CN114686892B - Z-type graphene-sulfide composite photo-anode material and preparation method and application thereof - Google Patents
Z-type graphene-sulfide composite photo-anode material and preparation method and application thereof Download PDFInfo
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- CN114686892B CN114686892B CN202210204794.8A CN202210204794A CN114686892B CN 114686892 B CN114686892 B CN 114686892B CN 202210204794 A CN202210204794 A CN 202210204794A CN 114686892 B CN114686892 B CN 114686892B
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- graphene
- sulfide
- manganese
- tin
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- 239000002131 composite material Substances 0.000 title claims abstract description 62
- 239000010405 anode material Substances 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000011521 glass Substances 0.000 claims abstract description 42
- 238000000151 deposition Methods 0.000 claims abstract description 39
- 239000000463 material Substances 0.000 claims abstract description 34
- 239000000758 substrate Substances 0.000 claims abstract description 20
- 239000004567 concrete Substances 0.000 claims abstract description 15
- 150000002500 ions Chemical class 0.000 claims abstract description 12
- 239000007769 metal material Substances 0.000 claims abstract description 10
- AFNRRBXCCXDRPS-UHFFFAOYSA-N tin(ii) sulfide Chemical compound [Sn]=S AFNRRBXCCXDRPS-UHFFFAOYSA-N 0.000 claims abstract description 9
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 43
- 239000011593 sulfur Substances 0.000 claims description 43
- 229910052717 sulfur Inorganic materials 0.000 claims description 43
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical class [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 32
- 230000008021 deposition Effects 0.000 claims description 31
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 28
- 239000000243 solution Substances 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 25
- 239000008367 deionised water Substances 0.000 claims description 25
- 229910021641 deionized water Inorganic materials 0.000 claims description 25
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 238000001035 drying Methods 0.000 claims description 21
- 238000004070 electrodeposition Methods 0.000 claims description 20
- 150000002696 manganese Chemical class 0.000 claims description 20
- 238000002791 soaking Methods 0.000 claims description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 17
- 229910021389 graphene Inorganic materials 0.000 claims description 17
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 16
- 239000003792 electrolyte Substances 0.000 claims description 15
- 239000003115 supporting electrolyte Substances 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 12
- 229910052748 manganese Inorganic materials 0.000 claims description 10
- 239000011572 manganese Substances 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 8
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 8
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical group [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims description 8
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims description 8
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 8
- PQUCIEFHOVEZAU-UHFFFAOYSA-N Diammonium sulfite Chemical compound [NH4+].[NH4+].[O-]S([O-])=O PQUCIEFHOVEZAU-UHFFFAOYSA-N 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 7
- 239000003599 detergent Substances 0.000 claims description 7
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 claims description 7
- 150000003839 salts Chemical class 0.000 claims description 7
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical group [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 6
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 6
- 238000011010 flushing procedure Methods 0.000 claims description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 6
- DPLVEEXVKBWGHE-UHFFFAOYSA-N potassium sulfide Chemical compound [S-2].[K+].[K+] DPLVEEXVKBWGHE-UHFFFAOYSA-N 0.000 claims description 6
- 235000010265 sodium sulphite Nutrition 0.000 claims description 6
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 5
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 5
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 5
- HYZQBNDRDQEWAN-LNTINUHCSA-N (z)-4-hydroxypent-3-en-2-one;manganese(3+) Chemical compound [Mn+3].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O HYZQBNDRDQEWAN-LNTINUHCSA-N 0.000 claims description 4
- OAVRWNUUOUXDFH-UHFFFAOYSA-H 2-hydroxypropane-1,2,3-tricarboxylate;manganese(2+) Chemical compound [Mn+2].[Mn+2].[Mn+2].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O OAVRWNUUOUXDFH-UHFFFAOYSA-H 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- 239000011564 manganese citrate Substances 0.000 claims description 4
- 235000014872 manganese citrate Nutrition 0.000 claims description 4
- 229940097206 manganese citrate Drugs 0.000 claims description 4
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims description 4
- 229910052939 potassium sulfate Inorganic materials 0.000 claims description 4
- 235000011151 potassium sulphates Nutrition 0.000 claims description 4
- YJGJRYWNNHUESM-UHFFFAOYSA-J triacetyloxystannyl acetate Chemical compound [Sn+4].CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O YJGJRYWNNHUESM-UHFFFAOYSA-J 0.000 claims description 4
- YQMWDQQWGKVOSQ-UHFFFAOYSA-N trinitrooxystannyl nitrate Chemical compound [Sn+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YQMWDQQWGKVOSQ-UHFFFAOYSA-N 0.000 claims description 4
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 claims description 3
- CQMNNMLVXSWLCH-UHFFFAOYSA-B 2-hydroxypropane-1,2,3-tricarboxylate;tin(4+) Chemical compound [Sn+4].[Sn+4].[Sn+4].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O CQMNNMLVXSWLCH-UHFFFAOYSA-B 0.000 claims description 3
- 238000005536 corrosion prevention Methods 0.000 claims description 3
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims description 3
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims description 3
- 229940071125 manganese acetate Drugs 0.000 claims description 3
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 239000001103 potassium chloride Substances 0.000 claims description 3
- 235000011164 potassium chloride Nutrition 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- 239000002659 electrodeposit Substances 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims 1
- 239000002253 acid Substances 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 10
- 238000005260 corrosion Methods 0.000 abstract description 9
- 230000007797 corrosion Effects 0.000 abstract description 7
- 230000005764 inhibitory process Effects 0.000 abstract description 2
- CADICXFYUNYKGD-UHFFFAOYSA-N sulfanylidenemanganese Chemical compound [Mn]=S CADICXFYUNYKGD-UHFFFAOYSA-N 0.000 description 18
- 229910000831 Steel Inorganic materials 0.000 description 8
- 239000010959 steel Substances 0.000 description 8
- 238000005286 illumination Methods 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 229910001294 Reinforcing steel Inorganic materials 0.000 description 5
- 150000001450 anions Chemical class 0.000 description 5
- 150000001768 cations Chemical class 0.000 description 5
- 238000004210 cathodic protection Methods 0.000 description 4
- -1 manganese salt Chemical class 0.000 description 4
- 238000000103 photoluminescence spectrum Methods 0.000 description 4
- 239000011150 reinforced concrete Substances 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000010276 construction Methods 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- 230000032683 aging Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 150000003464 sulfur compounds Chemical class 0.000 description 2
- BWLBGMIXKSTLSX-UHFFFAOYSA-N 2-hydroxyisobutyric acid Chemical compound CC(C)(O)C(O)=O BWLBGMIXKSTLSX-UHFFFAOYSA-N 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- 230000010718 Oxidation Activity Effects 0.000 description 1
- 230000010757 Reduction Activity Effects 0.000 description 1
- 239000012080 ambient air Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910001437 manganese ion Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
Classifications
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- 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
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F13/00—Inhibiting corrosion of metals by anodic or cathodic protection
- C23F13/02—Inhibiting corrosion of metals by anodic or cathodic protection cathodic; Selection of conditions, parameters or procedures for cathodic protection, e.g. of electrical conditions
- C23F13/06—Constructional parts, or assemblies of cathodic-protection apparatus
- C23F13/08—Electrodes specially adapted for inhibiting corrosion by cathodic protection; Manufacture thereof; Conducting electric current thereto
- C23F13/12—Electrodes characterised by the material
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/006—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character
- C03C17/007—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character containing a dispersed phase, e.g. particles, fibres or flakes, in a continuous phase
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/3411—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials
- C03C17/3429—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials at least one of the coatings being a non-oxide coating
- C03C17/3464—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials at least one of the coatings being a non-oxide coating comprising a chalcogenide
- C03C17/347—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials at least one of the coatings being a non-oxide coating comprising a chalcogenide comprising a sulfide or oxysulfide
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- 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
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F13/00—Inhibiting corrosion of metals by anodic or cathodic protection
- C23F13/02—Inhibiting corrosion of metals by anodic or cathodic protection cathodic; Selection of conditions, parameters or procedures for cathodic protection, e.g. of electrical conditions
- C23F13/06—Constructional parts, or assemblies of cathodic-protection apparatus
- C23F13/08—Electrodes specially adapted for inhibiting corrosion by cathodic protection; Manufacture thereof; Conducting electric current thereto
- C23F13/20—Conducting electric current to electrodes
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D15/00—Electrolytic or electrophoretic production of coatings containing embedded materials, e.g. particles, whiskers, wires
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2218/00—Methods for coating glass
- C03C2218/10—Deposition methods
- C03C2218/11—Deposition methods from solutions or suspensions
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2218/00—Methods for coating glass
- C03C2218/10—Deposition methods
- C03C2218/11—Deposition methods from solutions or suspensions
- C03C2218/115—Deposition methods from solutions or suspensions electro-enhanced deposition
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- 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
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F2201/00—Type of materials to be protected by cathodic protection
- C23F2201/02—Concrete, e.g. reinforced
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- General Chemical & Material Sciences (AREA)
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Abstract
The application belongs to the technical field of corrosion inhibition of ocean engineering concrete structure metal materials, and particularly relates to a Z-shaped graphene-sulfide composite photo-anode material, and a preparation method and application thereof. The preparation method of the Z-type graphene-sulfide composite photo-anode material comprises the following steps: (1) pretreatment of conductive glass; (2) Electrochemically depositing on the surface of the conductive glass to obtain a graphene-manganese sulfide layer; (3) And (3) taking the sample obtained through the treatment in the step (2) as a substrate, and depositing a tin sulfide layer on the surface ion layer of the graphene-manganese sulfide layer to obtain the Z-type graphene-sulfide composite photo-anode material. The Z-type graphene-sulfide composite photo-anode material can effectively solve or improve the problem that the photo-anode protection material in the prior art has an unsatisfactory protection effect on a metal material of a marine engineering concrete structure, realize high-efficiency photo-cathode protection of the marine engineering structure and improve the durability of a marine engineering structure.
Description
Technical Field
The application belongs to the technical field of corrosion inhibition of ocean engineering concrete structure metal materials, and particularly relates to a Z-shaped graphene-sulfide composite photo-anode material, and a preparation method and application thereof.
Background
The reinforced concrete structure is widely applied to the construction engineering project, and particularly plays a role in building factory buildings and various foundation members. However, due to the self-characteristics of reinforced concrete, the related components are prone to aging over time. The phenomenon not only brings a certain potential safety hazard to engineering projects, but also leads the internal structure to be easily damaged; and a plurality of risks are derived to a certain extent, which is unfavorable for the construction and development of related industries. The aging phenomenon is caused by the corrosion of the steel bars in the concrete. Therefore, how to ensure the corrosion resistance of the reinforced concrete foundation and ensure the basic structure of the reinforced concrete becomes a problem to be solved urgently in the building industry.
The photoelectric cathode protection technology can realize cathode protection by only utilizing solar energy, is a green and environment-friendly cathode protection technology, and is worthy of intensive research and popularization and application. In principle, the protection is provided by photoelectrons generated by a semiconductor photoanode under the excitation of incident light, if the photo-generated electron potential is lower than the self-corrosion potential of metal, the photoelectrons can be transferred to the metal which is electrically connected with the photo-generated electron potential and form enrichment on the surface of the metal, so that the cathodic protection of the metal is realized. Thus, the reducibility of photoelectrons is one of the key factors determining the cathodic protection effect.
The photocathode protection photo-anode mostly adopts a heterojunction mode, so that the light utilization efficiency and the separation efficiency of photo-generated charges are improved, however, at present, most of the heterojunction is a type II heterojunction, but the reduction of photo-generated electrons is reduced at the cost of sacrificing the redox of a semiconductor material, and the photo-generated electrons are difficult to transfer to a steel bar to be protected, so that the cathode protection or the protection effect cannot be provided for the steel bar of the ocean building engineering concrete structure.
Accordingly, there is a need to provide an improved solution to the above-mentioned deficiencies of the prior art.
Disclosure of Invention
The application aims to provide a Z-shaped graphene-sulfide composite photo-anode material and a preparation method and application thereof, so as to solve or improve the problem that the photo-anode material in the prior art cannot realize the unsatisfactory protection effect of a metal material of a marine engineering concrete structure.
In order to achieve the above object, the present application provides the following technical solutions: the preparation method of the Z-type graphene-sulfide composite photo-anode material comprises the following steps: (1) pretreatment of conductive glass; (2) Electrochemically depositing on the surface of the conductive glass to obtain a graphene-manganese sulfide layer; (3) And (3) taking the sample obtained through the treatment in the step (2) as a substrate, and depositing a tin sulfide layer on the surface ion layer of the graphene-manganese sulfide layer to obtain the Z-type graphene-sulfide composite photo-anode material.
Preferably, step (1) comprises: sequentially placing conductive glass in aqueous solution containing detergent, ethanol solution of NaOH, ethanol and deionized water for ultrasonic cleaning, flushing with deionized water after the ultrasonic cleaning is finished, and drying after the flushing is finished; the ultrasonic cleaning time is 10-30min, and the drying temperature is 40-90 ℃.
Preferably, step (2) comprises: and placing the conductive glass serving as a working electrode, platinum serving as a counter electrode and saturated calomel serving as a reference electrode in electrolyte containing manganese salt, a first sulfur source, graphene and supporting electrolyte, and performing constant current electrodeposition to obtain the graphene-manganese sulfide layer on the surface of the conductive glass through electrochemical deposition.
Preferably, in the step (2), the manganese salt is a water-soluble manganese salt, and the water-soluble manganese salt is an inorganic salt containing manganese or an organic salt containing manganese; the first sulfur source is a water-soluble sulfur-containing compound; the constant current electrodeposition process further comprises the step of adding a pH regulator to the electrolyte.
Preferably, the manganese salt is at least one of manganese nitrate, manganese acetate, manganese citrate and manganese acetylacetonate; the first sulfur source is at least one of sodium sulfide, potassium sulfide, thiourea, thioacetamide, sodium sulfite and ammonium sulfite; the supporting electrolyte is at least one of potassium sulfate, potassium chloride, lithium perchlorate and ammonium sulfate; the pH regulator is at least one of hydrochloric acid, sulfuric acid, nitric acid and acetic acid.
Preferably, the constant current electrodeposit has a current density of 0.1-10mA/cm 2 The deposition time is 0.5-6h, the constant current deposition temperature is 20-80 ℃, and the pH of the electrolyte is 3-6; the concentration of the manganese salt, the first sulfur source and the supporting electrolyte are respectively and independently selected from 10mmol/L to 1mol/L, and the mass percentage of the graphene is 1-20wt%.
Preferably, step (3) comprises: A. immersing the substrate in a solution containing a tin salt; B. immersing the sample obtained after the treatment in the step A in a solution containing a second sulfur source; C. b, after the soaking is finished, washing with deionized water; D. drying and cooling to room temperature; E. and (3) circularly carrying out the steps A-D, so that the ion layer deposition of the tin sulfide on the surface of the graphene-manganese sulfide layer can be realized; in the step A, the tin salt is water-soluble tin salt, and the water-soluble tin salt is inorganic salt containing tin or organic salt containing tin; in the step B, the second sulfur source is a water-soluble sulfur-containing compound; the times of the steps A-D are 5-30 times; the order of steps a and B may be reversed.
Preferably, in the step a, the tin salt is at least one of tin nitrate, tin acetate, tin citrate and tin acetylacetonate; in the step B, the second sulfur source is at least one of sodium sulfide, potassium sulfide, thiourea, thioacetamide, sodium sulfite and ammonium sulfite; in steps A and B, the concentration of the tin salt and the second sulfur source are each independently selected from 1-50mmol/L; in the steps A and B, the soaking time is independently selected from 0.5-5min; in the step D, the drying temperature is 60-120 ℃, and the drying time is 1-20min.
The application also provides a Z-type graphene-sulfide composite photo-anode material, which adopts the following technical scheme: the Z-shaped graphene-sulfide composite photo-anode material is prepared by the method.
The application also provides application of the Z-shaped graphene-sulfide composite photo-anode material in corrosion prevention of ocean engineering concrete structure metal materials.
The beneficial effects are that:
the Z-type graphene-sulfide composite photo-anode material can effectively solve or improve the problem that the photo-anode protection material in the prior art has an unsatisfactory protection effect on a metal material of a marine engineering concrete structure, realize high-efficiency photo-cathode protection of the marine engineering structure and improve the durability of a marine engineering structure.
GO-MnS-SnS of the application 2 The preparation of the composite photo-anode material is to deposit SnS by electrochemical deposition of GO-MnS and ionic layer 2 Formed on the surface of conductive glass, the GO-MnS-SnS 2 The heterojunction of the composite photo-anode material is in a Z-type electron transmission mode, so that the redox performance of the composite material can be remarkably improved, the separation efficiency of photo-generated charges is improved, further, the high-efficiency photoelectric cathode protection of the ocean engineering structure concrete reinforcing steel bar can be realized, and the durability of the ocean engineering concrete structure is improved.
GO-MnS-SnS of the application 2 The composite photo-anode material can enable the corrosion potential of the steel bar to be shifted negatively by 0.5V under illumination. Both photoluminescence spectra (PL) and photocurrent-time curves illustrate GO-MnS-SnS 2 The composite photo-anode material effectively improves the separation efficiency of photo-generated electron-hole pairs.
Drawings
The accompanying drawings, which are included to provide a further understanding of the application and are incorporated in and constitute a part of this specification, illustrate embodiments of the application and together with the description serve to explain the application. Wherein:
FIG. 1 shows GO-MnS-SnS as provided in the first embodiment of the application under intermittent illumination 2 Composite photoanode material, mnS-SnS 2 Photoanode material, snS 2 Current-time curves for photoanode material and MnS photoanode material;
FIG. 2 shows a second embodiment of the present application under intermittent illuminationProvided GO-MnS-SnS 2 Composite photoanode material, mnS-SnS 2 Photoanode material, snS 2 Photoluminescence spectra of the photoanode material and MnS photoanode material;
FIG. 3 shows GO-MnS-SnS according to the third embodiment of the present application 2 Electrokinetic polarization curve graph of composite photo-anode material;
FIG. 4 shows GO-MnS-SnS provided by the second, third and fourth embodiments of the present application 2 Current-time curve of the composite photoanode material.
Detailed Description
The following description of the technical solutions in the embodiments of the present application will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present application, but not all embodiments. All other embodiments, which are derived by a person skilled in the art based on the embodiments of the application, fall within the scope of protection of the application.
The present application will be described in detail with reference to examples. It should be noted that, without conflict, the embodiments of the present application and features of the embodiments may be combined with each other.
Aiming at the problem that the protection effect on the metal material of the ocean engineering concrete structure is not ideal in the current photo-anode material for photocathode protection, the application provides a preparation method of a Z-type graphene-sulfide composite photo-anode material, which comprises the following steps: (1) pretreatment of conductive glass; (2) Electrochemical deposition is carried out on the surface of the conductive glass to obtain a graphene-manganese sulfide layer; (3) And (3) taking the sample obtained through the treatment in the step (2) as a substrate, and depositing a tin sulfide layer on the surface ion layer of the graphene-manganese sulfide layer to obtain the Z-type graphene-sulfide composite photo-anode material.
The Z-shaped graphene-sulfide composite photo-anode material prepared by the preparation method of the Z-shaped graphene-sulfide composite photo-anode material can effectively improve/solve the problem that the photo-anode material for photocathode protection in the prior art has an unsatisfactory protection effect on a metal material of a marine engineering concrete structure. This is because MnS (manganese sulfide) and SnS 2 (tin sulfide) has a matched band structure, GO (graphene)The charge transfer capability is further improved by introducing MnS with lower conduction band potential (-1.19V vs. NHE), and SnS 2 Has higher valence band potential (2.04V vs. NHE) and SnS 2 Is lower than the valence band potential of MnS (1.81V vs. NHE), snS 2 The photo-generated electrons on the conduction band can be transferred to the valence band of MnS and are recombined with photo-generated holes on the valence band of MnS, so that Z-shaped electron transmission is formed. Under illumination, GO-MnS-SnS 2 The photo-generated electrons of (2) are enriched on the conduction band of MnS, have high reduction activity, and are easily transferred to the surface of metal (reinforcing steel bar) which is electrically connected with the photo-generated electrons, so as to provide cathodic protection current for the metal (reinforcing steel bar). While at the same time, photo-generated holes remain in SnS 2 The cathode protection device has high oxidation activity on the valence band of the cathode protection device, can oxidize ambient air or water, promotes the whole charge movement loop, and improves the cathode protection effect.
In a preferred embodiment of the present application, step (1) comprises: sequentially placing conductive glass in aqueous solution containing detergent, ethanol solution of NaOH, ethanol and deionized water for ultrasonic cleaning, flushing with deionized water after ultrasonic cleaning is finished, and drying after flushing is finished; the ultrasonic cleaning time is 10-30min (e.g., 10min, 20min or 30 min), and the drying temperature is 40-90deg.C (e.g., 40deg.C, 60deg.C, 80deg.C or 90deg.C).
In a preferred embodiment of the present application, step (2) comprises: and placing the conductive glass serving as a working electrode, platinum serving as a counter electrode and saturated calomel serving as a reference electrode in electrolyte containing manganese salt, a first sulfur source, graphene and supporting electrolyte, and performing constant current electrodeposition to obtain the graphene-manganese sulfide layer on the surface of the conductive glass through electrochemical deposition.
In the preferred embodiment of the application, the manganese salt is water-soluble manganese salt (the electrolyte contains manganese ions), and the water-soluble manganese salt is manganese-containing inorganic salt or manganese-containing organic salt; the first sulfur source is a water-soluble sulfur-containing compound; the constant current electrodeposition may further comprise the step of adding a pH adjuster to the electrolyte.
In a preferred embodiment of the application, the manganese salt is at least one of manganese nitrate, manganese acetate, manganese citrate and manganese acetylacetonate; the first sulfur source is at least one of sodium sulfide, potassium sulfide, thiourea, thioacetamide, sodium sulfite and ammonium sulfite; the supporting electrolyte is at least one of potassium sulfate, potassium chloride, lithium perchlorate and ammonium sulfate; the pH regulator is at least one of hydrochloric acid, sulfuric acid, nitric acid and acetic acid.
In a preferred embodiment of the application, the current density is 0.1-10mA/cm during constant current electrodeposition 2 (e.g., 0.1 mA/cm) 2 、1mA/cm 2 、4mA/cm 2 、8mA/cm 2 Or 10mA/cm 2 ) The deposition time is 0.5-6h (e.g., 0.5h, 1h, 2h, 4h, or 6 h), the constant current deposition temperature is 20-80 ℃ (e.g., 20 ℃,40 ℃,60 ℃, or 80 ℃), and the pH of the electrolyte is 3-6 (e.g., 3, 4, 5, or 6); the concentrations of the manganese salt, the first sulfur source, and the supporting electrolyte are each independently selected from 10mmol/L to 1mol/L (e.g., the concentrations of the manganese salt, the first sulfur source, and the supporting electrolyte are each independently selected from 10mmol/L, 50mmol/L, 100mmol/L, 300mmol/L, 600mmol/L, 900mmol/L, or 1 mol/L), and the mass percent of the graphene is 1-20wt% (e.g., 1wt%, 5wt%, 10wt%, 15wt%, or 20 wt%). Wherein, the current density and the deposition time mainly play a role in regulating the amount of graphene-manganese sulfide products obtained by deposition; the deposition temperature and the pH value can influence the deposition potential, so that the graphene-manganese sulfide product can be ensured to be obtained by deposition; the concentration of manganese salt and sulfur source can affect the amount of graphene-manganese sulfide product deposited; the supporting electrolyte concentration can influence the conductivity of the electrolyte, influence the current magnitude, and further influence the amount of a graphene-manganese sulfide product obtained by deposition; the concentration of graphene mainly influences the doping amount of graphene in the product.
In a preferred embodiment of the present application, step (3) comprises: A. immersing the substrate in a solution containing a tin salt; B. immersing the sample obtained after the treatment in the step A in a solution containing a second sulfur source; C. after the soaking in the step B is finished, washing (removing excessive anions and cations adsorbed on the deionized water); D. drying and cooling to room temperature; E. and (3) circularly carrying out the steps A-D, so that the ion layer deposition of the tin sulfide on the surface of the graphene-manganese sulfide layer can be realized; in the step A, the tin salt is water-soluble tin salt, and the water-soluble tin salt is tin-containing tin-freeAn organic salt or a tin-containing organic salt; in the step B, the second sulfur source is a sulfur compound water-soluble sulfur compound; the number of steps a-D cycles is 5-30 (e.g., 5, 10, 15, 25, or 30). In the process of the steps A and B, the tin salt and the second sulfur source can react rapidly on the surface of the substrate to generate SnS 2 Further, by circularly performing the steps A-D, the ion layer deposition of the tin sulfide on the surface of the graphene-manganese sulfide can be realized. In addition, the sequence of steps A and B can be changed, the cycle sequence after the change of steps A and B is B-A-C-D, and the rest is the same as the above, and the details are not repeated here.
In a preferred embodiment of the present application, in step a, the tin salt is at least one of tin nitrate, tin acetate, tin citrate and tin acetylacetonate; in the step B, the second sulfur source is at least one of sodium sulfide, potassium sulfide, thiourea, thioacetamide, sodium sulfite and ammonium sulfite; in steps A and B, the concentration of the tin salt and the second sulfur source are each independently selected from 1-50mmol/L (e.g., the concentration of the tin salt and the second sulfur source are each independently selected from 1mmol/L, 5mmol/L, 10mmol/L, 20mmol/L, 30mmol/L, 40mmol/L, or 50 mmol/L); in step A, step B, the soaking time is independently selected from 0.5-5min (e.g., 0.5min, 1min, 2min, 3min, 4min, or 5 min); in step D, the drying temperature is 60-120deg.C (e.g., 60deg.C, 80deg.C, 100deg.C, or 120deg.C), and the drying time is 1-20min (e.g., 1min, 5min, 10min, 15min, or 20 min). Wherein the tin salt and the second sulfur source are responsible for the formation of a product (SnS 2 ) The amount of (2) has an influence.
The application also provides a Z-type graphene-sulfide composite photo-anode material, which is prepared by adopting the method.
The application also provides application of the Z-shaped graphene-sulfide composite photo-anode material in corrosion prevention of ocean engineering concrete structure metal materials.
The Z-type graphene-sulfide composite photo-anode material, the preparation method and the application thereof are described in detail through specific examples.
Example 1
1. The Z-type graphene-sulfide composite (GO-MnS-SnS) 2 ) The photo-anode material is prepared by the following steps:
(1) Pretreatment of conductive glass: before electrochemical deposition, the conductive glass (FTO conductive glass) needs to be thoroughly cleaned to improve the bonding strength between the photo-anode film and the conductive glass. Firstly, the conductive glass is put into a beaker containing aqueous solution of detergent, ethanol solution of NaOH, ethanol and deionized water in sequence, and is ultrasonically cleaned for 10min, and is dried at 60 ℃ for standby after being washed clean by the deionized water.
(2) Electrochemical deposition of GO-MnS: the FTO conductive glass, pt and saturated calomel obtained in the step (1) are respectively used as a working electrode, a counter electrode and a reference electrode, a solution containing manganese nitrate (manganese salt) with the final concentration of 10mmol/L, sodium sulfide (first sulfur source) with the final concentration of 10mmol/L, 1wt% graphene and potassium sulfate (supporting electrolyte) with the final concentration of 100mmol/L is used as electrolyte, the pH value is adjusted to 3 by hydrochloric acid, and constant current (current density is 0.1 mA/cm) is used at 20 DEG C 2 ) And depositing for 6 hours, washing with deionized water, and drying after washing is finished for later use.
(3) Preparation of GO-MnS-SnS by ion layer deposition 2 : A. soaking the sample obtained in the step (2) serving as a substrate in 1mmol/L tin nitrate (tin salt) solution for 5min; B. immersing the sample obtained after the treatment in the step A in a solution containing 1mmol/L sodium sulfide (second sulfur source) for 5min; C. after the soaking in the step B is finished, washing a film sample substrate (the sample obtained after the treatment in the step B) by a large amount of deionized water to remove redundant anions and cations adsorbed on the film sample substrate; D. drying at 60deg.C for 20min, and cooling to room temperature; E. steps a-D are repeated in sequence (i.e. steps a-D are cycled). One alternate soaking (A-D) is regarded as one deposition period (one cycle), 30 deposition periods (cycles) are followed to obtain the Z-type graphene-sulfide composite (GO-MnS-SnS) 2 ) A photoanode material.
2、MnS-SnS 2 The photo-anode material is prepared by the following steps: with the GO-MnS-SnS 2 The composite photoanode materials differ only in: and (3) omitting the addition of the graphene in the step (2), and keeping the rest consistent.
3、SnS 2 The photo-anode material is prepared according to the following method: with the GO-MnS-SnS 2 The composite photoanode materials differ only in: step (2) is omitted, and the rest are kept consistent.
4. The MnS photo-anode material is prepared by the following method: with the GO-MnS-SnS 2 The composite photoanode materials differ only in: and (3) omitting the addition of the graphene in the step (2) and the step (3), and keeping the rest consistent.
5. Under intermittent illumination, the obtained GO-MnS-SnS is measured 2 Composite photoanode material, mnS-SnS 2 Photoanode material, snS 2 The current-time curves of the photoanode material and MnS photoanode material are shown in fig. 1.
As can be seen from fig. 1: snS (SnS) 2 The photocurrent density of the photo-anode material was 5. Mu.A/cm 2 The photocurrent density of the MnS photo-anode material is 10 mu A/cm 2 ，MnS-SnS 2 The photocurrent density of the photo-anode material was 20. Mu.A/cm 2 And GO-MnS-SnS 2 The current density of the composite photo-anode material is more than 35 mu A/cm 2 . This suggests GO-MnS-SnS 2 The construction of the Z-shaped heterojunction in the composite photo-anode material remarkably improves the separation efficiency of photo-generated electrons and holes, thereby improving the photo-generated current density.
Example two
1. The Z-type graphene-sulfide composite (GO-MnS-SnS) 2 ) The photo-anode material is prepared by the following steps:
(1) Pretreatment of conductive glass: before electrochemical deposition, the conductive glass (FTO conductive glass) needs to be thoroughly cleaned to improve the bonding strength between the photo-anode film and the conductive glass. Firstly, the conductive glass is put into a beaker containing aqueous solution of detergent, ethanol solution of NaOH, ethanol and deionized water in sequence, and is ultrasonically cleaned for 30min, washed by deionized water, and dried at 40 ℃ for later use.
(2) Electrochemical deposition of GO-MnS: the FTO conductive glass, pt and saturated calomel obtained in the step (1) are respectively used as a working electrode, a counter electrode and a reference electrode to contain chloridizing with the final concentration of 1mol/LManganese (manganese salt), 500mmol/L thiourea (first sulfur source), 5wt% graphene and 1mol/L ammonium sulfate (supporting electrolyte) were used as an electrolyte and the pH was adjusted to 6 with sulfuric acid at 80℃with constant current (current density of 10 mA/cm) 2 ) After 0.5h of deposition, the mixture is washed by deionized water and dried for standby.
(3) Preparation of GO-MnS-SnS by ion layer deposition 2 : A. soaking the sample obtained in the step (2) serving as a substrate in a solution of 50mmol/L tin acetate (tin salt) for 0.5min; B. immersing the sample obtained after the treatment in the step A in a solution containing 50mmol/L thiourea (second sulfur source) for 0.5min; C. after the soaking in the step B is finished, washing a film sample substrate (the sample obtained after the treatment in the step B) by a large amount of deionized water to remove redundant anions and cations adsorbed on the film sample substrate; D. drying at 120deg.C for 1min, and cooling to room temperature; E. steps a-D are repeated in sequence (i.e. steps a-D are cycled). One alternate soaking (A-D) is regarded as one deposition period (one cycle), and after 10 deposition periods (cycles), the Z-type graphene-sulfide composite (GO-MnS-SnS) of the embodiment is obtained 2 ) A photoanode material.
2、MnS-SnS 2 The photo-anode material is prepared by the following steps: with the GO-MnS-SnS 2 The composite photoanode materials differ only in: and (3) omitting the addition of the graphene in the step (2), and keeping the rest consistent.
3、SnS 2 The photo-anode material is prepared according to the following method: with the GO-MnS-SnS 2 The composite photoanode materials differ only in: step (2) is omitted, and the rest are kept consistent.
4. The MnS photo-anode material is prepared by the following method: with the GO-MnS-SnS 2 The composite photoanode materials differ only in: and (3) omitting the addition of the graphene in the step (2) and the step (3), and keeping the rest consistent.
5. For the obtained GO-MnS-SnS 2 Composite photoanode material, mnS-SnS 2 Photoanode material, snS 2 Photo-anode material and MnS photo-anode material were subjected to photoluminescence spectrum test, and the test results are shown in fig. 2.
As can be seen from fig. 2: mnS-SnS 2 The strength of the photoanode material is much lower than that of the photoanode material aloneSnS 2 Photo-anode material and MnS photo-anode material, GO-MnS-SnS 2 The strength of the composite photo-anode material is the lowest; description of MnS and SnS 2 Is matched with the energy band structure, and the introduced GO further reduces the resistance of charge transfer, snS 2 The photo-generated electrons on the guide band can be transferred to and react with the valence band of MnS, so that photo-generated electron holes are respectively remained in the guide band and SnS of MnS 2 And the valence band of the electron-hole photo-generated is efficiently separated.
Example III
1. The Z-type graphene-sulfide composite (GO-MnS-SnS) 2 ) The photo-anode material is prepared by the following steps:
(1) Pretreatment of conductive glass: before electrochemical deposition, the conductive glass (FTO conductive glass) needs to be thoroughly cleaned to improve the bonding strength between the photo-anode film and the conductive glass. Firstly, the conductive glass is put into a beaker containing aqueous solution of detergent, ethanol solution of NaOH, ethanol and deionized water in sequence, and is ultrasonically cleaned for 15min, and is dried at 90 ℃ for standby after being washed clean by the deionized water.
(2) Electrochemical deposition of GO-MnS: the FTO conductive glass, pt and saturated calomel obtained in the step (1) are respectively used as a working electrode, a counter electrode and a reference electrode, a solution containing 100mmol/L final concentration of manganese acetylacetonate (manganese salt), 1mol/L ammonium sulfite (first sulfur source), 10wt% graphene and 10mmol/L ammonium sulfate (supporting electrolyte) is used as electrolyte, the pH is adjusted to 4 by nitric acid, and a constant current (current density is 5 mA/cm) is used at 60 DEG C 2 ) After 1h of deposition, the solution is washed by deionized water and dried after washing is finished for standby.
(3) Preparation of GO-MnS-SnS by ion layer deposition 2 : A. soaking the sample obtained in the step (2) serving as a substrate in a tin (tin salt) citrate solution with the concentration of 25mmol/L for 2min; B. immersing the sample obtained after the treatment in the step A in a solution containing 20mmol/L ammonium sulfite (second sulfur source) for 2min; C. after the soaking in the step B is finished, washing a film sample substrate (the sample obtained after the treatment in the step B) by a large amount of deionized water to remove redundant anions and cations adsorbed on the film sample substrate; D. drying at 80deg.C for 20min, and cooling to room temperature; E. sequentially repeating the stepsSteps a-D (i.e., steps a-D are cycled). One alternate soaking (A-D) is regarded as one deposition period (one cycle), and after 15 deposition periods (cycles), the Z-type graphene-sulfide composite (GO-MnS-SnS) of the embodiment is obtained 2 ) A photoanode material.
2. Under the irradiation of simulated sunlight, the prepared GO-MnS-SnS is tested 2 Judging the GO-MnS-SnS of the embodiment by using an electrokinetic polarization curve of the coupled composite photo-anode material and ocean constructional engineering concrete structure steel bar (Q235) 2 The photocathode protection performance of the composite photoanode material on the reinforcing steel bar (Q235) is shown in the test result of FIG. 3.
As can be seen from fig. 3, the self-corrosion potential of the steel bar (Q235) is-0.6 v vs. Coupling GO-MnS-SnS of the third example 2 The corrosion potential of the steel bar (Q235) of the composite photo-anode material is negatively shifted to about-1.0V vs. SCE under the illumination, and the corrosion potential of the steel bar (Q235) is negatively shifted by more than 400 mV, which shows that the GO-MnS-SnS of the third embodiment 2 The composite photo-anode material has a good cathode protection effect.
Example IV
1. The Z-type graphene-sulfide composite (GO-MnS-SnS) 2 ) The photo-anode material is prepared by the following steps:
(1) Pretreatment of conductive glass: before electrochemical deposition, the conductive glass (FTO conductive glass) needs to be thoroughly cleaned to improve the bonding strength between the photo-anode film and the conductive glass. Firstly, the conductive glass is put into a beaker containing aqueous solution of detergent, ethanol solution of NaOH, ethanol and deionized water in sequence, and is ultrasonically cleaned for 20min, and is dried at 60 ℃ for standby after being washed clean by the deionized water.
(2) Electrochemical deposition of GO-MnS: the FTO conductive glass, pt and saturated calomel obtained in the step (1) are respectively used as a working electrode, a counter electrode and a reference electrode, a solution containing 500mmol/L final concentration of manganese citrate (manganese salt), 500mmol/L thioacetamide (first sulfur source), 20wt% of graphene and 100mmol/L supporting electrolyte is used as electrolyte, the pH is adjusted to 5 by acetic acid, and a constant current (current density is 3 mA/cm) is used at 50 DEG C 2 ) After 3h of deposition, the wafer is rinsed with deionized water and after rinsingAnd drying for standby after finishing.
(3) Preparation of GO-MnS-SnS by ion layer deposition 2 : A. soaking the sample obtained in the step (2) serving as a substrate in 15mmol/L of a tin acetonate (tin salt) solution for 3.5min; B. immersing the sample obtained after the treatment in the step A in a solution containing 35mmol/L thioacetamide (second sulfur source) for 3.5min; C. after the soaking in the step B is finished, washing a film sample substrate (the sample obtained after the treatment in the step B) by a large amount of deionized water to remove redundant anions and cations adsorbed on the film sample substrate; D. drying at 100deg.C for 10min, and cooling to room temperature; E. steps a-D are repeated in sequence (i.e. steps a-D are cycled). One alternate soaking (A-D) is regarded as one deposition period (one cycle), and after 25 deposition periods (cycles), the Z-type graphene-sulfide composite (GO-MnS-SnS) of the embodiment is obtained 2 ) A photoanode material.
Experimental example
GO-MnS-SnS obtained in examples two, three and four, respectively 2 The photocurrent-time curve of the composite photoanode material was tested and the test results are shown in fig. 4.
From fig. 4, it can be seen that: the photocurrent density of the different embodiments can be greater than 35 muA/cm under illumination 2 Can provide good cathodic protection effect for the reinforcing steel bars.
The above description is only of the preferred embodiments of the present application and is not intended to limit the present application, but various modifications and variations can be made to the present application by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application should be included in the protection scope of the present application.
Claims (6)
- The preparation method of the 1.Z graphene-sulfide composite photo-anode material is characterized by comprising the following steps of: (1) pretreatment of conductive glass; (2) Electrochemically depositing on the surface of the conductive glass to obtain a graphene-manganese sulfide layer; (3) Depositing a tin sulfide layer on the surface ion layer of the graphene-manganese sulfide layer by taking the sample treated in the step (2) as a substrate to obtain the Z-type graphene-sulfide composite photo-anode material;the step (2) comprises: placing conductive glass serving as a working electrode, platinum serving as a counter electrode and saturated calomel serving as a reference electrode in electrolyte containing manganese salt, a first sulfur source, graphene and supporting electrolyte, and performing constant current electrodeposition to obtain a graphene-manganese sulfide layer on the surface of the conductive glass by electrochemical deposition;in the step (2), the manganese salt is water-soluble manganese salt, and the water-soluble manganese salt is manganese-containing inorganic salt or manganese-containing organic salt; the first sulfur source is a water-soluble sulfur-containing compound; the constant current electrodeposition process further comprises the step of adding a pH regulator into the electrolyte;the constant current electrodeposit has a current density of 0.1-10mA/cm 2 The deposition time is 0.5-6h, the constant current deposition temperature is 20-80 ℃, and the pH of the electrolyte is 3-6; the concentration of the manganese salt, the first sulfur source and the supporting electrolyte are respectively and independently selected from 10mmol/L to 1mol/L, and the mass percentage of the graphene is 1-20wt%;the step (3) comprises: A. immersing the substrate in a solution containing a tin salt; B. immersing the sample obtained after the treatment in the step A in a solution containing a second sulfur source; C. b, after the soaking is finished, washing with deionized water; D. drying and cooling to room temperature; E. and (3) circularly carrying out the steps A-D, so that the ion layer deposition of the tin sulfide on the surface of the graphene-manganese sulfide layer can be realized;in the step A, the tin salt is water-soluble tin salt, and the water-soluble tin salt is inorganic salt containing tin or organic salt containing tin; in the step B, the second sulfur source is a water-soluble sulfur-containing compound; the times of the steps A-D are 5-30 times; the order of the steps A and B can be exchanged;in steps A and B, the concentration of the tin salt and the second sulfur source are each independently selected from 1-50mmol/L; in the steps A and B, the soaking time is independently selected from 0.5-5min; in the step D, the drying temperature is 60-120 ℃, and the drying time is 1-20min.
- 2. The method for preparing a Z-type graphene-sulfide composite photoanode material according to claim 1, wherein step (1) includes: sequentially placing conductive glass in aqueous solution containing detergent, ethanol solution of NaOH, ethanol and deionized water for ultrasonic cleaning, flushing with deionized water after the ultrasonic cleaning is finished, and drying after the flushing is finished;the ultrasonic cleaning time is 10-30min, and the drying temperature is 40-90 ℃.
- 3. The method for preparing the Z-type graphene-sulfide composite photo-anode material according to claim 1,the manganese salt is at least one of manganese nitrate, manganese acetate, manganese citrate and manganese acetylacetonate;the first sulfur source is sodium sulfide, potassium sulfide, thiourea, thioacetamide, sodium sulfite and sulfurAt least one of ammonium acid;the supporting electrolyte is at least one of potassium sulfate, potassium chloride, lithium perchlorate and ammonium sulfate;the pH regulator is at least one of hydrochloric acid, sulfuric acid, nitric acid and acetic acid.
- 4. The method for preparing a Z-type graphene-sulfide composite photoanode material according to claim 1, wherein in the step a, the tin salt is at least one of tin nitrate, tin acetate, tin citrate, and tin acetylacetonate;in the step B, the second sulfur source is at least one of sodium sulfide, potassium sulfide, thiourea, thioacetamide, sodium sulfite and ammonium sulfite.
- 5. A Z-shaped graphene-sulfide composite photo-anode material, wherein the Z-shaped graphene-sulfide composite photo-anode material is prepared by the method according to any one of claims 1 to 4.
- 6. The application of the Z-shaped graphene-sulfide composite photo-anode material in corrosion prevention of a metal material of a marine engineering concrete structure according to claim 5.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
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| KR20140145678A (en) * | 2013-06-13 | 2014-12-24 | 주식회사 포스코 | Method for electrophoretic deposition of nano-ceramics for the photo-generated non-sacrificial cathodic corrosion protection of metal substrates and the metal substrate thereof |
| WO2018024183A1 (en) * | 2016-08-01 | 2018-02-08 | 福建新峰二维材料科技有限公司 | Method for preparing three-dimensional graphene/mos2 composite material |
| CN108365185A (en) * | 2018-01-09 | 2018-08-03 | 上海大学 | The preparation method of porous manganese sulfide and graphene composite material |
| CN109735847A (en) * | 2019-02-02 | 2019-05-10 | 青岛大学 | AgInS for photoproduction cathodic protection2/ graphene/TiO2Nano composite membrane light anode and preparation and application |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR20140145678A (en) * | 2013-06-13 | 2014-12-24 | 주식회사 포스코 | Method for electrophoretic deposition of nano-ceramics for the photo-generated non-sacrificial cathodic corrosion protection of metal substrates and the metal substrate thereof |
| WO2018024183A1 (en) * | 2016-08-01 | 2018-02-08 | 福建新峰二维材料科技有限公司 | Method for preparing three-dimensional graphene/mos2 composite material |
| CN108365185A (en) * | 2018-01-09 | 2018-08-03 | 上海大学 | The preparation method of porous manganese sulfide and graphene composite material |
| CN109735847A (en) * | 2019-02-02 | 2019-05-10 | 青岛大学 | AgInS for photoproduction cathodic protection2/ graphene/TiO2Nano composite membrane light anode and preparation and application |
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