2 S 4 Nanomaterial, add to 100mL triethanolamine and deionized water (V Deionized water :V Triethanolamine salt =9:1). The reactor was evacuated and a 300W xenon lamp light source with a 420nm cut-off filter was placed 7cm above the reactor for illumination for 21h. The reactor reaction temperature was maintained at 10 ℃ during the light irradiation process using circulating cooling water. After the reaction is finished, centrifugally separating a sample, and washing the sample with deionized water for 4 times; washing with absolute ethanol for 1 time. Drying at 80deg.C for 6 hr to obtain p-n-n type Ni (OH) 2 /NiIn 2 S 4 /ZnIn 2 S 4 Heterojunction materials.
FIG. 1 is an XRD pattern of various samples of the method of the invention for inhibiting the photo-corrosiveness of zinc indium sulfide using an in situ photochemical reaction, from which: small addition of nickel source to NiIn II 2 S 4 /ZnIn 2 S 4 Heterojunction phases are not greatly affected, and all peaks of XRD correspond to hexagonal phase ZnIn 2 S 4 But a distinct cubic phase NiIn appears as the nickel source increases 2 S 4 A peak; after the photocatalytic reaction, niIn 2 S 4 The peaks gradually disappeared and all the peaks regressed to hexagonal phase ZnIn again 2 S 4 Peaks, indicating that NiIn after photochemical reaction 2 S 4 Gradually disappeared and reacted in situ to form other products.
FIG. 2 is a p-n-n Ni (OH) type of method of inhibiting the photo-corrosiveness of zinc indium sulfide using in situ photochemical reaction of the present invention 2 /NiIn 2 S 4 /ZnIn 2 S 4 The narrow scan of Ni element for heterojunction materials, from which it can be seen: ni 2p at 856eV after photocatalytic reaction 3/2 Demonstration of Ni 2+ The presence of valence states.
FIG. 3 is a p-n-n Ni (OH) type of method of inhibiting the photo-corrosiveness of zinc indium sulfide using in situ photochemical reaction according to the invention 2 /NiIn 2 S 4 /ZnIn 2 S 4 The narrow scan of the O element of the heterojunction material, from which it can be seen: the O1s peak after the photocatalytic reaction corresponds to-Ni-OH, confirming Ni (OH) 2 Is present.
FIG. 4 is a Raman diagram of various samples of the method of inhibiting the photo-corrosiveness of zinc indium sulfide using in situ photochemical reaction according to the present invention, from which: all samples had major peaksCorresponding to the main phase ZnIn 2 S 4 But type II NiIn 2 S 4 /ZnIn 2 S 4 Obvious cubic NiIn phase appears in the heterojunction 2 S 4 After the photochemical reaction, the cubic phase NiIn 2 S 4 The peak gradually disappeared.
FIG. 5 is a type II NiIn of the method of inhibiting the photo-corrosiveness of zinc indium sulfide using in situ photochemical reaction of the present invention 2 S 4 /ZnIn 2 S 4 HRTEM diagram of heterojunction intermediate product, from which it can be seen: two groups of obviously different lattice fringes appear in the sample, the distances between the fringes are respectively 0.32nm and 0.202nm, and the fringes correspond to hexagonal phase ZnIn 2 S 4 (102) crystal face and cubic phase NiIn 2 S 4 The (511) crystal face of (C) shows that the product contains the two phase structures.
FIG. 6 is a p-n-n Ni (OH) type of method of inhibiting the photo-corrosiveness of zinc indium sulfide using in situ photochemical reaction of the present invention 2 /NiIn 2 S 4 /ZnIn 2 S 4 The HRTEM diagram of heterojunction material after photocatalytic reaction can be seen from the following: three distinct groups of lattice fringes appear in the sample, the fringe spacing being 0.392nm, 0.244nm and 0.461nm, respectively, corresponding to hexagonal phase ZnIn 2 S 4 (102) crystal face of (a) cubic phase NiIn 2 S 4 (511) crystal face and hexagonal phase Ni (OH) 2 (001) crystal plane indicating that the product after the photochemical reaction contains NiIn 2 S 4 、Ni(OH) 2 ZnIn 2 S 4 Three phase structures.
FIG. 7 shows NiIn type II in the method of inhibiting the photo-corrosiveness of zinc indium sulfide by in situ photochemical reaction 2 S 4 /ZnIn 2 S 4 The heterojunction material hydrogen evolution rate diagram can be known from the following: under the irradiation of visible light, niIn 2 S 4 And the construction of heterojunction has obvious influence on hydrogen evolution performance, wherein the hydrogen production rate of the optimal sample is 3409.4 mu mol.g -1 ·h -1 About pure phase ZnIn 2 S 4 6.6 times of hydrogen production rate.
FIG. 8 illustrates the inhibition of sulfur by in situ photochemical reactions in accordance with the present inventionP-n-n type Ni (OH) for zinc indium oxide photo-etching method 2 /NiIn 2 S 4 /ZnIn 2 S 4 Heterojunction hydrogen evolution rate plot, from which it can be seen: under the irradiation of visible light, the hydrogen evolution rate is obviously improved, wherein the hydrogen production rate of the optimal sample is 5480.5 mu mol.g -1 ·h -1 About pure phase ZnIn 2 S 4 10.6 times of hydrogen production rate.
FIG. 9 is a p-n-n Ni (OH) type of method of inhibiting the photo-corrosiveness of zinc indium sulfide using in situ photochemical reaction according to the invention 2 /NiIn 2 S 4 /ZnIn 2 S 4 Heterojunction material and pure-phase ZnIn 2 S 4 From the hydrogen evolution cycle repeatability curve of (2): under the irradiation of visible light, p-n-n type Ni (OH) 2 /NiIn 2 S 4 /ZnIn 2 S 4 After the third cycle, the hydrogen evolution amount of the heterojunction material increased to 157%, and then the hydrogen evolution amount increased remained around 145%, indicating ZnIn 2 S 4 The photo-corrosiveness is obviously inhibited; however, pure phase ZnIn 2 S 4 The hydrogen evolution amount after the fourth illumination cycle is reduced by 12.7%, which indicates that the pure phase ZnIn 2 S 4 Is severely photo-corrosive.
FIG. 10 is an ICP-MS diagram of different samples of the method of inhibiting the photo-corrosiveness of zinc indium sulfide using in situ photochemical reaction according to the present invention, from which: along with the extension of illumination time, pure-phase ZnIn 2 S 4 Zn of (2) 2+ The ion precipitation amount gradually increases; and NiIn type II 2 S 4 /ZnIn 2 S 4 Heterojunction with Ni (OH) 2 Generating, zn 2+ The ion elution amount increases slightly and then decreases, indicating the Ni (OH) with the decrease 2 Generating, for Zn 2+ The ion precipitation has obvious inhibition effect.
Table 1: pure phase ZnIn 2 S 4 Type II NiIn 2 S 4 /ZnIn 2 S 4 Heterojunction and p-n-n type Ni (OH) 2 /NiIn 2 S 4 /ZnIn 2 S 4 Transient photocurrent cracking rate statistics for heterojunction materials:
note that:
table 1 is a statistical table of the transient photocurrent density cracking rate after 8 cycles for different samples of the method of the present invention for inhibiting the photocrosivity of zinc indium sulfide using in situ photochemical reactions, as follows: pure phase ZnIn 2 S 4 The transient photocurrent density cracking rate reaches 27.78%, and the II type NiIn 2 S 4 /ZnIn 2 S 4 Heterojunction cracking rate was 18.51%, while p-n-n type Ni (OH) 2 /NiIn 2 S 4 /ZnIn 2 S 4 The cracking rate of the heterojunction material is-14.81%, which shows that the photo-corrosiveness is obviously improved.
The embodiments of the present invention have been described above, but the embodiments of the present invention are only illustrative of the present invention and not limiting the present invention, and the scope of the present invention is pointed out in the claims. Thus, without departing from the basic idea of the invention, only the p-n-n type Ni (OH) is prepared by this method 2 /NiIn 2 S 4 /ZnIn 2 S 4 Heterojunction should be considered to fall within the scope of the present invention. The upper and lower limits and interval values of the raw materials, and the upper and lower limits and interval values of the process parameters (time, temperature, etc.) of the present invention can be realized, and are not listed here.
Claims (9)
1. A method for inhibiting the photo-corrosiveness of zinc indium sulfide by utilizing in-situ photochemical reaction, which is characterized by comprising the following steps: adding a nickel source, an indium source and a sulfur source into a mixed solvent of ethylene glycol and N, N-dimethylformamide, stirring uniformly, transferring the solution into a reaction kettle for hydrothermal reaction, and centrifugally separating, cleaning and drying the product after the reaction is finished; dispersing the dried product in water, ultrasonic treating for a period of time, adding zinc chloride, indium nitrate and thioacetamide, stirring to dissolve, and then carrying out water bath reaction to finish the reactionThen centrifugally separating, cleaning and drying the product to obtain the II-type NiIn 2 S 4 /ZnIn 2 S 4 A heterojunction material; for type II NiIn 2 S 4 /ZnIn 2 S 4 Carrying out photochemical treatment on the heterojunction to enable part of n-type NiIn 2 S 4 In situ formation of p-type Ni (OH) 2 The material finally obtains the p-n-n type Ni (OH) 2 /NiIn 2 S 4 /ZnIn 2 S 4 And a heterojunction.
2. The method for inhibiting the photo-corrosiveness of zinc indium sulfide according to claim 1, wherein the p-n-n type Ni (OH) with good photo-activity and photo-corrosiveness resistance is constructed in situ by a simple hydrothermal/water bath/photochemical three-step method 2 /NiIn 2 S 4 /ZnIn 2 S 4 A heterojunction material;
the method comprises the following specific steps:
step 1, stirring and mixing ethylene glycol and N, N-dimethylformamide according to the volume ratio of (0.5-2): 1, and sequentially adding the mixture into a mixed solution of the ethylene glycol and the N, N-dimethylformamide according to the molar ratio of 1 (4-6) of a nickel source to an indium source and a sulfur source with the concentration of 0.01-0.05 mol/L as a standard, and continuously stirring until the mixture is completely dissolved;
step 2, pouring the uniformly mixed solution into a reactor with a Teflon lining, sealing, and then placing the reactor into a baking oven for hydrothermal reaction, wherein the oxidation of reaction products is reduced through glycol in the solution in the hydrothermal reaction process;
step 3, after the hydrothermal reaction is finished, separating out a precipitate through centrifugation, cleaning the precipitate by adopting deionized water and absolute ethyl alcohol in sequence, and then putting the precipitate into an oven for drying to obtain a precursor NiIn 2 S 4 A product;
step 4, converting the zinc source into NiIn according to the molar ratio 2 S 4 Zinc source=0.05-0.3, weighing the NiIn 2 S 4 Adding the precursor product into deionized water, and performing ultrasonic treatment to obtain uniform dispersion;
step 5, converting the concentration of the zinc source to be 0.03-0.1 mol/L as standard, sequentially adding the zinc source, the indium source and the sulfur source into the dispersion liquid according to the molar ratio of 1:2 (4-6), and fully stirring until the zinc source, the indium source and the sulfur source are completely dissolved;
step 6, transferring the solution into a constant-temperature water bath kettle for water bath reaction;
step 7, after the water bath reaction is finished, separating out a precipitate through centrifugation, cleaning the precipitate by deionized water and absolute ethyl alcohol in sequence, and then putting the precipitate into a drying oven for drying, wherein the dried product is the II type NiIn 2 S 4 /ZnIn 2 S 4 A heterojunction;
step 8, weighing the II-type NiIn 2 S 4 /ZnIn 2 S 4 Heterojunction which is dispersed to H in the proportion of 500-800 mg/L 2 Transferring into O solvent, transferring into photochemical reactor, continuously stirring, vacuumizing, washing with nitrogen, turning on light source to make photochemical reaction, and making type II NiIn 2 S 4 /ZnIn 2 S 4 Partial n-type NiIn in heterojunction 2 S 4 In situ formation of p-type Ni (OH) 2 A material;
step 9, centrifugally separating a product after photochemical reaction, cleaning the product by deionized water and absolute ethyl alcohol in sequence, and then drying in a drying oven to obtain p-n-n type Ni (OH) 2 /NiIn 2 S 4 /ZnIn 2 S 4 And a heterojunction.
3. A method of inhibiting the photo-corrosiveness of zinc indium sulfide using in situ photochemical reactions according to claim 2, wherein: in the step 1, the nickel source is nickel acetylacetonate or nickel chloride, the indium source is indium chloride or indium nitrate, and the sulfur source is thioacetamide or thiourea; the stirring and mixing time of the mixed solution of the glycol and the N, N-dimethylformamide is 0.5-1 h.
4. A method of inhibiting the photo-corrosiveness of zinc indium sulfide using in situ photochemical reactions according to claim 2, wherein: in the step 2, the hydrothermal reaction conditions are as follows: the hydrothermal temperature is 180-220 ℃, and the hydrothermal time is 12-24 h.
5. A method of inhibiting the photo-corrosiveness of zinc indium sulfide using in situ photochemical reactions according to claim 2, wherein: in the steps 3, 7 and 9, the washing times of the deionized water are 3 to 4 times, and the washing times of the absolute ethyl alcohol are 1 to 2 times; the drying conditions are as follows: the drying temperature is 70-80 ℃ and the drying time is 6-10 h.
6. A method of inhibiting the photo-corrosiveness of zinc indium sulfide using in situ photochemical reactions according to claim 2, wherein: in step 4, the precursor NiIn 2 S 4 The ultrasonic time of the dispersion liquid of the product is 1-4 h.
7. A method of inhibiting the photo-corrosiveness of zinc indium sulfide using in situ photochemical reactions according to claim 2, wherein: in the step 5, the zinc source is zinc acetate or zinc chloride, the indium source is indium chloride or indium nitrate, and the sulfur source is thioacetamide or sodium sulfide; the stirring time for sequentially adding the zinc source, the indium source and the sulfur source into the dispersion liquid is 0.5-1 h.
8. A method of inhibiting the photo-corrosiveness of zinc indium sulfide using in situ photochemical reactions according to claim 2, wherein: in the step 6, the temperature of the constant-temperature water bath is 70-100 ℃, and the time of the constant-temperature water bath is 2-6 h.
9. A method of inhibiting the photo-corrosiveness of zinc indium sulfide using in situ photochemical reactions according to claim 2, wherein: in step 8, niIn type II 2 S 4 /ZnIn 2 S 4 Heterojunction addition to H 2 Stirring time in the O solvent is 30min, and vacuumizing time is 15-30 min after transferring to the photochemical reactor; the light source in the photocatalysis reaction process is a 300W xenon lamp; the wavelength of the light source is 420-1100 nm, the illumination time is 2-30 h, and the light intensity is high200-400 mW/cm 2 。
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