CN114086185A - Photoanode film and preparation method and application thereof - Google Patents
Photoanode film and preparation method and application thereof Download PDFInfo
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- CN114086185A CN114086185A CN202210057824.7A CN202210057824A CN114086185A CN 114086185 A CN114086185 A CN 114086185A CN 202210057824 A CN202210057824 A CN 202210057824A CN 114086185 A CN114086185 A CN 114086185A
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- strontium
- salt
- cobalt
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- conductive glass
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- 238000002360 preparation method Methods 0.000 title abstract description 28
- 229910019096 CoTiO3 Inorganic materials 0.000 claims abstract description 48
- 239000011521 glass Substances 0.000 claims abstract description 48
- 239000011259 mixed solution Substances 0.000 claims abstract description 22
- 150000001868 cobalt Chemical class 0.000 claims abstract description 21
- 159000000008 strontium salts Chemical class 0.000 claims abstract description 21
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000001354 calcination Methods 0.000 claims abstract description 20
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 18
- 238000010276 construction Methods 0.000 claims abstract description 9
- 229910002367 SrTiO Inorganic materials 0.000 claims description 35
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 28
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 229910000831 Steel Inorganic materials 0.000 claims description 19
- 239000010959 steel Substances 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 238000005260 corrosion Methods 0.000 claims description 15
- 239000000243 solution Substances 0.000 claims description 14
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 12
- 230000007797 corrosion Effects 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- 229910052712 strontium Inorganic materials 0.000 claims description 11
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 11
- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Chemical compound [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 claims description 10
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 8
- 229910017052 cobalt Inorganic materials 0.000 claims description 8
- 239000010941 cobalt Substances 0.000 claims description 8
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 8
- 239000003599 detergent Substances 0.000 claims description 8
- 229960001484 edetic acid Drugs 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 7
- 150000003839 salts Chemical class 0.000 claims description 7
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 6
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 6
- XJWSAJYUBXQQDR-UHFFFAOYSA-M dodecyltrimethylammonium bromide Chemical compound [Br-].CCCCCCCCCCCC[N+](C)(C)C XJWSAJYUBXQQDR-UHFFFAOYSA-M 0.000 claims description 6
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 6
- 229940011182 cobalt acetate Drugs 0.000 claims description 5
- SCNCIXKLOBXDQB-UHFFFAOYSA-K cobalt(3+);2-hydroxypropane-1,2,3-tricarboxylate Chemical compound [Co+3].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O SCNCIXKLOBXDQB-UHFFFAOYSA-K 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 5
- RXSHXLOMRZJCLB-UHFFFAOYSA-L strontium;diacetate Chemical compound [Sr+2].CC([O-])=O.CC([O-])=O RXSHXLOMRZJCLB-UHFFFAOYSA-L 0.000 claims description 5
- QGAPCDHPGCYAKM-UHFFFAOYSA-H tristrontium;2-hydroxypropane-1,2,3-tricarboxylate Chemical compound [Sr+2].[Sr+2].[Sr+2].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O QGAPCDHPGCYAKM-UHFFFAOYSA-H 0.000 claims description 5
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 3
- 229940045032 cobaltous nitrate Drugs 0.000 claims description 3
- 229910001631 strontium chloride Inorganic materials 0.000 claims description 3
- AHBGXTDRMVNFER-UHFFFAOYSA-L strontium dichloride Chemical compound [Cl-].[Cl-].[Sr+2] AHBGXTDRMVNFER-UHFFFAOYSA-L 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000002203 pretreatment Methods 0.000 claims 1
- 230000002787 reinforcement Effects 0.000 claims 1
- 229910002370 SrTiO3 Inorganic materials 0.000 description 16
- 239000000047 product Substances 0.000 description 15
- 238000004140 cleaning Methods 0.000 description 12
- 238000012360 testing method Methods 0.000 description 12
- 229910052751 metal Inorganic materials 0.000 description 10
- 239000002184 metal Substances 0.000 description 10
- 238000001816 cooling Methods 0.000 description 9
- 238000004210 cathodic protection Methods 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 229910001294 Reinforcing steel Inorganic materials 0.000 description 6
- 238000005536 corrosion prevention Methods 0.000 description 6
- 239000007787 solid Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000005286 illumination Methods 0.000 description 4
- 229910017053 inorganic salt Inorganic materials 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 230000008878 coupling Effects 0.000 description 3
- 238000010168 coupling process Methods 0.000 description 3
- 238000005859 coupling reaction Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000031700 light absorption Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 241000627951 Osteobrama cotio Species 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000000693 micelle Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 239000002073 nanorod Substances 0.000 description 2
- 239000002070 nanowire Substances 0.000 description 2
- 238000006303 photolysis reaction Methods 0.000 description 2
- 230000015843 photosynthesis, light reaction Effects 0.000 description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- RCEAADKTGXTDOA-UHFFFAOYSA-N OS(O)(=O)=O.CCCCCCCCCCCC[Na] Chemical compound OS(O)(=O)=O.CCCCCCCCCCCC[Na] RCEAADKTGXTDOA-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000000627 alternating current impedance spectroscopy Methods 0.000 description 1
- MPMSMUBQXQALQI-UHFFFAOYSA-N cobalt phthalocyanine Chemical compound [Co+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 MPMSMUBQXQALQI-UHFFFAOYSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- -1 light Substances 0.000 description 1
- 230000004298 light response Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000004530 micro-emulsion Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000003335 steric effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Images
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
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
- C23C18/1208—Oxides, e.g. ceramics
- C23C18/1216—Metal oxides
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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
- C23F13/14—Material for sacrificial anodes
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Ceramic Engineering (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrodes For Compound Or Non-Metal Manufacture (AREA)
Abstract
The invention belongs to the technical field of marine building engineering anticorrosion, and particularly relates to a photoanode film and a preparation method and application thereof. The preparation method of the photoanode film comprises the following steps: (1) conducting pretreatment on the conductive glass; (2) placing the conductive surface of the conductive glass pretreated in the step (1) downwards in a mixed solution containing strontium salt, cobalt salt and tetrabutyl titanate, and carrying out hydrothermal reaction; (3) calcining the product obtained by the treatment in the step (2) to obtain SrTiO3‑CoTiO3And (3) a photoanode film. The SrTiO3‑CoTiO3The photoanode film can be used for improving the durability of ocean construction engineering (concrete structures and the like).
Description
Technical Field
The invention belongs to the technical field of marine building engineering anticorrosion, and particularly relates to a photoanode film and a preparation method and application thereof.
Background
In the ocean atmospheric environment, the relative humidity in the air is high, and seawater and salt fog have strong corrosivity to steel, so how to reduce the influence of corrosion and reduce the maintenance cost becomes an important problem which must be considered in design and construction. With the gradual depletion of land resources, the development of marine resources attracts general attention of countries in the world. Therefore, the research on the related technical field is not slow, and especially the prevention and control on the durability, corrosion resistance and corrosion resistance of the marine concrete are all problems to be solved urgently.
The cathodic protection technology is generally applied to the field of corrosion protection of concrete structures in ocean building engineering, and can be divided into sacrificial anode cathodic protection and impressed current cathodic protection. The former uses magnesium or zinc, which is more negative than the reinforcing steel bar potential, as an anode to protect the reinforcing steel bar by corrosion of its own; the latter connects the negative pole of the DC power supply to the protected steel bar and the positive pole to the insoluble auxiliary anode to provide a protective current to protect the steel bar from cathodic polarization. The traditional cathodic protection technology has the defects of loss of a sacrificial anode, energy consumption, environmental pollution and the like. At present, photocathode protection is a relatively new protection technology, and has achieved good effects in the field of metal protection at present. The method can realize the corrosion resistance protection of metal at normal temperature and normal pressure by only using semiconductor photoelectric materials, light, air and water.
However, most of the semiconductor materials used for the current photocathode protection photoanode are ultraviolet light response, which can not be well matched with the solar spectrum, and thus can not effectively utilize solar energy. More importantly, the potential of a conduction band of the photoanode semiconductor material is higher than or slightly lower than the self-corrosion potential of the steel bar, so that photo-generated electrons cannot be rapidly transferred or cannot be transferred to the protected steel bar at all, and the protection effect of photoelectrochemical cathode protection on the steel bar of the concrete structure of the ocean building engineering is not ideal.
Therefore, there is a need to provide an improved solution to the above-mentioned deficiencies of the prior art.
Disclosure of Invention
The invention aims to provide a photo-anode film which can effectively solve or relieve the problem that the photo-anode material used for photo-cathode protection in the prior art has poor corrosion prevention effect on metals used in ocean building engineering.
In order to achieve the above purpose, the invention provides the following technical scheme: the photo-anode film is prepared by adopting a method comprising the following steps: (1) conducting pretreatment on the conductive glass; (2) placing the conductive glass pretreated in the step (1) with the conductive surface facing downwards into a mixed solution containing strontium salt, cobalt salt and tetrabutyl titanate, and carrying out hydrothermal reaction to obtain a product with SrTiO deposited on the surface3-CoTiO3The conductive glass of (1); (3) and (3) calcining the product obtained by the treatment in the step (2) to obtain the photo-anode film.
Preferably, the pretreatment is specifically that the conductive glass is sequentially placed in water containing a detergent, an ethanol solution of NaOH, ethanol and deionized water for ultrasonic cleaning.
Preferably, the time of each ultrasonic cleaning is 10-30 min.
Preferably, the conductive glass is FTO conductive glass or ITO conductive glass.
Preferably, the concentration of the strontium salt is 0.05mmol L-1Or 2 mmoleL-1The concentration of the cobalt salt is 0.05mmol L-1Or 2 mmoleL-1The concentration of the tetrabutyl titanate is 0.01mmol L-1Or 4m mol L-1。
Preferably, the concentration of the strontium salt and the cobalt salt is the same, and the ratio of the sum of the number of moles of strontium in the strontium salt and the number of moles of cobalt in the cobalt salt to the number of moles of titanium in the tetrabutyl titanate is 1: 1.
Preferably, the strontium salt is an inorganic salt or an organic salt containing strontium, and the cobalt salt is an inorganic salt or an organic salt containing cobalt; during the hydrothermal reaction, the mixed solution in the step (2) also contains a morphology control agent.
Preferably, the temperature of the hydrothermal reaction is 90-200 ℃, and the reaction time is 8-24 h.
Preferably, the strontium salt is any one of strontium nitrate, strontium oxynitrate, strontium chloride, strontium acetate and strontium citrate; the cobalt salt is any one of cobalt nitrate, cobaltous nitrate oxide, cobalt chloride, cobalt acetate and cobalt citrate; the morphology control agent is any one of N-polyvinylpyrrolidone, sodium dodecyl sulfate, ethylene diamine tetraacetic acid and dodecyl trimethyl ammonium bromide.
Preferably, the calcining temperature is 450-900 ℃, and the calcining time is 1-24 h.
Preferably, the calcination is carried out in a muffle furnace, and the temperature rise rate is 1-20 ℃/min.
The invention also provides a preparation method of the photo-anode film, which adopts the following technical scheme: the preparation method of the photoanode film comprises the following steps: (1) conducting pretreatment on the conductive glass; (2) placing the conductive glass pretreated in the step (1) with the conductive surface facing downwards into a mixed solution containing strontium salt, cobalt salt and tetrabutyl titanate, and carrying out hydrothermal reaction to obtain a product with SrTiO deposited on the surface3-CoTiO3The conductive glass of (1); (3) and (3) calcining the product obtained by the treatment in the step (2) to obtain the photo-anode film.
The invention also provides the application of the above-mentioned glazing anodic film, which adopts the following technical scheme: the photo-anode film is applied to the corrosion prevention of the steel bars in the ocean construction engineering.
Has the advantages that: SrTiO of the invention3-CoTiO3The preparation method of the photo-anode film can realize the construction of a heterojunction, obviously expand the light absorption and utilization efficiency, improve the separation efficiency of photo-generated charges, improve the corrosion prevention effect of metals in ocean building engineering, and further can be used for improving the durability of ocean building engineering (concrete structures and the like).
SrTiO of the invention3-CoTiO3The preparation method of the photo-anode film adopts a one-step hydrothermal method, wherein the hydrothermal method is to dissolve substances which are insoluble or difficultly soluble under atmospheric conditions by using a high-temperature and high-pressure aqueous solution or react to generate a dissolved product of the substances, and the temperature difference of the solution in an autoclave is controlled to generate convection so as to form a supersaturated state and precipitate crystals. The hydrothermal method provides a method for generating various precursors which cannot be obtained under the normal pressure conditionThe precursor is formed by the processes of dissolution and crystallization in the special physical and chemical environment. The preparation method has the characteristics of simple and easy operation and high and stable product performance.
SrTiO adopted by the invention3The forbidden band width is 3.4eV, the band edge for absorbing the sunlight is theoretically 365nm, and the utilization rate of the light is very low; and CoTiO3The forbidden band width of the solar cell is 2.25eV, and the band edge for absorbing sunlight is theoretically 550nm, so that the light absorption range can be remarkably expanded through the heterojunction structure, and the utilization efficiency of solar energy is improved. SrTiO, on the other hand3The position of the conduction band is-1.26 eV, which is obviously lower than the self-corrosion potential of the steel bar, theoretically, the photoelectric cathodic protection current can be provided for the steel bar, but the cathodic protection effect is poor due to the low light utilization efficiency mentioned above. CoTiO 23In addition to the introduction of (2) to expand the light utilization range, more importantly, its band structure and SrTiO3The energy band structures of the two groups are matched. CoTiO 23The conduction band potential of the electrode is 0.14eV negative to SrTiO3The valence band potential of 2.14eV, so that under illumination, CoTiO3The conduction band electron can be in contact with SrTiO3So that electrons remain in the SrTiO3Enough negative potential is reserved on the conduction band to provide cathodic protection current for the reinforcing steel bar, and meanwhile, a cavity is reserved in the CoTiO3Has enough strong oxidizing power to oxidize the surrounding air or water and realize the closed loop of the electronic path. Thus, the SrTiO of the present invention is used3-CoTiO3The preparation method of the photo-anode film can realize the construction of a heterojunction, obviously expand the light absorption and utilization efficiency, improve the separation efficiency of photo-generated charges, improve the corrosion prevention effect of metals in ocean building engineering, and further can be used for improving the durability of ocean building engineering (concrete structures and the like).
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this application, illustrate embodiments of the invention and, together with the description, serve to explain the invention and not to limit the invention. Wherein:
FIG. 1 shows SrTiO provided in example 1 of the present invention3-CoTiO3Guang YangSEM image of polar film;
fig. 2 is a schematic view of an Open Circuit Potential (OCP) testing apparatus provided in embodiment 1 of the present invention;
FIG. 3 shows SrTiO provided in example 1 of the present invention under intermittent light irradiation3-CoTiO3Photoanode film and SrTiO3Photo-anode film coupled steel bar photo-induced Open Circuit Potential (OCP) test result graph;
FIG. 4 shows SrTiO provided in example 2 of the present invention under intermittent light irradiation3-CoTiO3Photoanode film and SrTiO3Current-voltage (J-V) profile of photoanode film;
FIG. 5 shows SrTiO provided in example 3 of the present invention3-CoTiO3Photoanode film and SrTiO3Ac impedance spectroscopy of the photoanode film;
FIG. 6 shows SrTiO provided in example 4 of the present invention3-CoTiO3Photoanode film and SrTiO3Mott schottky curve of photo-anodic film.
Detailed Description
The technical solutions in the embodiments of the present invention will be described clearly and completely below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments that can be derived by one of ordinary skill in the art from the embodiments given herein are intended to be within the scope of the present invention.
The present invention will be described in detail with reference to examples. It should be noted that the embodiments and features of the embodiments may be combined with each other without conflict.
Aiming at the problem that the existing photocathode protection photoanode material has poor protection effect on metals such as reinforcing steel bars and the like used in ocean building engineering, the invention provides SrTiO3-CoTiO3Photoanode film of said SrTiO3-CoTiO3The photoanode film is prepared by the method comprising the following steps: (1) conducting pretreatment on the conductive glass; (2) placing the conductive glass pretreated in the step (1) in a mixed solution containing strontium salt, cobalt salt and tetrabutyl titanate with the conductive surface facing downwards to obtain the conductive glassSurface deposited with SrTiO3-CoTiO3The conductive glass of (1); (3) calcining the product obtained by the treatment in the step (2) to obtain the SrTiO3-CoTiO3And (3) a photoanode film.
In the preferred embodiment of the invention, the pretreatment is specifically that the conductive glass is sequentially placed in water containing detergent, ethanol solution of NaOH, ethanol and deionized water for ultrasonic cleaning; the time of each ultrasonic cleaning is 10-30 min (for example, 10min, 15min, 20min, 25min or 30 min); the conductive glass is FTO conductive glass or ITO conductive glass. The conductive glass is thoroughly cleaned before the hydrothermal reaction, and the purpose is to improve the adhesive force between the film and the conductive glass generated by the subsequent hydrothermal reaction. Wherein the detergent can be washing powder, soap, washing liquid, etc.
Preferably, the concentration of the strontium salt is 0.05mmol L-1Or 2 mmoleL-1The concentration of the cobalt salt is 0.05mmol L-1Or 2 mmoleL-1The concentration of the tetrabutyl titanate is 0.1mmol L-1Or 4mmol L-1。
In a preferred embodiment of the invention, the ratio of the sum of the number of moles of strontium in the strontium salt and the number of moles of cobalt in the cobalt salt to the number of moles of titanium in the tetrabutyl titanate is 1: 1.
In a preferred embodiment of the present invention, the strontium salt is an inorganic salt or an organic salt containing strontium, and the strontium salt is any one of strontium nitrate, strontium oxynitrate, strontium chloride, strontium acetate, and strontium citrate.
In a preferred embodiment of the invention, the cobalt salt is an inorganic salt or an organic salt containing cobalt, and the cobalt salt is any one of cobalt nitrate, cobaltous nitrate oxide, cobalt chloride, cobalt acetate and cobalt citrate.
In a preferred embodiment of the present invention, the temperature of the hydrothermal reaction is 90 to 200 ℃ (e.g., 90 ℃, 120 ℃, 150 ℃, 180 ℃ or 200 ℃) and the reaction time is 8 to 24 hours (e.g., 8 hours, 12 hours, 16 hours, 20 hours or 24 hours).
In a preferred embodiment of the present invention, during the hydrothermal reaction, the mixed solution of step (2) further contains a morphology control agent.
In a preferred embodiment of the present invention, the morphology controlling agent is a surfactant. The surfactant has amphipathy and can be adsorbed on the surface of a solid, and the steric effect of a long molecular chain can avoid the agglomeration of nano particles; the nano material can be self-assembled into ordered aggregates such as micelles, reverse micelles, micro-emulsion and the like in a solution, and the microenvironment of the aggregates can be used as a template to regulate and control the morphology of the nano material.
In a preferred embodiment of the invention, the morphology control agent is any one of N-polyvinylpyrrolidone, sodium dodecyl sulfate, ethylene diamine tetraacetic acid and dodecyl trimethyl ammonium bromide.
In a preferred embodiment of the invention, the calcination temperature is 450-900 ℃ (for example, 450 ℃, 550 ℃, 650 ℃, 750 ℃, 850 ℃ or 900 ℃), and the calcination time is 1-24 h (for example, 1h, 5h, 10h, 15h, 20h or 24 h); the calcination is carried out in a muffle furnace, and the heating rate is 1-20 ℃/min (for example, 1 ℃/min, 5 ℃/min, 10 ℃/min, 15 ℃/min or 20 ℃/min).
The invention also provides SrTiO3-CoTiO3The preparation method of the photo-anode film adopts the following technical scheme: the method comprises the following steps: (1) conducting pretreatment on the conductive glass; (2) placing the conductive glass pretreated in the step (1) with the conductive surface facing downwards into a mixed solution containing strontium salt, cobalt salt and tetrabutyl titanate, and carrying out hydrothermal reaction to obtain a product with SrTiO deposited on the surface3-CoTiO3The conductive glass of (1); (3) calcining the product obtained by the treatment in the step (2) to obtain the SrTiO3-CoTiO3And (3) a photoanode film.
The invention also provides SrTiO as described above3-CoTiO3The application of the photo-anode film adopts the following technical scheme: SrTiO as described above3-CoTiO3The photo-anode film is applied to the corrosion prevention of the steel bars in the ocean construction engineering.
The SrTiO of the invention is illustrated by the following specific examples3-CoTiO3The photoanode film and its preparation method and application are described in detail.
Example 1
1. SrTiO of this example3-CoTiO3The photoanode film is prepared according to the following method, and comprises the following steps:
(1) pretreating the conductive glass: sequentially putting the FTO conductive glass into beakers containing water solution of detergent, ethanol solution of NaOH, ethanol and deionized water, respectively ultrasonically cleaning for 15min, and cleaning completely (before hydrothermal reaction, the FTO conductive glass needs to be thoroughly cleaned, so as to improve the adhesive force between the film and the glass);
(2) adding strontium nitrate, cobalt nitrate and tetrabutyl titanate into water, stirring, adding N-polyvinylpyrrolidone (PVP), stirring to dissolve, and making into the product containing 0.05mmol L-1Strontium nitrate, 0.05mmol L-1Cobalt nitrate, 0.1mmol L-1Tetrabutyl titanate and 10mmol of N-polyvinylpyrrolidone (PVP) mixed solution, and the mixed solution is poured into a reaction kettle; then placing the FTO conductive glass pretreated in the step (1) into the mixed solution with the conductive surface facing downwards, reacting for 24 hours at 90 ℃, cooling, and cleaning and drying the obtained solid;
(3) putting the product obtained by the treatment in the step (2) into a muffle furnace, heating to 450 ℃ at the temperature rise and fall rate of 10 ℃/min for calcination time of 24 hours, and naturally cooling to room temperature to obtain the SrTiO of the embodiment3-CoTiO3And (3) a photoanode film.
2、SrTiO3Preparation of the photoanode film: omitting only the above SrTiO3-CoTiO3In the preparation method of the photoanode film, the step of adding cobalt nitrate is added, and the rest is the same as the SrTiO of the embodiment (embodiment 1)3-CoTiO3The preparation method of the photo-anode film is the same.
3. The photo-anode film prepared above was subjected to a morphology test, and the results are shown in fig. 1. From the figure, SrTiO can be seen3-CoTiO3The nano-wire/rod array structure has the advantages that the nano-wires/rods are uniformly distributed, and the diameter is about 100-200 nm.
4. The photo-generated cathodic protection test is carried out on the photo-anode film prepared by the method, and the specific test method comprises the following steps:
and (3) respectively coupling the 2 photo-anode films obtained by the preparation with metal, and then carrying out open-circuit potential test. Under intermittent visible light irradiation, the photoelectric cathode protection performance of different photo-anode materials on the reinforcing steel bars is judged by testing the potential change of the prepared photo-anode film after the photo-anode film is coupled with the reinforcing steel bars of the concrete structure of the ocean building engineering.
The conventional three-electrode system is adopted for the photoinduced open circuit potential test, the test device is shown in fig. 2, the test device is a double-electrolytic cell system and is divided into a photolysis cell and a corrosion cell, and the dupont proton exchange membrane (N117) is used for separating two electrolytes while ensuring the ion conduction. The photolysis pool and the corrosion pool both contain 3.5% of NaCl solution by mass fraction, protected metal (steel bars) is placed in the corrosion pool and connected by adopting a traditional three-electrode system, a Pt sheet is used as a Counter Electrode (CE), a Saturated Calomel Electrode (SCE) is used as a Reference Electrode (RE), and the protected steel bars and a photoanode coupling electrode are used as Working Electrodes (WE). Under the irradiation of visible light, the light source is turned on or off every 200 s, and the open-circuit potential change curve of the photo-anode film obtained by the preparation method after the photo-anode film is coupled with metal (steel bar) is tested, and the test result is shown in fig. 3.
As can be seen in fig. 3: SrTiO of this example (example 1) under illumination3The corrosion potential of the steel bar of the photo-anode film is negatively shifted from minus 0.58V to minus 1.16V in a dark state, and the potential negative shift quantity is 580 mV; under the same conditions, SrTiO3The corrosion potential of the coupling steel bar is negatively shifted from minus 0.5V to minus 0.8V in a dark state, and the potential negative shift quantity is 300 mV. This demonstrates the heterojunction architecture, significantly enhances the photocathode protective properties of the composite film.
Example 2
1. SrTiO of this example3-CoTiO3The photoanode film is prepared according to the following method, and comprises the following steps:
(1) pretreating the conductive glass: sequentially putting the FTO conductive glass into a beaker containing an aqueous solution of a detergent, an ethanol solution of NaOH, ethanol and deionized water, ultrasonically cleaning for 15min, and cleaning;
(2) adding strontium acetate, cobalt acetate and tetrabutyl titanate into water, and uniformly stirringMixing, adding sodium dodecyl sulfate, stirring to dissolve, and making into tablet containing 2.0mmol L-1Strontium acetate, 2.0mmol L-1Cobalt acetate, 4mmol L-1A mixed solution of tetrabutyl titanate and 16mmol of lauryl sodium sulfate, and pouring the mixed solution into a reaction kettle; then, adding the FTO conductive glass obtained through pretreatment in the step (1) into the mixed solution with the conductive surface facing downwards, reacting for 12 hours at 150 ℃, cooling, and cleaning and drying the obtained solid;
(3) putting the product obtained by the treatment in the step (2) into a muffle furnace, heating to 650 ℃ at a temperature rise and fall rate of 5 ℃/min, calcining for 12 hours, and naturally cooling to room temperature to obtain the SrTiO of the embodiment3-CoTiO3And (3) a photoanode film.
2、SrTiO3Preparation of the photoanode film: omitting only the above SrTiO3-CoTiO3In the preparation method of the photoanode film, the step of adding cobalt acetate is added, and the rest is the same as the SrTiO of the embodiment (embodiment 2)3-CoTiO3The preparation method of the photo-anode film is the same.
3. The Photo-anode film obtained by the above preparation is subjected to a Photo-induced current-voltage curve (Photo-induced current-voltage current) test under intermittent visible light, which is abbreviated as J-V. The mechanism of the enhancement of the photoelectrochemical properties of the photoanode film was investigated by the J-V curve.
The test results are shown in FIG. 4. from FIG. 4, it can be seen that SrTiO3The current density under a bias of 0.8V was 0.2mA/cm2And SrTiO3-CoTiO3The photo-generated current under the bias of 0.8V is 1.6 mA/cm2This is SrTiO alone3The current density is 8 times, the photo-generated current is obviously increased, and the light utilization efficiency is improved.
Example 3
1. SrTiO of this example3-CoTiO3The photoanode film is prepared according to the following method, and comprises the following steps:
(1) pretreating the conductive glass: sequentially putting the FTO conductive glass into a beaker containing an aqueous solution of a detergent, an ethanol solution of NaOH, ethanol and deionized water, ultrasonically cleaning for 15min, and cleaning;
(2) adding strontium oxynitrate, cobaltous oxynitrate and tetrabutyl titanate into water, stirring uniformly, adding Ethylene Diamine Tetraacetic Acid (EDTA), continuously stirring until the EDTA is dissolved, and preparing to obtain the product containing 0.05mmol L-1Strontium oxynitrate, 0.05mmol L-1Cobalt oxy-nitrate, 0.1mmol L-1A mixed solution of tetrabutyl titanate and 10mmol of Ethylene Diamine Tetraacetic Acid (EDTA), and pouring the mixed solution into a reaction kettle; then, adding the FTO conductive glass into the mixed solution with the conductive surface facing downwards, reacting for 4 hours at 190 ℃, cooling, and cleaning and drying the obtained solid;
(3) putting the product obtained by the treatment in the step (2) into a muffle furnace, increasing and decreasing the temperature at the rate of 8 ℃/min, calcining at 750 ℃ for 12h, and naturally cooling to room temperature to obtain the SrTiO of the embodiment3-CoTiO3And (3) a photoanode film.
2、SrTiO3Preparation of the photoanode film: omitting only the above SrTiO3-CoTiO3In the preparation method of the photoanode film, the step of adding cobalt oxynitrate is added, and the rest is the same as the SrTiO of the embodiment (embodiment 3)3-CoTiO3The preparation method of the photo-anode film is the same.
3. The obtained photoanode film was tested for its alternating current impedance (EIS) and its photo-generated charge separation efficiency, and the experimental results are shown in fig. 5.
As can be seen from fig. 5: under illumination, SrTiO3-CoTiO3The charge transfer resistance of the photoanode film is much lower than that of SrTiO alone3The construction of the heterojunction is shown to significantly enhance the separation efficiency of photo-generated charges.
Example 4
1. SrTiO of this example3-CoTiO3The photoanode film is prepared according to the following method, and comprises the following steps:
(1) pretreating the conductive glass: and sequentially putting the FTO conductive glass into a beaker containing an aqueous solution of a detergent, an ethanol solution of NaOH, ethanol and deionized water, ultrasonically cleaning for 15min, and cleaning.
(2) Adding strontium citrate and citric acid into waterCobalt and tetrabutyl titanate are evenly stirred, dodecyl trimethyl ammonium bromide is added, the mixture is continuously stirred until the mixture is dissolved, and the solution is prepared to contain 0.05mmol L-1Strontium citrate, 0.05mmol L-1Cobalt citrate, 0.1 mmoleL-1A mixed solution of tetrabutyl titanate and 50mmol of Dodecyl Trimethyl Ammonium Bromide (DTAB), and pouring the mixed solution into a reaction kettle; then, adding the FTO conductive glass into the mixed solution with the conductive surface facing downwards, reacting for 8 hours at 120 ℃, cooling, and cleaning and drying the obtained solid;
(3) putting the product obtained by the treatment in the step (2) into a muffle furnace, heating and cooling at the rate of 12 ℃/min, calcining at 850 ℃ for 12h, and naturally cooling to room temperature to obtain SrTiO of the embodiment3-CoTiO3And (3) a photoanode film.
2、SrTiO3Preparation of the photoanode film: only omitting the SrTiO for marine construction engineering metal corrosion prevention3-CoTiO3In the preparation method of the photoanode film, the step of adding the cobalt citrate is added, and the rest is the same as the SrTiO of the embodiment (embodiment 4)3-CoTiO3The preparation method of the photo-anode film is the same.
3. The photo-anodic film obtained was tested for its flat band potential and the mott schottky results are shown in fig. 6.
As can be seen from fig. 6: SrTiO3And SrTiO3-CoTiO3The slope of the mott schottky curves of (a) are all positive values, indicating that they are all n-type semiconductors. Meanwhile, SrTiO3-CoTiO3The flat band potential of the composite material is-1.15V, and the flat band potential of SrTiO3 is-1.12V, which shows that the composite material retains a lower conduction band potential, so that the heterojunction is a Z-type heterojunction. The flat potential is far lower than the self-corrosion potential of the steel bar, so that the cathode protection can be provided for the steel bar in the concrete structure of the ocean building engineering under the illumination.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The photoanode film is characterized by being prepared by adopting a method comprising the following steps:
(1) conducting pretreatment on the conductive glass;
(2) placing the conductive glass pretreated in the step (1) with the conductive surface facing downwards into a mixed solution containing strontium salt, cobalt salt and tetrabutyl titanate, and carrying out hydrothermal reaction to obtain a product with SrTiO deposited on the surface3-CoTiO3The conductive glass of (1);
(3) and (3) calcining the product obtained by the treatment in the step (2) to obtain the photo-anode film.
2. The photoanode film of claim 1, wherein the pre-treatment is specifically that the conductive glass is sequentially placed in water containing a detergent, an ethanol solution of NaOH, ethanol and deionized water for ultrasonic cleaning;
the time of each ultrasonic cleaning is 10-30 min;
the conductive glass is FTO conductive glass or ITO conductive glass.
3. The photoanode film of claim 1, wherein the concentration of the strontium salt is 0.05mmol l-1Or 2 mmoleL-1The concentration of the cobalt salt is 0.05mmol L-1Or 2 mmoleL-1The concentration of the tetrabutyl titanate is 0.1mmol L-1Or 4mmol L-1。
4. The photoanode film of claim 3, wherein the strontium salt and the cobalt salt are at the same concentration, and a ratio of a sum of moles of strontium in the strontium salt and moles of cobalt in the cobalt salt to moles of titanium in the tetrabutyl titanate is 1: 1.
5. The photoanode film of claim 1, wherein the strontium salt is an inorganic or organic salt comprising strontium and the cobalt salt is an inorganic or organic salt comprising cobalt;
during the hydrothermal reaction, the mixed solution in the step (2) also contains a morphology control agent.
6. The photoanode film of claim 1, wherein the hydrothermal reaction is carried out at a temperature of 90 to 200 ℃ for 8 to 24 hours.
7. The photoanode film of claim 5, wherein the strontium salt is any one of strontium nitrate, strontium oxynitrate, strontium chloride, strontium acetate, and strontium citrate;
the cobalt salt is any one of cobalt nitrate, cobaltous nitrate oxide, cobalt chloride, cobalt acetate and cobalt citrate;
the morphology control agent is any one of N-polyvinylpyrrolidone, sodium dodecyl sulfate, ethylene diamine tetraacetic acid and dodecyl trimethyl ammonium bromide.
8. The photoanode film of claim 1, wherein the calcination temperature is 450 to 900 ℃ and the calcination time is 1 to 24 hours;
the calcination is carried out in a muffle furnace, and the heating rate is 1-20 ℃/min.
9. The method for producing a photoanode film according to any one of claims 1 to 8, comprising the steps of:
(1) conducting pretreatment on the conductive glass;
(2) placing the conductive glass pretreated in the step (1) with the conductive surface facing downwards into a mixed solution containing strontium salt, cobalt salt and tetrabutyl titanate, and carrying out hydrothermal reaction to obtain a product with SrTiO deposited on the surface3-CoTiO3The conductive glass of (1);
(3) and (3) calcining the product obtained by the treatment in the step (2) to obtain the photo-anode film.
10. Use of the photoanode film of any of claims 1 to 8 in the corrosion protection of steel reinforcement in marine construction engineering.
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