CN107268021B - A kind of NiCoAl-LDH modification di-iron trioxide complex light anode material and its preparation method and application - Google Patents
A kind of NiCoAl-LDH modification di-iron trioxide complex light anode material and its preparation method and application Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 55
- 239000010405 anode material Substances 0.000 title claims abstract description 20
- 238000012986 modification Methods 0.000 title claims description 16
- 230000004048 modification Effects 0.000 title claims description 15
- DQMUQFUTDWISTM-UHFFFAOYSA-N O.[O-2].[Fe+2].[Fe+2].[O-2] Chemical compound O.[O-2].[Fe+2].[Fe+2].[O-2] DQMUQFUTDWISTM-UHFFFAOYSA-N 0.000 title description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims abstract description 96
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 47
- 238000006243 chemical reaction Methods 0.000 claims abstract description 32
- 239000004202 carbamide Substances 0.000 claims abstract description 18
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt(II) nitrate Inorganic materials [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims abstract description 18
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000010438 heat treatment Methods 0.000 claims abstract description 17
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 16
- 238000001035 drying Methods 0.000 claims abstract description 14
- 239000008367 deionised water Substances 0.000 claims abstract description 13
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 13
- 238000002156 mixing Methods 0.000 claims abstract description 12
- 230000003647 oxidation Effects 0.000 claims abstract description 11
- 239000012266 salt solution Substances 0.000 claims abstract description 11
- 239000002028 Biomass Substances 0.000 claims abstract description 9
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000000758 substrate Substances 0.000 claims abstract description 7
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 4
- 239000011259 mixed solution Substances 0.000 claims abstract description 4
- 239000003792 electrolyte Substances 0.000 claims description 21
- 229910052760 oxygen Inorganic materials 0.000 claims description 21
- 230000007935 neutral effect Effects 0.000 claims description 20
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 10
- 239000001301 oxygen Substances 0.000 claims description 10
- 238000000354 decomposition reaction Methods 0.000 claims description 6
- 239000000446 fuel Substances 0.000 claims description 6
- 239000000243 solution Substances 0.000 abstract description 21
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 4
- 238000013508 migration Methods 0.000 abstract description 4
- 230000005012 migration Effects 0.000 abstract description 4
- 238000011065 in-situ storage Methods 0.000 abstract description 3
- 238000000926 separation method Methods 0.000 abstract description 3
- 239000003054 catalyst Substances 0.000 abstract description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 40
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 18
- 238000003756 stirring Methods 0.000 description 18
- 229910052759 nickel Inorganic materials 0.000 description 14
- 238000000034 method Methods 0.000 description 13
- 239000003643 water by type Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 239000007788 liquid Substances 0.000 description 10
- 229910021645 metal ion Inorganic materials 0.000 description 10
- 230000003287 optical effect Effects 0.000 description 10
- 238000007789 sealing Methods 0.000 description 10
- 238000001291 vacuum drying Methods 0.000 description 9
- 238000005406 washing Methods 0.000 description 9
- 239000010410 layer Substances 0.000 description 8
- 230000005518 electrochemistry Effects 0.000 description 7
- 238000005286 illumination Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 229910002915 BiVO4 Inorganic materials 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000005868 electrolysis reaction Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 230000005622 photoelectricity Effects 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 229910006020 NiCoAl Inorganic materials 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000007853 buffer solution Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 239000011229 interlayer Substances 0.000 description 3
- 238000013112 stability test Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229910003145 α-Fe2O3 Inorganic materials 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
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- 239000007789 gas Substances 0.000 description 2
- 239000008103 glucose Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000011241 protective layer Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 230000010718 Oxidation Activity Effects 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
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- 239000010953 base metal Substances 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
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- 239000003426 co-catalyst Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000002761 deinking Substances 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 229960001545 hydrotalcite Drugs 0.000 description 1
- 229910001701 hydrotalcite Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 125000001967 indiganyl group Chemical group [H][In]([H])[*] 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000029553 photosynthesis Effects 0.000 description 1
- 238000010672 photosynthesis Methods 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
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- 235000009566 rice Nutrition 0.000 description 1
- 239000011833 salt mixture Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000010408 sweeping Methods 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
-
- B01J35/33—
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/50—Processes
- C25B1/55—Photoelectrolysis
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/8647—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites
- H01M4/8657—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites layered
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8825—Methods for deposition of the catalytic active composition
- H01M4/8846—Impregnation
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9016—Oxides, hydroxides or oxygenated metallic salts
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The present invention relates to a kind of NiCoAl-LDH to modify Fe2O3The preparation method of complex light anode material, specifically: 1) by Ni (NO3)2、Co(NO3)2With Al (NO3)3It is dissolved in deionized water and is configured to mixing salt solution, the total mol concentration of mixing salt solution is 0.010 ~ 0.200 mol/L；2) by urea and NH4F is separately added into above-mentioned mixing salt solution, wherein urea molar concentration is 0.025 ~ 0.500 mol/L, NH4F concentration is 0.010 ~ 0.200 mol/L；3) mixed solution obtained by step 2 is transferred in water heating kettle, and by Fe2O3Electrode slice is placed in water heating kettle, and 80 ~ 150 DEG C of isothermal reaction 1-6 h, take out after reaction in baking oven, washed, be drying to obtain.The present invention is to load Fe2O3FTO be that substrate by hydro-thermal method growth in situ NiCoAl-LDH " active protection layer " not only increases the electric conductivity of catalyst, promote the separation and migration of photo-generated carrier；Active site is provided for the oxidation of water or biomass simultaneously, effectively reduces reaction overpotential；It can promote H again+It is migrated into solution, inhibits Fe2O3Hydrolysis, improves its stability.
Description
Technical field
The invention belongs to new energy materials and optical electro-chemistry catalysis technical fields, and in particular to a kind of NiCoAl hydrotalcite
Modify Fe2O3Complex light anode material, preparation method and its in neutral electrolyte photoelectric decomposition water Oxygen anodic evolution reaction and light help
Photoelectrocatalysis application in fuel cell light anode oxidative biological qualitative response.
Background technique
As the mankind are continuously increased cleaning and sustainable energy demand, efficient, the low cost and environmentally friendly sun
The research and development of energy conversion system have become the hot spot of research.The mankind gain enlightenment from the photosynthesis of natural plant,
The storage and conversion of solar energy are successfully realized using Driven by Solar Energy water decomposition or the power generation of solar energy oxidizing biomass.Wherein,
Optical electro-chemistry cell system is to realize one of solar energy storage and the ideal device of conversion.However, the photoelectric activity of optical anode material
And stability is the bottleneck for limiting optical electro-chemistry cell system application and development.
In recent years, there is visible light-responded semiconductor material, such as WO3、BiVO4、Fe2O3Equal metal oxides, it is a large amount of
Ground development and utilization, and it is increasingly becoming " hot spot " of people's research.Wherein, Fe2O3With forbidden bandwidth narrow (1.9-2.2 eV), member
The advantages that element composition is abundant, nontoxic, stable in strong alkali solution, and its theoretical photoelectric current maximum is up to 12.6 mA/cm2, quilt
It is considered a kind of ideal optical anode material.But the result actually get also differs greatly with theoretical value, such as: theoretical photoelectric current
With the difference of practical photoelectric current, flat-band potential and open current potential and mismatch etc..This is mainly as caused by following reason:
(1) Fe2O3The migration rate of poorly conductive, light induced electron is low, about 0.1 cm2·V-1·s-1；(2) diffusion of photohole away from
From short, only 2-4 nm；(3) dynamic process of water oxidation reaction is slow, reaction rate s-1(Tilley S D, Cornuz M,
Sivula K, Graetzel M, Angew. Chem. Int. Edit. 2010, 49, 6405-6408；Sivula K,
Le Formal F, Graetzel M, ChemSusChem 2011,4,432-449.).
In order to solve Fe2O3Light anode there are the problem of, further increase its incident photon-to-electron conversion efficiency, people are conductive from improving
Property, reduce that photo-generated carrier is compound etc. to propose numerous solutions.Such as: by pattern control, element doping, constructing
Hetero-junctions and surface modification etc. can improve nanometer Fe2O3Light anode photoelectrocatalysis decomposes aqueous energy.Although by Fe2O3Into
A series of modifications of row can make its photoelectric current reach mA grades, but Fe2O3Light anode facile hydrolysis in neutral or faintly acid electrolyte,
Cause its stability in weakly acidic pH environment it is poor (Kim J Y, Jang J, Youn D H, Magesh G, Lee J S,Adv. Energy Mater. 2014, 4, 1400476.).Current a lot of research work primary limitation is electrolysed in strong basicity
Liquid, such as 1molL-1In NaOH.This is Fe2O3Sizable application bring following problem: (1) highly basic electrolyte can be to electrolytic cell
Equipment causes heavy corrosion；(2) a large amount of CO can be absorbed in the long-term use of alkaline electrolyte2, so as to cause battery performance
It destroys；(3) decomposing in aqueous systems in optical electro-chemistry makes alkali steam be mixed into H2In and reduce be made gas purity.Therefore, it explores
With the Fe of exploitation steady operation under near-neutral sulfite deinking2O3Light anode meets the requirement of Green Chemistry and sustainable development, can be greatly
Fe is expanded on ground2O3The application of light anode.
Layered double hydroxide (LDHs) is a kind of typical anionic intercalation material, and chemical composition can be with table
It is shown as [M2+ 1-xM3+ x(OH)2](An-)x/n∙yH2O.Wherein, M2+、M3+For metal cation, An-For interlayer anion, y is interlayer
Moisture subnumber.The structure of LDHs can be regarded as positively charged main layer board and interlayer anion and pass through the mutual of non-covalent bond
Effect assembles, thus its Nomenclature Composition and Structure of Complexes has very strong Modulatory character.LDHs relevant to Co active sites is as production
Oxygen co-catalyst shows excellent catalytic activity performance.He et al. passes through in BiVO4The surface of light anode grows CoAl-LDH
Nm wall network structure has constructed LDH@BiVO4Complex light anode.The photoelectric current take-off potential of the complex light anode is more simple
BiVO4Change significantly reduces 610 mV, and incident photon-to-electron conversion efficiency and oxidation efficiency be obviously improved (He WH, Wang RR,
Zhang L, Zhu J, Xiang X, Li F, J. Mater. Chem. A, 2015,3,17977-17982).Research
Personnel pass through in α-Fe2O3The introducing of photoanode surface growth in situ CoAl-LDH, discovery CoAl-LDH protective layer can be mentioned significantly
High α-Fe2O3The performance of water oxygen in neutral electrolyte, and density of photocurrent is almost kept during its stability test
Constant (Chong RF, Wang BY, Su CH, Li DL, Mao LQ, Chang ZX, Zhang L, J. Mater.
Chem. A, 2017,5,8583-8590).Although CoAl-LDH has excellent electro-chemical activity, itself electric conductivity
Difference causes material internal charge transport rate lower.Crystal structure can not changed by the method for metal ion mixing
On the basis of, change the electronic structure of CoAl-LDH to a certain extent, improves conductivity, enhance the migration performance (Ueda of charge
K, Tabata H, Kawai T, Appl. Phys. Lett., 2001, 79, 988)。
The present invention is by introducing Ni into CoAl-LDH2+Ion constructs NiCoAl ternary LDH as Fe2O3Light anode is " living
Property protective layer ", can provide more active sites, higher electric conductivity and preferably dispersibility, give full play to three kinds of groups
The collaboration advantage divided is expected to construct the Fe of a kind of high activity and high stability in neutral electrolyte2O3Complex light anode material,
And there is important theoretical and practical significance to exploitation novel photoanode material.
Summary of the invention
Present invention aims to overcome that prior art defect, provides a kind of NiCoAl-LDH modification Fe2O3Complex light anode material
Material, the complex light anode material can be used for the reaction of photoelectric decomposition water Oxygen anodic evolution and fuel cell light in neutral and alkaline electrolyte
Anode biomass oxidation reaction.
The invention also discloses above-mentioned NiCoAl-LDH to modify Fe2O3The preparation method and application of complex light anode material.
To achieve the above object, the present invention adopts the following technical scheme:
A kind of NiCoAl-LDH modification Fe2O3The preparation method of complex light anode material comprising following steps:
1) by Ni (NO3)2、Co(NO3)2With Al (NO3)3It is dissolved in deionized water and is configured to mixing salt solution, salt-mixture is molten
The total mol concentration of liquid is 0.010 ~ 0.200 mol/L；
2) by urea and NH4F is separately added into above-mentioned mixing salt solution, wherein urea molar concentration is 0.025 ~ 0.500
mol/L、NH4F concentration is 0.010 ~ 0.200 mol/L；
3) mixed solution obtained by step 2 is transferred in water heating kettle, and by Fe2O3Electrode slice is placed in water heating kettle, in baking
80 ~ 150 DEG C of isothermal reaction 1-6 h, take out after reaction in case, washed, be drying to obtain.
Specifically, in step 1), (Ni2++Co2+)/Al3+Molar ratio be 1/3 ~ 3, Ni2+/Co2+Molar ratio be 1/5 ~
5.That is Ni (NO3)2With Co (NO3)2The sum of molal quantity be Al (NO3)31/3 ~ 3 times of molal quantity, Ni (NO3)2With Co (NO3)2's
Molar ratio is 0.2 ~ 5:1.
Fe is modified using the NiCoAl-LDH that above-mentioned preparation method is prepared2O3Complex light anode material, with load
Fe2O3FTO as substrate, make the NiCoAl-LDH nanometer sheet with 2D layer structure with reticular structure by Situ Hydrothermal method
Deposition is covered on Fe2O3Surface, and NiCoAl-LDH layers with a thickness of 100-1000 nm.
Above-mentioned NiCoAl-LDH modifies Fe2O3The application of complex light anode material, specifically, can be used for neutral and alkaline electro
Solve the reaction of photoelectric decomposition water Oxygen anodic evolution and fuel cell light anode biomass oxidation reaction in liquid.
The present invention is to load Fe2O3FTO be substrate, by hydro-thermal method growth in situ NiCoAl-LDH " active protection layer ",
The electric conductivity for not only increasing catalyst promotes the separation and migration of photo-generated carrier；The oxidation for water or biomass mentions simultaneously
For active site, reaction overpotential is effectively reduced；It can promote H again+It is migrated into solution, inhibits Fe2O3It is steady to improve it for hydrolysis
It is qualitative.
Compared with prior art, the present invention have following major advantage and the utility model has the advantages that
1) " active protection layer " of the present invention is base metal composite material, raw materials used to be easy to buy and prepare,
Resourceful and price is lower, and large scale preparation is at low cost；
2) stability that complex light anode material of the present invention has had, reacts for a long time in neutral electrolyte,
Its photoelectric activity can be used for a long time almost without decaying and keep good catalytic activity；
3) Fe of ternary LDH modification of the present invention2O3It is a kind of novel composite material, there is preferable photoelectricity water
Oxidation and biomass oxidation activity, the bimetallic LDH/Fe reported more at present2O3Complex light anode is aoxidized with more significant photoelectricity
Performance；
4) complex light anode preparation method of the present invention is simple, easily operated, convenient for large-scale production.
Detailed description of the invention
Fig. 1 is Fe obtained by comparative example 1-32O3、Co3Al-LDH/Fe2O3、Ni3Al-LDH/Fe2O3Not with embodiment 1-7 gained
The NiCoAl-LDH/Fe of same Ni, Co molar ratio2O3The XRD spectrum of combination electrode；
Fig. 2 is Fe obtained by comparative example 1-32O3、Co3Al-LDH/Fe2O3、Ni3Al-LDH/Fe2O3With 4 gained Ni/ of embodiment
The NiCoAl-LDH/Fe for the 1:1 that Co molar ratio is2O3The surface SEM and Element area profile of combination electrode；
Fig. 3 is the NiCoAl-LDH/Fe for the 1:1 that 4 gained Ni, Co molar ratio of embodiment is2O3The section SEM of combination electrode
And distribution diagram of element；
Fig. 4 is the NiCoAl-LDH/Fe of difference Ni/Co molar ratio obtained by embodiment 1-72O3Combination electrode is in neutral electricity
Solve the linear voltammetric scan map of water oxygen under the conditions of dark-state in liquid；
Fig. 5 is the NiCoAl-LDH/Fe of difference Ni, Co molar ratio obtained by embodiment 1-72O3Combination electrode is in Neutral Electrolysis
Illumination condition is lauched the linear voltammetric scan map of oxidation in liquid；
Fig. 6 and 7 is respectively Fe obtained by comparative example 1-32O3、Co3Al-LDH/Fe2O3、Ni3Al-LDH/Fe2O3With embodiment 4
Gained Ni, Co molar ratio is the NiCoAl-LDH/Fe of 1:12O3Combination electrode dark-state and illumination condition in neutral electrolyte are lauched
The linear voltammetric scan map of oxidation；
Fig. 8 is the Fe obtained by comparative example 1-32O3、Co3Al-LDH/Fe2O3、Ni3Al-LDH/Fe2O3With 4 gained of embodiment
The NiCoAl-LDH/Fe for the 1:1 that Ni/Co molar ratio is2O3Grape is glycoxidative under illumination condition in neutral electrolyte for combination electrode
Linear voltammetric scan map；
Fig. 9 has gone out the NiCoAl-LDH/Fe for the 1:1 that 4 gained Ni, Co molar ratio of embodiment is2O3Combination electrode is 1.23
V vs.Electrolyte is 0.1 molL at RHE-1In Na-Pi buffer solution (pH=7), the reaction time be 2 h optical electro-chemistry
Stability test curve.
Specific embodiment
Technical solution of the present invention is further discussed in detail with reference to embodiments, but protection scope of the present invention
It is not limited thereto.
Embodiment 1
A kind of NiCoAl-LDH modification Fe2O3The preparation method of complex light anode comprising following steps:
(a) Fe2O3The preparation of electrode slice
Weigh the FeCl of 1.0812 g3Urea with 0.5405 g is added in 50 mL deionized waters in 100 mL beakers
It makes it dissolve；Then cleaned FTO substrate is placed in a beaker, is placed the beaker after sealing in baking oven and reacts 4 in 100 DEG C
h；It is cooled to room temperature, takes out.Then it is cleaned with deionized water, 80 DEG C of 12 h of drying；It is finally putting into 500 DEG C of calcinings 3 in Muffle furnace
H, it is cooling after in Muffle furnace 750 DEG C of 15 min of annealing to get Fe2O3Electrode slice；
(b) Ni2.5Co0.5Al-LDH/Fe2O3The preparation of complex light anode
By Ni (NO3)2·6H2O、Co(NO3)2·6H2O and Al (NO3)3·9H2O, according to [Ni2++Co2+]/Al3+Molar ratio
For 3:1, Ni2+/Co2+Molar ratio is 5:1, metal ion total concentration is 20 mmol/L, is added into 25 mL deionized waters, stirs
It mixes to being completely dissolved.A certain amount of urea and NH is added into solution again4F, making its concentration is respectively 50 mmol/L and 20
Mmol/L, stirring is to being completely dissolved.Finally, above-mentioned solution is transferred in 50mL water heating kettle, while being put into step (a) preparation
Fe2O3Electrode slice, sealing, is placed in 100 baking ovens and reacts 2 h.After reaction, electrode slice is taken out, respectively with deionized water and
Ethanol washing three times, and in vacuum drying oven 80 DEG C of 12 h of drying to get.
Embodiment 2
A kind of NiCoAl-LDH modification Fe2O3The preparation method of complex light anode comprising following steps:
(a) Fe2O3The preparation of electrode slice
According to the method and condition preparation of step (a) in embodiment 1；
(b) Ni2.25Co0.75Al-LDH/Fe2O3The preparation of complex light anode
By Ni (NO3)2·6H2O、Co(NO3)2·6H2O and Al (NO3)3·9H2O, according to [Ni2++Co2+]/Al3+Molar ratio
For 3:1, Ni2+/Co2+Molar ratio is 3:1, metal ion total concentration is 20 mmol/L, is added into 25 mL deionized waters, stirs
It mixes to being completely dissolved.A certain amount of urea and NH is added into solution again4F, making its concentration is respectively 50 mmol/L and 20
Mmol/L, stirring is to being completely dissolved.Finally, above-mentioned solution is transferred in 50mL water heating kettle, while being put into step (a) preparation
Fe2O3Electrode slice, sealing, is placed in 100 DEG C of baking ovens and reacts 2 h.After reaction, electrode slice is taken out, uses deionized water respectively
Three times with ethanol washing, and in vacuum drying oven 80 DEG C of 12 h of drying to get.
Embodiment 3
A kind of NiCoAl-LDH modification Fe2O3The preparation method of complex light anode comprising following steps:
(a) Fe2O3The preparation of electrode slice
According to the method and condition preparation of step (a) in embodiment 1；
(b) Ni2CoAl-LDH/Fe2O3The preparation of complex light anode
By Ni (NO3)2·6H2O、Co(NO3)2·6H2O and Al (NO3)3·9H2O, according to [Ni2++Co2+]/Al3+Molar ratio
For 3:1, Ni2+/Co2+Molar ratio is 2:1, metal ion total concentration is 20 mmol/L, is added into 25 mL deionized waters, stirs
It mixes to being completely dissolved.A certain amount of urea and NH is added into solution again4F, making its concentration is respectively 50 mmol/L and 20
Mmol/L, stirring is to being completely dissolved.Finally, above-mentioned solution is transferred in 50mL water heating kettle, while being put into step (a) preparation
Fe2O3Electrode slice, sealing, is placed in 100 DEG C of baking ovens and reacts 2 h.After reaction, electrode slice is taken out, uses deionized water respectively
Three times with ethanol washing, and in vacuum drying oven 80 DEG C of 12 h of drying to get.
Embodiment 4
A kind of NiCoAl-LDH modification Fe2O3The preparation method of complex light anode comprising following steps:
(a) Fe2O3The preparation of electrode slice
According to the method and condition preparation of step (a) in embodiment 1；
(b) Ni1.5Co1.5Al-LDH/Fe2O3The preparation of complex light anode
By Ni (NO3)2·6H2O、Co(NO3)2·6H2O and Al (NO3)3·9H2O, according to [Ni2++Co2+]/Al3+Molar ratio
For 3:1, Ni2+/Co2+Molar ratio is 1:1, metal ion total concentration is 20 mmol/L, is added into 25 mL deionized waters, stirs
It mixes to being completely dissolved.A certain amount of urea and NH is added into solution again4F, making its concentration is respectively 50 mmol/L and 20
Mmol/L, stirring is to being completely dissolved.Finally, above-mentioned solution is transferred in 50 mL water heating kettles, while being put into step (a) preparation
Fe2O3Electrode slice, sealing, is placed in 100 DEG C of baking ovens and reacts 2 h.After reaction, electrode slice is taken out, uses deionization respectively
Water and ethanol washing three times, and in vacuum drying oven 80 DEG C of 12 h of drying to get.
Embodiment 5
A kind of NiCoAl-LDH modification Fe2O3The preparation method of complex light anode comprising following steps:
(a) Fe2O3The preparation of electrode slice
According to the method and condition preparation of step (a) in embodiment 1；
(b) NiCo2Al-LDH/Fe2O3The preparation of complex light anode
By Ni (NO3)2·6H2O、Co(NO3)2·6H2O and Al (NO3)3·9H2O, according to [Ni2++Co2+]/Al3+Molar ratio
For 3:1, Ni2+/Co2+Molar ratio is 1:2, metal ion total concentration is 20 mmol/L, is added into 25 mL deionized waters, stirs
It mixes to being completely dissolved.A certain amount of urea and NH is added into solution again4F, making its concentration is respectively 50 mmol/L and 20
Mmol/L, stirring is to being completely dissolved.Finally, above-mentioned solution is transferred in 50mL water heating kettle, while being put into step (a) preparation
Fe2O3Electrode slice, sealing, is placed in 100 DEG C of baking ovens and reacts 2 h.After reaction, electrode slice is taken out, uses deionized water respectively
Three times with ethanol washing, 80 DEG C of 12 h of drying and in vacuum drying oven.
Embodiment 6
A kind of NiCoAl-LDH modification Fe2O3The preparation method of complex light anode comprising following steps:
(a) Fe2O3The preparation of electrode slice
According to the method and condition preparation of step (a) in embodiment 1；
(b) Ni0.75Co2.25Al-LDH/Fe2O3The preparation of complex light anode
By Ni (NO3)2·6H2O、Co(NO3)2·6H2O and Al (NO3)3·9H2O, according to [Ni2++Co2+]/Al3+Molar ratio
For 3:1, Ni2+/Co2+Molar ratio is 1:3, metal ion total concentration is 20 mmol/L, is added into 25 mL deionized waters, stirs
It mixes to being completely dissolved.A certain amount of urea and NH is added into solution again4F, making its concentration is respectively 50 mmol/L and 20
Mmol/L, stirring is to being completely dissolved.Finally, above-mentioned solution is transferred in 50mL water heating kettle, while being put into step (a) preparation
Fe2O3Electrode slice, sealing, is placed in 100 DEG C of baking ovens and reacts 2 h.After reaction, electrode slice is taken out, uses deionized water respectively
Three times with ethanol washing, and in vacuum drying oven 80 DEG C of 12 h of drying to get.
Embodiment 7
A kind of NiCoAl-LDH modification Fe2O3The preparation method of complex light anode comprising following steps:
(a) Fe2O3The preparation of electrode slice
According to the method and condition preparation of step (a) in embodiment 1；
(b) Ni0.5Co2.5Al-LDH/Fe2O3The preparation of complex light anode
By Ni (NO3)2·6H2O、Co(NO3)2·6H2O and Al (NO3)3·9H2O, according to [Ni2++Co2+]/Al3+Molar ratio
For 3:1, Ni2+/Co2+Molar ratio is 1:5, metal ion total concentration is 20 mmol/L, is added into 25 mL deionized waters, stirs
It mixes to being completely dissolved.A certain amount of urea and NH is added into solution again4F, making its concentration is respectively 50 mmol/L and 20
Mmol/L, stirring is to being completely dissolved.Finally, above-mentioned solution is transferred in 50mL water heating kettle, while being put into step (a) preparation
Fe2O3Electrode slice, sealing, is placed in 100 DEG C of baking ovens and reacts 2 h.After reaction, electrode slice is taken out, uses deionized water respectively
Three times with ethanol washing, and in vacuum drying oven 80 DEG C of 12 h of drying to get.
Comparative example 1
(a) Fe2O3The preparation of electrode slice
According to the method and condition preparation of step (a) in embodiment 1.
Comparative example 2
(a) Fe2O3The preparation of electrode slice
According to the method and condition preparation of step (a) in embodiment 1；
(b) Co3Al-LDH/Fe2O3The preparation of complex light anode
By Co (NO3)2·6H2O and Al (NO3)3·9H2O, according to Co2+/Al3+Molar ratio is 3:1, metal ion is always dense
Degree is 20 mmol/L, and addition is added in 25 mL deionized waters into 25 mL deionized waters, and stirring is to being completely dissolved.Xiang Rong again
A certain amount of urea and NH are added in liquid4F makes its concentration be respectively 50 mmol/L and 20 mmol/L, and stirring is to being completely dissolved.
Finally, above-mentioned solution is transferred in 50 mL water heating kettles, while being put into the Fe of step (a) preparation2O3Electrode slice, sealing, is placed in
2 h are reacted in 100 DEG C of baking ovens.After reaction, electrode slice is taken out, respectively three times with deionized water and ethanol washing, and
80 DEG C of 12 h of drying in vacuum drying oven.
Comparative example 3
(a) Fe2O3The preparation of electrode slice
According to the method and condition preparation of step (a) in embodiment 1；
(b)Ni3Al-LDH/Fe2O3The preparation of complex light anode
By Ni (NO3)2·6H2O and Al (NO3)3·9H2O, according to Ni2+/Al3+Molar ratio is 3:1, metal ion is always dense
Degree is 20 mmol/L, and addition is added in 25 mL deionized waters into 25 mL deionized waters, and stirring is to being completely dissolved.Xiang Rong again
A certain amount of urea and NH are added in liquid4F makes its concentration be respectively 50 mmol/L and 20 mmol/L, and stirring is to being completely dissolved.
Finally, above-mentioned solution is transferred in 50 mL water heating kettles, while being put into the Fe of step (a) preparation2O3Electrode slice, sealing, is placed in
2 h are reacted in 100 DEG C of baking ovens.After reaction, electrode slice is taken out, respectively three times with deionized water and ethanol washing, and
80 DEG C of 12 h of drying in vacuum drying oven.
Application Example
The above-mentioned PhotoelectrocatalytiPerformance Performance test for preparing resulting complex light anode is with saturated calomel electrode (SCE) for reference
Electrode, Pt electrode are to electrode, and sweeping speed is 5 mV/s, and electrolyte is the buffer solution of sodium phosphate (pH=7) of 0.5 mol/L.One
The calculating of reversible electrode potential under the conditions of pH is determined according to Nernst equation (ERHE=Eref+ 0.244 V+0.059 V × pH), test
Preceding to carry out bubbling about 30 min of processing to electrolyte using high-purity argon gas, electrode area is fixed with insulating cement, linear scan (LSV)
It is completed by electrochemical workstation (CH Instruments 760D potentiostat), light source is AM 1.5G solar energy mould
Quasi- device (100 mW cm-2).The oxidation test of photoelectricity biomass selects 0.1 mol/L glucose as reaction substrate, remaining test-strips
Part is as described above.
Fig. 1 is Fe obtained by comparative example 1-32O3、Co3Al-LDH/Fe2O3、Ni3Al-LDH/Fe2O3Not with embodiment 1-7 gained
The NiCoAl-LDH/Fe of same Ni, Co molar ratio2O3The XRD spectrum of combination electrode.From figure 1 it appears that in addition to the diffraction of FTO
Except peak, 2Өα-Fe is respectively corresponded in the diffraction maximum of 35.4o and 64.5o2O3(110) and (300) crystal face (PDF no.33-
0664).In α-Fe2O3After surface deposits LDH, 2ӨOccurs a new diffraction maximum at 34.3o, which belongs to
LDH (009) crystal face, shows LDH and Fe2O3Success is compound.
Fig. 2 is Fe obtained by comparative example 1-32O3、Co3Al-LDH/Fe2O3、Ni3Al-LDH/Fe2O3With 4 gained Ni/ of embodiment
The NiCoAl-LDH/Fe for the 1:1 that Co molar ratio is2O3The surface SEM and Element area profile of combination electrode.It can be with from Fig. 2A
Find out Fe2O3It in club shaped structure and is equably grown in the surface of FTO, diameter is about 150 nm, and average length is about 250
nm.In Fe2O3Surface grown after LDH (Fig. 2 B, C and D), it can be seen that Fe2O3Surface is covered by LDH nanometer sheet completely, and is received
Rice piece is interlaced and perpendicular to substrate, constitutes nano-chip arrays structure.Elemental map characterize (Fig. 2A-D) it can be seen that
Fe, O element are equally distributed in all electrode materials.Simultaneously it can also be seen that Co, Al are evenly distributed on Co3Al-LDH/
Fe2O3In, Ni, Al are evenly distributed on Ni3Al-LDH/Fe2O3In；Ni, Co, Al are evenly distributed on NiCoAl-LDH/Fe2O3In.
As a result it further demonstrates and successfully constructs LDH/Fe under the conditions of claim2O3Complex light anode material.
Fig. 3 is the NiCoAl-LDH/Fe for the 1:1 that 4 gained Ni, Co molar ratio of embodiment is2O3The section SEM of combination electrode
And distribution diagram of element.From figure 3, it can be seen that Fe2O3Thickness be about 180 nm, NiCoAl-LDH nanometer sheet is in Fe2O3Table
The quasi- Vertical Square in face is grown up, and nanometer layer thickness is about 400 nm.It can be with NiCoAl-LDH/Fe from Element area profile2O3
Middle Ni, Co, Al, Fe, O Elemental redistribution is corresponding with each layer element composition of combination electrode, further demonstrates NiCoAl-LDH with layer
Shape structure is evenly distributed in Fe2O3Surface.
Fig. 4 is the NiCoAl-LDH/Fe of difference Ni/Co molar ratio obtained by embodiment 1-72O3Combination electrode is in Neutral Electrolysis
In liquid under the conditions of dark-state water oxygen linear voltammetric scan map.It can be seen from the figure that in applying bias > 1.6 V vs.
When RHE, there is the oxidation current of water.
Fig. 5 is the NiCoAl-LDH/Fe of difference Ni, Co molar ratio obtained by embodiment 1-72O3Combination electrode is in Neutral Electrolysis
Illumination condition is lauched the linear voltammetric scan map of oxidation in liquid.As shown, the density of photocurrent of light anode is whole under illumination
It is above dark-state photoelectric current in a voltage tester scope, and when Ni, Co molar ratio are 1:1, density of photocurrent highest.
Fig. 6 and 7 is respectively Fe obtained by comparative example 1-32O3、Co3Al-LDH/Fe2O3、Ni3Al-LDH/Fe2O3With embodiment 4
Gained Ni, Co molar ratio is the NiCoAl-LDH/Fe of 1:12O3Combination electrode dark-state and illumination condition in neutral electrolyte are lauched
The linear voltammetric scan map of oxidation.It can be seen from the figure that with simple Fe2O3It compares, LDH/Fe2O3Combination electrode photoelectricity
The take-off potential of stream moves nearly 200 mV than compound forward direction cathode direction, and photoelectric current significantly improves.It is multiple with binary LDH
Light combination electrode is compared, NiCoAl-LDH/Fe2O3There is no significant changes for the photoelectric current take-off potential of combination electrode, but ternary is multiple
Zoarium system photoelectric current is put up the best performance, and shows that ternary LDH can effectively facilitate the separation of photo-generated carrier, to accelerate water oxygen
The progress of reaction.
Fig. 8 is the Fe obtained by comparative example 1-32O3、Co3Al-LDH/Fe2O3、Ni3Al-LDH/Fe2O3With 4 gained of embodiment
The NiCoAl-LDH/Fe for the 1:1 that Ni/Co molar ratio is2O3Grape is glycoxidative under illumination condition in neutral electrolyte for combination electrode
Linear voltammetric scan map.As seen from the figure, with simple Fe2O3With binary LDH/Fe2O3Combination electrode is compared,
NiCoAl-LDH/Fe2O3The photoelectric current take-off potential of combination electrode moves about 100 mV to cathode direction, and photoelectric current is obvious
It improves, shows the compound Fe of NiCoAl ternary LDH2O3The progress of glucose oxidation reaction can be effectively facilitated.
Fig. 9 gives the NiCoAl-LDH/Fe for the 1:1 that 4 gained Ni, Co molar ratio of embodiment is2O3Combination electrode is 1.23
V vs.Electrolyte is 0.1 molL at RHE-1In Na-Pi buffer solution (pH=7), the reaction time be 2 h optical electro-chemistry
Stability test curve.It is as shown in the figure: by the test of 2 h, NiCoAl-LDH/Fe2O3The density of photocurrent of combination electrode is almost
It remains unchanged, this explanation is in Neutral Electrolysis liquid system, NiCoAl-LDH/Fe2O3Photoanode surface hardly happens hydrolysis and corruption
Erosion, it was demonstrated that Fe can be improved by the load of NiCoAl-LDH2O3Stability in neutral electrolyte.
In conclusion the Fe of NiCoAl-LDH modification2O3Electrode has preferable stability, and phase in neutral electrolyte
Fe is modified for binary LDH2O3Electrode shows higher photoelectric activity, can be used as optical electro-chemistry in neutral electrolyte and decomposes
Water and light help the optical anode material of microbial fuel cell.
Claims (4)
1. one kind is anti-for photoelectric decomposition water Oxygen anodic evolution reaction in neutral electrolyte and the oxidation of fuel cell light anode biomass
The NiCoAl-LDH modification Fe answered2O3Complex light anode material, which is characterized in that it is to load Fe2O3FTO as substrate, lead to
Crossing Situ Hydrothermal method makes the NiCoAl-LDH nanometer sheet with 2D layer structure be covered on Fe with reticular structure deposition2O3Surface, and
NiCoAl-LDH layers with a thickness of 100-1000 nm；Specifically prepared through following step:
1) by Ni (NO3)2、Co(NO3)2With Al (NO3)3It is dissolved in deionized water and is configured to mixing salt solution, mixing salt solution
Total mol concentration is 0.020 mol/L；
2) by urea and NH4F is separately added into above-mentioned mixing salt solution, wherein urea molar concentration is 0.050 mol/L mol/
L、NH4F concentration is 0.020 mol/L；
3) mixed solution obtained by step 2 is transferred in water heating kettle, and by Fe2O3Electrode slice is placed in water heating kettle, in baking oven
80 ~ 150 DEG C of isothermal reaction 1-6 h, take out after reaction, washed, be drying to obtain.
2. NiCoAl-LDH described in claim 1 modifies Fe2O3The preparation method of complex light anode material, which is characterized in that including
Following steps:
1) by Ni (NO3)2、Co(NO3)2With Al (NO3)3It is dissolved in deionized water and is configured to mixing salt solution, mixing salt solution
Total mol concentration is 0.010 ~ 0.200 mol/L；
2) by urea and NH4F is separately added into above-mentioned mixing salt solution, wherein urea molar concentration is 0.025 ~ 0.500 mol/
L、NH4F concentration is 0.010 ~ 0.200 mol/L；
3) mixed solution obtained by step 2 is transferred in water heating kettle, and by Fe2O3Electrode slice is placed in water heating kettle, in baking oven
80 ~ 150 DEG C of isothermal reaction 1-6 h, take out after reaction, washed, be drying to obtain.
3. NiCoAl-LDH modifies Fe according to claim 22O3The preparation method of complex light anode material, which is characterized in that
In step 1), (Ni2++Co2+)/Al3+Molar ratio be 1/3 ~ 3, Ni2+/Co2+Molar ratio be 1/5 ~ 5.
4. NiCoAl-LDH described in claim 1 modifies Fe2O3The application of complex light anode material, which is characterized in that for neutrality
The reaction of photoelectric decomposition water Oxygen anodic evolution and fuel cell light anode biomass oxidation reaction in electrolyte.
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| CN105040025A (en) * | 2015-05-12 | 2015-11-11 | 北京化工大学 | Double metal hydroxide-composited porous bismuth vanadate photo-electrode and preparation method thereof |
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