CN113293382B - BiVO 4 MnOOH film electrode, preparation method thereof and application thereof in photo-generated cathode corrosion prevention - Google Patents
BiVO 4 MnOOH film electrode, preparation method thereof and application thereof in photo-generated cathode corrosion prevention Download PDFInfo
- Publication number
- CN113293382B CN113293382B CN202011204756.XA CN202011204756A CN113293382B CN 113293382 B CN113293382 B CN 113293382B CN 202011204756 A CN202011204756 A CN 202011204756A CN 113293382 B CN113293382 B CN 113293382B
- Authority
- CN
- China
- Prior art keywords
- bivo
- electrode
- film electrode
- mnooh
- bismuth
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 229910003174 MnOOH Inorganic materials 0.000 title claims abstract description 63
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 238000005536 corrosion prevention Methods 0.000 title claims abstract description 12
- 239000010408 film Substances 0.000 claims abstract description 60
- 239000010409 thin film Substances 0.000 claims abstract description 53
- 239000000243 solution Substances 0.000 claims abstract description 51
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 105
- 229910052797 bismuth Inorganic materials 0.000 claims description 33
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 33
- FSJSYDFBTIVUFD-SUKNRPLKSA-N (z)-4-hydroxypent-3-en-2-one;oxovanadium Chemical compound [V]=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O FSJSYDFBTIVUFD-SUKNRPLKSA-N 0.000 claims description 28
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- 238000001354 calcination Methods 0.000 claims description 27
- 239000011259 mixed solution Substances 0.000 claims description 26
- 229910000416 bismuth oxide Inorganic materials 0.000 claims description 22
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 claims description 22
- 230000008021 deposition Effects 0.000 claims description 20
- 239000011521 glass Substances 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 17
- 239000011248 coating agent Substances 0.000 claims description 16
- 238000000576 coating method Methods 0.000 claims description 16
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 16
- 239000007864 aqueous solution Substances 0.000 claims description 15
- 239000003513 alkali Substances 0.000 claims description 13
- 238000002791 soaking Methods 0.000 claims description 13
- 239000000758 substrate Substances 0.000 claims description 13
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 11
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 11
- 235000002867 manganese chloride Nutrition 0.000 claims description 11
- 239000011565 manganese chloride Substances 0.000 claims description 11
- 229940099607 manganese chloride Drugs 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 claims description 10
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N dimethyl sulfoxide Natural products CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 9
- 239000003792 electrolyte Substances 0.000 claims description 9
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 8
- 239000000010 aprotic solvent Substances 0.000 claims description 8
- 229910052697 platinum Inorganic materials 0.000 claims description 8
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 8
- JHXKRIRFYBPWGE-UHFFFAOYSA-K bismuth chloride Chemical compound Cl[Bi](Cl)Cl JHXKRIRFYBPWGE-UHFFFAOYSA-K 0.000 claims description 3
- 229910000380 bismuth sulfate Inorganic materials 0.000 claims description 3
- BEQZMQXCOWIHRY-UHFFFAOYSA-H dibismuth;trisulfate Chemical compound [Bi+3].[Bi+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O BEQZMQXCOWIHRY-UHFFFAOYSA-H 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 238000005260 corrosion Methods 0.000 abstract description 22
- 230000007797 corrosion Effects 0.000 abstract description 16
- 239000007769 metal material Substances 0.000 abstract description 13
- 238000005215 recombination Methods 0.000 abstract description 4
- 230000006798 recombination Effects 0.000 abstract description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 abstract description 3
- 238000010521 absorption reaction Methods 0.000 abstract description 3
- 239000000969 carrier Substances 0.000 abstract description 3
- 239000010406 cathode material Substances 0.000 abstract description 3
- 239000000460 chlorine Substances 0.000 abstract description 3
- 229910052801 chlorine Inorganic materials 0.000 abstract description 3
- 238000002347 injection Methods 0.000 abstract description 3
- 239000007924 injection Substances 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 3
- 238000001228 spectrum Methods 0.000 abstract description 3
- 239000010963 304 stainless steel Substances 0.000 description 20
- 229910000589 SAE 304 stainless steel Inorganic materials 0.000 description 20
- 230000008878 coupling Effects 0.000 description 14
- 238000010168 coupling process Methods 0.000 description 14
- 238000005859 coupling reaction Methods 0.000 description 14
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 238000001816 cooling Methods 0.000 description 4
- 238000005286 illumination Methods 0.000 description 4
- 229910052720 vanadium Inorganic materials 0.000 description 4
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 4
- 230000005622 photoelectricity Effects 0.000 description 3
- 230000001681 protective effect Effects 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 238000009210 therapy by ultrasound Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000001548 drop coating Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 229910001935 vanadium oxide Inorganic materials 0.000 description 2
- 229910002915 BiVO4 Inorganic materials 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 1
- 230000010718 Oxidation Activity Effects 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 229910000963 austenitic stainless steel Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910001451 bismuth ion Inorganic materials 0.000 description 1
- 238000004210 cathodic protection Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- -1 hydroxide ions Chemical class 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 229910001437 manganese ion Inorganic materials 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Images
Classifications
-
- 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
-
- 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
-
- 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
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/04—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material
- C23C28/042—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material including a refractory ceramic layer, e.g. refractory metal oxides, ZrO2, rare earth oxides
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D9/00—Electrolytic coating other than with metals
- C25D9/04—Electrolytic coating other than with metals with inorganic materials
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Metallurgy (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Mechanical Engineering (AREA)
- Ceramic Engineering (AREA)
- Electrochemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Electroplating And Plating Baths Therefor (AREA)
- Hybrid Cells (AREA)
Abstract
The invention provides a BiVO 4 A preparation method of a/MnOOH film electrode belongs to the technical field of anticorrosive materials. BiVO obtained by the invention 4 the/MnOOH thin-film electrode can absorb visible light, so that the absorption range of a photo-solar spectrum is effectively widened; the load of MnOOH accelerates BiVO under open-circuit potential 4 The hole transfer speed on the surface of the electrode reduces the recombination rate of current carriers, and when the cathode material is used for corrosion prevention of a photo-generated cathode, the injection efficiency of photo-generated electrons to the cathode metal material can be greatly increased, and the negative shift of the self-corrosion potential of the cathode metal material is effectively promoted, so that the corrosion resistance of the cathode metal material in a chlorine-containing environment is enhanced. At the same time, the load of MnOOH avoids BiVO 4 The direct contact between the photoelectrode and the solution avoids BiVO 4 Thereby improving BiVO 4 Stability of/MnOOH thin film electrode.
Description
Technical Field
The invention relates to the technical field of anticorrosive materials, and particularly relates to BiVO 4 A MnOOH film electrode, a preparation method thereof and application thereof in photo-generated cathode corrosion prevention.
Background
The corrosion phenomenon of metal materials is ubiquitous in life, and not only pollution and waste of resources are caused, but also various potential threats exist. The traditional electrochemical corrosion prevention technology, such as impressed current and cathodic protection of a sacrificial anode, can realize the corrosion prevention function of metal by an impressed energy or sacrificial anode method, but the method consumes a large amount of electric energy and anode materials, and is not beneficial to industrial application. The photoelectrochemistry anticorrosion technology utilizes solar energy to drive photo-generated electrons on a semiconductor photo-anode to be transferred to metal so as to achieve the metal corrosion inhibition effect, does not sacrifice the photo-anode, has low cost and long service life, and has important application value in the future.
BiVO as a potential photo-generated cathode anti-corrosion electrode material 4 The material not only has a proper band gap structure (Eg ≈ 2.4 eV), can drive the water oxidation reaction under the drive of visible light, but also has a relatively negative conduction band potential, and is favorable for the transfer of electrons to a protective metal in thermodynamics. However, biVO 4 The electron hole recombination rate of the electrode is high, the water oxidation activity is poor, and BiVO is caused 4 The photoinduced charge separation and transfer capability is weak, so that the transfer of photoproduction electrons to protective metal is difficult to be effectively driven, and the photoproduction cathode protection capability of the metal is limited. Furthermore, biVO 4 The electrode has low stability and is easy to generate chemical corrosion and photo-corrosion.
Disclosure of Invention
In view of the above, the present invention is to provide a BiVO 4 The invention relates to a/MnOOH film electrode, a preparation method thereof and application thereof in photo-generated cathode corrosion prevention, and BiVO provided by the invention 4 the/MnOOH film electrode has good stability and good photoproduction cathode protection performance.
In order to achieve the purpose of the invention, the invention provides the following technical scheme:
the invention provides a BiVO 4 the/MnOOH thin film electrode comprises BiVO 4 Film substrate and BiVO loaded on the film substrate 4 And a MnOOH layer on the surface of the film substrate.
Preferably, the BiVO 4 The thickness of the film electrode is 1-300 μm; the thickness of the MnOOH layer is 1-50 mu m.
The invention provides a BiVO 4 The preparation method of the/MnOOH thin-film electrode comprises the following steps:
(1) Providing BiVO 4 A thin film electrode;
(2) Taking manganese chloride solution as electrolyte, and adopting a three-electrode system to carry out photoelectric deposition, wherein a working electrode in the three-electrode system is BiVO 4 Film electrode to obtain BiVO 4 a/MnOOH thin film electrode.
Preferably, the reference electrode in the three-electrode system is a silver chloride electrode, the counter electrode is a platinum mesh electrode, and the light source is simulated sunlight.
Preferably, the molar concentration of the manganese chloride solution is 0.1-1 mol/L.
Preferably, the photoelectric deposition is constant current deposition, and the current density of the photoelectric deposition is 1-50 muA/cm 2 The deposition time is 5-60 min.
Preferably, the BiVO 4 The preparation method of the thin film electrode comprises the following steps:
(1) Mixing a soluble bismuth source with a citric acid aqueous solution to obtain a bismuth source citric acid mixed solution;
coating the bismuth source citric acid mixed solution on the surface of FTO glass, and performing first calcination to obtain a bismuth oxide thin film electrode on the surface of the FTO glass;
(2) Mixing vanadyl acetylacetonate with an aprotic solvent to obtain a vanadyl acetylacetonate solution;
coating the vanadyl acetylacetonate solution on the surface of the bismuth oxide film electrode, and sequentially carrying out secondary calcination and alkali liquor soaking to obtain BiVO 4 And a thin film electrode.
Preferably, the soluble bismuth source is one or more of bismuth nitrate, bismuth chloride and bismuth sulfate;
the molar concentration of the citric acid aqueous solution is 0.1-1 mol/L; the molar concentration of the bismuth source in the bismuth source citric acid mixed solution is 0.01-1 mol/L; the coating amount of the bismuth source citric acid mixed solution coated on the surface of the FTO glass is 40-80 mu L/cm 2 (ii) a The temperature of the first calcination is 500-650 ℃ and the time is1～6h。
Preferably, the aprotic solvent is dimethyl sulfoxide; the molar concentration of the vanadyl acetylacetonate solution is 0.3-1 mol/L; the coating amount of the vanadyl acetylacetonate solution on the surface of the bismuth oxide film electrode is 60-120 mu L/cm 2 (ii) a The temperature of the second calcination is 400-600 ℃, and the time is 1-6 h; the alkali liquor is 1mol/L sodium hydroxide solution, and the soaking time of the alkali liquor is 20-60 min.
The invention provides the BiVO 4 The application of the/MnOOH film electrode in photo-generated cathode corrosion prevention.
The invention provides a BiVO 4 a/MnOOH thin film electrode comprising BiVO 4 A film substrate and BiVO loaded on the film substrate 4 And a MnOOH layer on the surface of the film substrate. BiVO provided by the invention 4 the/MnOOH thin-film electrode can absorb visible light, so that the absorption range of a photo-solar spectrum is effectively widened; the load of MnOOH accelerates BiVO under open-circuit potential 4 The hole transfer speed on the surface of the electrode reduces the recombination rate of current carriers, and when the cathode material is used for corrosion prevention of a photo-generated cathode, the injection efficiency of photo-generated electrons to a cathode metal material can be greatly increased, and the negative shift of a self-corrosion potential of the cathode metal material is effectively promoted, so that the corrosion resistance of the cathode metal material in a chlorine-containing environment is enhanced. Meanwhile, mnOOH has good corrosion resistance, and the load of MnOOH avoids BiVO 4 The direct contact between the photoelectrode and the solution avoids BiVO 4 Thereby improving BiVO 4 Stability of/MnOOH thin film electrode.
The invention provides a BiVO 4 The method for preparing the/MnOOH film electrode loads the MnOOH layer on the BiVO by adopting a three-electrode system to carry out photoelectric deposition 4 The method has the advantages of simple operation, low cost and easy realization of industrialized mass production.
Drawings
FIG. 1 shows BiVO obtained in example 1 4 Open circuit potential-time curve diagram of MnOOH film electrode;
FIG. 2 is BiVO in example 2 4 304 stainless steel coupling electrode and BiVO 4 /MnOOH-304 stainless SteelOpen circuit potential-time curve graph of the steel coupling electrode under dark state and illumination;
FIG. 3 shows 304 stainless steel and BiVO under irradiation of visible light in example 3 4 304 stainless steel coupling electrode, biVO 4 Polarization curve diagram of MnOOH-304 stainless steel coupling electrode.
Detailed Description
The invention provides a BiVO 4 the/MnOOH thin film electrode comprises BiVO 4 Film substrate and BiVO loaded on the film substrate 4 And a MnOOH layer on the surface of the film substrate. In the invention, the BiVO 4 The thickness of the thin-film electrode is preferably 1 to 300 μm, more preferably 50 to 200 μm; the thickness of the MnOOH layer is preferably 1 to 50 μm, and more preferably 10 to 40 μm.
In the invention, the BiVO 4 the/MnOOH thin-film electrode can absorb visible light, so that the absorption range of a photo-solar spectrum is effectively widened; biVO under open-circuit potential is accelerated by MnOOH load 4 The hole transfer speed on the surface of the electrode reduces the recombination rate of current carriers, and when the cathode material is used for corrosion prevention of a photo-generated cathode, the injection efficiency of photo-generated electrons to a cathode metal material can be greatly increased, and the negative shift of a self-corrosion potential of the cathode metal material is effectively promoted, so that the corrosion resistance of the cathode metal material in a chlorine-containing environment is enhanced. Meanwhile, mnOOH has good corrosion resistance, and the load of the MnOOH avoids BiVO 4 The direct contact between the photoelectrode and the solution avoids BiVO 4 Thereby improving BiVO 4 Stability of/MnOOH thin film electrode.
The invention provides the BiVO 4 The preparation method of the/MnOOH thin-film electrode comprises the following steps:
(1) Providing BiVO 4 A thin film electrode;
(2) Taking manganese chloride solution as electrolyte, and adopting a three-electrode system to carry out photoelectric deposition, wherein a working electrode in the three-electrode system is BiVO 4 Film electrode to obtain BiVO 4 a/MnOOH thin film electrode.
The invention firstly provides BiVO 4 And a thin film electrode. In the invention, the BiVO 4 Preparation method of film electrode optimization bagThe method comprises the following steps:
(1) Mixing a soluble bismuth source with a citric acid aqueous solution to obtain a bismuth source citric acid mixed solution;
coating the bismuth source citric acid mixed solution on the surface of FTO glass, and performing first calcination to obtain a bismuth oxide thin film electrode on the surface of the FTO glass;
(2) Mixing vanadyl acetylacetonate with an aprotic solvent to obtain a vanadyl acetylacetonate solution;
coating the vanadyl acetylacetonate solution on the surface of the bismuth oxide film electrode, and sequentially carrying out secondary calcination and alkali liquor soaking to obtain BiVO 4 And a thin film electrode.
The method comprises the step of mixing a soluble bismuth source with a citric acid aqueous solution to obtain a bismuth source citric acid mixed solution. In the invention, the soluble bismuth source is preferably one or more of bismuth nitrate, bismuth chloride and bismuth sulfate, and is more preferably bismuth nitrate; the molar concentration of the aqueous citric acid solution is preferably 0.1 to 1mol/L, and more preferably 0.4 to 0.6mol/L. In the present invention, the mixing is preferably ultrasonic mixing; the power of the ultrasonic mixing is preferably 200-600W, more preferably 300-500W; the time is preferably 1 to 6 hours, more preferably 2 to 4 hours; according to the invention, through the ultrasonic mixing, the soluble bismuth source is completely dissolved in the citric acid aqueous solution. In the present invention, the molar concentration of bismuth ions in the bismuth-source citric acid mixed solution is preferably 0.01 to 1mol/L, and more preferably 0.1 to 0.5mol/L.
After the bismuth source citric acid mixed solution is obtained, the bismuth source citric acid mixed solution is coated on the surface of FTO glass, first calcination is carried out, and the bismuth oxide film electrode is obtained on the surface of the FTO glass. In the present invention, the coating is preferably performed by drop coating; in the laboratory protocol of the present invention, the dispensing is preferably performed using a pipette. In the invention, the coating amount of the bismuth source citric acid mixed solution coated on the surface of the FTO glass is preferably 40-80 mu L/cm 2 More preferably 50 to 70. Mu.L/cm 2 . The present invention preferably performs the first calcination in a muffle furnace; the temperature of the first calcination is preferably 500 to 650 ℃, more preferably 550 to 600 ℃, and the time is preferably 1 to 6 hours, more preferably2 to 4 hours. According to the invention, through the first calcination, organic matters in the mixed solution can be removed, and the bismuth source is converted into bismuth oxide.
The invention mixes vanadyl acetylacetonate with an aprotic solvent to obtain vanadyl acetylacetonate solution. In the present invention, the aprotic solvent is preferably dimethyl sulfoxide. The invention does not require any particular mixing means, such as stirring, known to the person skilled in the art. In the present invention, the molar concentration of the vanadyl acetylacetonate solution is preferably 0.3 to 1mol/L, and more preferably 0.5 to 0.8mol/L.
After the vanadyl acetylacetonate solution is obtained, the surface of the bismuth oxide film electrode is coated with the vanadyl acetylacetonate solution, and then secondary calcination and alkali liquor soaking are sequentially carried out to obtain BiVO 4 And a thin film electrode. In the present invention, the coating is preferably performed by drop coating; in the laboratory protocol of the present invention, the dispensing is preferably performed using a pipette. In the invention, the coating amount of the vanadyl acetylacetonate solution on the surface of the bismuth oxide film electrode is preferably 60-120 mu L/cm 2 More preferably 80 to 100. Mu.L/cm 2 . The invention preferably performs the second calcination in a muffle furnace; the temperature of the second calcination is preferably 400-600 ℃, and more preferably 450-550 ℃; the time is preferably 1 to 6 hours, more preferably 2 to 4 hours. According to the invention, through the second calcination, vanadyl acetylacetonate can be decomposed into vanadium oxide, and then the vanadium oxide and bismuth oxide generated by the first calcination are subjected to high-temperature solid-phase reaction and converted into bismuth vanadate.
The invention preferably carries out the alkali liquor soaking after cooling. In the invention, the alkali liquor is preferably sodium hydroxide solution with the concentration of 1mol/L; the time for soaking in the alkali liquor is preferably 20-60 min, and more preferably 30-50 min. The invention can remove the excessive V in the film electrode by soaking in the alkali liquor 2 O 5 . After the alkaline solution is soaked, the membrane electrode is preferably cleaned by deionized water and naturally dried in the air.
Obtaining the BiVO 4 After the film electrode, the invention takes manganese chloride solution as electrolyte and adopts a three-electrode systemPerforming photoelectric deposition, wherein the working electrode in the three-electrode system is the BiVO 4 Film electrode to obtain BiVO 4 a/MnOOH thin film electrode. In the invention, the reference electrode in the three-electrode system is a silver chloride electrode, the counter electrode is a platinum mesh electrode, and the light source is simulated sunlight. The invention has no special requirements on the types and specifications of the silver chloride electrode and the platinum mesh electrode, and the silver chloride electrode and the platinum mesh electrode which are well known by the technical personnel in the field can be used.
In the present invention, the molar concentration of the manganese chloride solution is preferably 0.1 to 1mol/L, more preferably 0.2 to 0.8mol/L, and still more preferably 0.5mol/L; in the invention, the photoelectric deposition is preferably constant current deposition, and the current density of the photoelectric deposition is preferably 1-50 mu A/cm 2 More preferably 10 to 40. Mu.A/cm 2 The deposition time is preferably 5 to 60min, more preferably 15 to 40min. The invention uses the photoelectric deposition to deposit BiVO 4 The surface of the thin film electrode is loaded with a MnOOH layer in situ to obtain BiVO 4 a/MnOOH thin film electrode. In the process of the photoelectric deposition, biVO 4 The thin film electrode generates a hole with strong oxidizing property, divalent manganese ions in the solution are oxidized into trivalent manganese, and the trivalent manganese reacts with hydroxide ions in the solution to generate MnOOH.
The invention provides the BiVO adopting the scheme 4 The application of the/MnOOH film electrode in photo-generated cathode corrosion prevention. In the present invention, the cathode metal material in the application is preferably stainless steel or metallic copper; the stainless steel is preferably 304 stainless steel or austenitic stainless steel.
In the present invention, the method of application is preferably:
BiVO (bismuth oxide) is added 4 the/MnOOH film electrode is connected with the cathode metal material through a lead to obtain a coupling electrode;
subjecting the BiVO to 4 the/MnOOH film electrode is arranged in the photo-anode pool, and the cathode metal material is arranged in the corrosion pool; the photo-anode pool and the corrosion pool are connected through a salt bridge.
And placing the coupling electrode under the condition of irradiating visible light.
In the invention, the electrolyte in the photoanode cell is preferably 1mol/L NaOH solution; the electrolyte in the corrosion cell is preferably a 3.5wt% NaCl solution.
BiVO provided by the invention is combined with the embodiment 4 the/MnOOH thin-film electrode, the preparation method thereof and the application thereof in the corrosion prevention of a photoproduction cathode are explained in detail, but the invention is not to be construed as limiting the protection scope of the invention.
Example 1
(1) Adding bismuth nitrate solid into 0.1mol/L citric acid aqueous solution, and performing ultrasonic treatment for 2h at the power of 300W to dissolve bismuth nitrate to obtain 0.3mol/L bismuth source citric acid mixed solution;
transferring the bismuth source citric acid mixed solution to the surface of FTO glass by using a liquid transfer gun, and dripping the mixed solution to the surface of the FTO glass with the dripping amount of 40 mu L/cm 2 Then calcining for 2 hours at 550 ℃ to obtain a bismuth oxide film electrode;
(2) Mixing vanadyl acetylacetonate with dimethyl sulfoxide solution to obtain 0.3mol/L vanadyl acetylacetonate solution, and transferring the vanadyl acetylacetonate solution by using a liquid transfer gun to drop on a bismuth oxide film electrode with the dropping amount of 60 mu L/cm 2 Calcining at 500 deg.C for 2 hr in a muffle furnace, naturally cooling to room temperature, taking out the membrane electrode, soaking in 1mol/L sodium hydroxide solution for 20min, and removing excessive V 2 O 5 To obtain BiVO 4 A thin film electrode;
(3) Preparing 0.3mol/L manganese chloride aqueous solution by using BiVO 4 The thin film electrode is used as a working electrode, ag/AgCl is used as a reference electrode, a platinum mesh electrode is used as a counter electrode, simulated sunlight is used as a light source to irradiate the working electrode, and the thickness of the working electrode is 2 mu A/cm 2 The constant current photoelectricity is deposited for 10min to obtain BiVO 4 a/MnOOH thin film electrode.
The obtained BiVO 4 the/MnOOH film electrode is placed in 1mol/L NaOH solution, the open-circuit potential of the electrode at different time is tested, and the obtained open-circuit potential-time curve chart is shown in figure 1. As can be seen from FIG. 1, biVO was observed after illumination 4 The open circuit potential change of the/MnOOH film electrode is small within the time range of 12 hours of illumination, which fully shows that the BiVO prepared by the invention 4 the/MnOOH film electrode is stableHigh qualitative, can realize long-time stable operation without reducing the photo-generated corrosion resistance.
Example 2
(1) Adding bismuth nitrate solid into 0.2mol/L citric acid aqueous solution, and performing ultrasonic treatment for 2h at the power of 300W to dissolve bismuth nitrate to obtain 0.5mol/L bismuth source citric acid mixed solution;
transferring the bismuth source citric acid mixed solution to the surface of FTO glass by using a liquid transfer gun, wherein the dropping amount is 80 mu L/cm 2 Then calcining for 2 hours at 550 ℃ to obtain a bismuth oxide film electrode;
(2) Mixing vanadyl acetylacetonate with dimethyl sulfoxide solution to obtain vanadium source solution with concentration of 0.5mol/L, and transferring the vanadium source solution by using a liquid transfer gun to drop on a bismuth oxide film electrode, wherein the dropping amount is 80 mu L/cm 2 Calcining at 450 deg.C for 2 hr in muffle furnace, naturally cooling to room temperature, taking out the film electrode, soaking in 1mol/L sodium hydroxide solution for 30min, and removing excessive V 2 O 5 To obtain BiVO 4 A thin film electrode;
(3) Preparing 0.2mol/L manganese chloride aqueous solution by using BiVO 4 The thin film electrode is used as a working electrode, ag/AgCl is used as a reference electrode, a platinum mesh electrode is used as a counter electrode, simulated sunlight is used as a light source to irradiate the working electrode, and the thickness of the working electrode is 5 mu A/cm 2 The constant current photoelectricity is deposited for 15min to obtain BiVO 4 a/MnOOH thin film electrode.
The obtained BiVO 4 the/MnOOH film electrode is connected with 304 stainless steel through a copper wire to prepare BiVO 4 a/MnOOH-304 stainless steel coupling electrode, in which BiVO 4 the/MnOOH film electrode is arranged in a photo-anode pool, and electrolytes in the photo-anode pool are 1mol/L NaOH and 1mol/L Na 2 S, mixed aqueous solution; the 304 stainless steel is placed in a corrosion tank, and the electrolyte in the corrosion tank is 3.5wt% of NaCl solution; the photo-anode pool and the corrosion pool are connected through a salt bridge.
Using the BiVO obtained in step (2) 4 The film electrode is connected with 304 stainless steel according to the method to prepare BiVO 4 304 stainless steel coupling electrodes as control group.
BiVO 4 -304 stainless steel couplingPolar and BiVO 4 The open circuit potential-time curve of the/MnOOH-304 stainless steel coupling electrode in the dark state and the illumination is shown in figure 2. In the dark state, the open circuit potential is positive, and when visible light irradiates, the open circuit potential of the coupling electrode is shifted negatively, and finally the stable state is achieved. However, biVO 4 The open circuit potential of the/MnOOH-304 stainless steel coupling electrode is more negative, which shows that BiVO 4 The ratio of the protective action of the/MnOOH thin film electrode on the photocathode of 304 stainless steel to BiVO 4 The thin film electrode is more preferable.
Example 3
(1) Adding bismuth nitrate solid into 0.2mol/L citric acid aqueous solution, and performing ultrasonic treatment for 2h at the power of 300W to dissolve bismuth nitrate to obtain 0.4mol/L bismuth source citric acid mixed solution;
transferring the bismuth source citric acid mixed solution to the surface of FTO glass by using a liquid transfer gun, and dripping the mixed solution to the surface of the FTO glass with the dripping amount of 60 mu L/cm 2 Then calcining for 3h at 600 ℃ to obtain a bismuth oxide film electrode;
(2) Mixing vanadyl acetylacetonate with dimethyl sulfoxide solution to obtain vanadium source solution with concentration of 0.2mol/L, and transferring the vanadium source solution by using a liquid transfer gun to drop on a bismuth oxide film electrode, wherein the dropping amount is 100 mu L/cm 2 Calcining at 500 deg.C for 3 hr in muffle furnace, naturally cooling to room temperature, taking out the film electrode, soaking in 1mol/L sodium hydroxide solution for 40min, and removing excess V 2 O 5 To obtain BiVO 4 A thin film electrode;
(3) Preparing 0.5mol/L manganese chloride aqueous solution as BiVO 4 The thin film electrode is used as a working electrode, ag/AgCl is used as a reference electrode, a platinum mesh electrode is used as a counter electrode, simulated sunlight is used as a light source to irradiate the working electrode, and the thickness of the working electrode is 3 mu A/cm 2 The constant current photoelectricity is deposited for 20min to obtain BiVO 4 a/MnOOH thin film electrode.
The obtained BiVO 4 /MnOOH film electrode and BiVO obtained in step (2) 4 The film electrodes are respectively connected with 304 stainless steel to be used as coupling electrodes, and the 304 stainless steel and the BiVO are respectively tested under the irradiation of visible light 4 304 stainless steel coupling electrode, biVO 4 Tafel polarization curve of/MnOOH-304 stainless steel coupling electrode, obtainedThe results are shown in FIG. 3. As can be seen from FIG. 3, the self-etching potential of 304 stainless steel in the 3.5wt% NaCl solution was-206 mV, when 304 stainless steel in the etching cell and BiVO in the photoanode cell were etched 4 After connection, the corrosion potential is negatively shifted to-345 mV to be connected with BiVO 4 The self-corrosion potential after the/MnOOH thin film electrode is coupled is more negative and reaches-447 mV, and the results fully show that the load of MnOOH is helpful for improving BiVO 4 And the photo-anode protects the stainless steel.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and amendments can be made without departing from the principle of the present invention, and these modifications and amendments should also be considered as the protection scope of the present invention.
Claims (9)
1. BiVO 4 the/MnOOH thin film electrode comprises BiVO 4 Film substrate and BiVO loaded on the film substrate 4 A MnOOH layer on the surface of the film substrate;
the BiVO 4 The preparation method of the/MnOOH film electrode comprises the following steps:
(1) Providing BiVO 4 A thin film electrode;
(2) Taking manganese chloride solution as electrolyte, and adopting a three-electrode system to carry out photoelectric deposition, wherein a working electrode in the three-electrode system is BiVO 4 Film electrode to obtain BiVO 4 a/MnOOH thin film electrode;
BiVO 4 The preparation method of the thin film electrode comprises the following steps:
(1) Mixing a soluble bismuth source with a citric acid aqueous solution to obtain a bismuth source citric acid mixed solution;
coating the bismuth source citric acid mixed solution on the surface of FTO glass, and performing first calcination to obtain a bismuth oxide thin film electrode on the surface of the FTO glass;
(2) Mixing vanadyl acetylacetonate with an aprotic solvent to obtain a vanadyl acetylacetonate solution;
coating the vanadyl acetylacetonate solution on the surface of the bismuth oxide film electrode, sequentially carrying out secondary calcination and alkali liquor soaking,obtaining BiVO 4 And a thin film electrode.
2. BiVO according to claim 1 4 the/MnOOH thin film electrode is characterized in that the BiVO 4 The thickness of the film substrate is 1 to 300 mu m; the thickness of the MnOOH layer is 1 to 50 mu m.
3. BiVO according to claim 1 or 2 4 The preparation method of the/MnOOH thin-film electrode is characterized by comprising the following steps:
(1) Providing BiVO 4 A thin film electrode;
(2) Taking manganese chloride solution as electrolyte, and adopting a three-electrode system to carry out photoelectric deposition, wherein a working electrode in the three-electrode system is BiVO 4 Film electrode to obtain BiVO 4 a/MnOOH thin film electrode;
BiVO 4 The preparation method of the thin film electrode comprises the following steps:
(1) Mixing a soluble bismuth source with a citric acid aqueous solution to obtain a bismuth source citric acid mixed solution;
coating the bismuth source citric acid mixed solution on the surface of FTO glass, and performing first calcination to obtain a bismuth oxide thin film electrode on the surface of the FTO glass;
(2) Mixing vanadyl acetylacetonate with an aprotic solvent to obtain a vanadyl acetylacetonate solution;
coating the vanadyl acetylacetonate solution on the surface of the bismuth oxide film electrode, and sequentially carrying out secondary calcination and alkali liquor soaking to obtain BiVO 4 And a thin film electrode.
4. The preparation method according to claim 3, wherein the reference electrode in the three-electrode system is a silver chloride electrode, the counter electrode is a platinum mesh electrode, and the light source is simulated sunlight.
5. The method according to claim 3, wherein the molar concentration of the manganese chloride solution is 0.1 to 1mol/L.
6. The method for preparing the solar cell, wherein the photoelectric deposition is constant current deposition, and the current density of the photoelectric deposition is 1 to 50 μ A/cm 2 The deposition time is 5 to 60min.
7. The preparation method of claim 3, wherein the soluble bismuth source is one or more of bismuth nitrate, bismuth chloride and bismuth sulfate;
the molar concentration of the citric acid aqueous solution is 0.1 to 1mol/L; the molar concentration of the bismuth source in the bismuth-source citric acid mixed solution is 0.01 to 1mol/L; the coating amount of the bismuth-source citric acid mixed solution coated on the surface of the FTO glass is 40 to 80 mu L/cm 2 (ii) a The temperature of the first calcination is 500 to 650 ℃, and the time is 1 to 6h.
8. The production method according to claim 3, wherein the aprotic solvent is dimethyl sulfoxide; the molar concentration of the vanadyl acetylacetonate solution is 0.3 to 1mol/L; the coating amount of the vanadyl acetylacetonate solution on the surface of the bismuth oxide film electrode is 60 to 120 mu L/cm 2 (ii) a The temperature of the second calcination is 400-600 ℃, and the time is 1-6 h; the alkali liquor is 1mol/L sodium hydroxide solution, and the soaking time of the alkali liquor is 20 to 60min.
9. BiVO according to claim 1 or 2 4 The application of the/MnOOH film electrode in photo-generated cathode corrosion prevention.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011204756.XA CN113293382B (en) | 2020-11-02 | 2020-11-02 | BiVO 4 MnOOH film electrode, preparation method thereof and application thereof in photo-generated cathode corrosion prevention |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011204756.XA CN113293382B (en) | 2020-11-02 | 2020-11-02 | BiVO 4 MnOOH film electrode, preparation method thereof and application thereof in photo-generated cathode corrosion prevention |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113293382A CN113293382A (en) | 2021-08-24 |
| CN113293382B true CN113293382B (en) | 2023-03-10 |
Family
ID=77318419
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011204756.XA Active CN113293382B (en) | 2020-11-02 | 2020-11-02 | BiVO 4 MnOOH film electrode, preparation method thereof and application thereof in photo-generated cathode corrosion prevention |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113293382B (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2015104686A (en) * | 2013-11-28 | 2015-06-08 | 一般財団法人 東京薬科大学付属社会医療研究所 | Visible light region response catalyst body and method for decomposing water utilizing the same |
| CN107324441A (en) * | 2017-07-07 | 2017-11-07 | 黄河科技学院 | Ferronickel oxyhydroxide modification pucherite optoelectronic pole and preparation method thereof, application |
| CN109569630A (en) * | 2019-01-23 | 2019-04-05 | 西北师范大学 | A kind of pucherite composite material preparation loading nickel cobalt hydrotalcite nano particle and the application in photoelectricity water oxygen |
| CN109772355A (en) * | 2019-03-11 | 2019-05-21 | 辽宁石油化工大学 | Amorphous FeOOH/alum acid bismuth composite photocatalyst material preparation method |
| CN111146004A (en) * | 2020-01-10 | 2020-05-12 | 北京化工大学 | Metal oxyhydroxide composite B-BiVO4Photoelectric anode and preparation method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9856567B2 (en) * | 2014-06-16 | 2018-01-02 | Wisconsin Alumni Research Foundation | Synthesis of high-surface-area nanoporous BiVO4 electrodes |
-
2020
- 2020-11-02 CN CN202011204756.XA patent/CN113293382B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2015104686A (en) * | 2013-11-28 | 2015-06-08 | 一般財団法人 東京薬科大学付属社会医療研究所 | Visible light region response catalyst body and method for decomposing water utilizing the same |
| CN107324441A (en) * | 2017-07-07 | 2017-11-07 | 黄河科技学院 | Ferronickel oxyhydroxide modification pucherite optoelectronic pole and preparation method thereof, application |
| CN109569630A (en) * | 2019-01-23 | 2019-04-05 | 西北师范大学 | A kind of pucherite composite material preparation loading nickel cobalt hydrotalcite nano particle and the application in photoelectricity water oxygen |
| CN109772355A (en) * | 2019-03-11 | 2019-05-21 | 辽宁石油化工大学 | Amorphous FeOOH/alum acid bismuth composite photocatalyst material preparation method |
| CN111146004A (en) * | 2020-01-10 | 2020-05-12 | 北京化工大学 | Metal oxyhydroxide composite B-BiVO4Photoelectric anode and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113293382A (en) | 2021-08-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101575713B (en) | Optical anode used for hydrogen production by photoelectrochemistry decomposition water and preparation method thereof | |
| CN108597886B (en) | A kind of organic solution and its application for modified oxidized iron light anode | |
| CN107557789B (en) | A kind of optical anode material and its preparation and application | |
| CN108328692B (en) | Photocatalytic fuel cell system and method for recovering noble metal silver and degrading organic matters through photoelectrocatalysis | |
| CN106257729A (en) | Self-respiration type light helps microbial fuel cell and application thereof | |
| CN108950570A (en) | A kind of preparation method of negative electrode of lithium ion battery collector porous copper foil | |
| CN102360958B (en) | Preparation method of photo-anode of ZnS/Au/TiO2 nano composite film | |
| CN103928690A (en) | Visible light photocatalytic fuel cell and preparation method thereof | |
| CN104357852A (en) | MnSe/TiO2 composite film for photogenerated cathode protection as well as preparation and application thereof | |
| CN105386061A (en) | Method for preparing Bi2S3/TiO2 nanorod composite-film photo-anodes | |
| CN101956194A (en) | Method for preparing TiO2 thin film modified titanium-based beta-PbO2 photoelectrode | |
| CN113502513A (en) | Method for directly depositing copper metal by utilizing solar energy | |
| CN113293382B (en) | BiVO 4 MnOOH film electrode, preparation method thereof and application thereof in photo-generated cathode corrosion prevention | |
| CN104498990A (en) | Semiconductor substrate/chromium-containing bimetallic alkaline phosphate photoelectrode and preparation method thereof | |
| CN109824126B (en) | Tin oxide anode electrode with high oxygen evolution potential and preparation method | |
| WO2022188503A1 (en) | Photogenerated anti-corrosion electrode material and preparation method and application thereof | |
| CN113293381B (en) | SrFeO3/Fe2O3 photoelectrode material, preparation method thereof and application thereof in photo-generated cathode corrosion prevention | |
| CN115092991A (en) | Wastewater fuel cell based on carbon quantum dot and ferrocene co-doped p-type MOF photocathode and preparation and application thereof | |
| CN109133259A (en) | A method of utilizing light anode activation sulfuric acid salt treatment waste water and by-product hydrogen | |
| CN111663140B (en) | Preparation of double-layer energy storage type photoelectric anode and application thereof in metal cathode protection | |
| CN114250472A (en) | BiVO4CoP thin film electrode and preparation method and application thereof | |
| CN114016082B (en) | Method for directly depositing and recovering metal bismuth on conductive substrate by utilizing solar energy | |
| CN114182263B (en) | Polydopamine-sensitized spacing type titanium dioxide composite membrane photo-anode and preparation method and application thereof | |
| CN114959823B (en) | Copper-based coordination polymer photocathode material and preparation method and application thereof | |
| CN104562077A (en) | Artificial zeolite modified titanium-based fluorine-containing lead dioxide electrode and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |