CN110394179A - A method of it is surface modified by anion exchange for promoting hydroxide oxygen evolution reaction performance - Google Patents

A method of it is surface modified by anion exchange for promoting hydroxide oxygen evolution reaction performance Download PDF

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CN110394179A
CN110394179A CN201910603302.0A CN201910603302A CN110394179A CN 110394179 A CN110394179 A CN 110394179A CN 201910603302 A CN201910603302 A CN 201910603302A CN 110394179 A CN110394179 A CN 110394179A
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solution
oxygen evolution
evolution reaction
hydroxide
sample
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曹传宝
韩占立
乔辰
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Beijing University of Technology
Beijing Institute of Technology BIT
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/007Mixed salts
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74Iron group metals
    • B01J23/75Cobalt
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74Iron group metals
    • B01J23/755Nickel
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/78Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali- or alkaline earth metals
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25BELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00Electrolytic production of inorganic compounds or non-metals
    • C25B1/01Products
    • C25B1/02Hydrogen or oxygen
    • C25B1/04Hydrogen or oxygen by electrolysis of water
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25BELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30Hydrogen technology
    • Y02E60/36Hydrogen production from non-carbon containing sources, e.g. by water electrolysis

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  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Electrochemistry (AREA)
  • Metallurgy (AREA)
  • Inorganic Chemistry (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
  • Catalysts (AREA)

Abstract

The invention discloses a kind of methods being surface modified by anion exchange for promoting hydroxide oxygen evolution reaction performance.It is primarily adapted for use in hydrotalcite/hydrotalcite-like materials oxygen evolution reaction performance promotion of iron, cobalt, the hydroxide of nickel or mixed metal.The present invention is mainly for the problems such as existing hydroxide catalyst stability of solution is poor, current density is low, overpotential is high.The anion in the anion salting liquid on hydroxide catalyst surface is replaced by simple experimental implementation, and then optimizes the performance of original catalyst.The present invention has a wide range of application, is low in cost, being simple to operate and friendly to environment, and does not need special equipment during whole operation, easy to industrialized production.Obtained catalyst has many advantages, such as that stability is good, active site is more, catalytic performance is high through the invention.The present invention provides a kind of very with the oxygen evolution reaction catalysts optimization method of industrial prospect.

Description

One kind is surface modified anti-for promoting hydroxide analysis oxygen by anion exchange The method for answering performance
Technical field
Present invention relates particularly to hydroxide, hydrotalcite structure hydroxide, hydrotalcite-like compound hydroxide nano materials The modification of material belongs to the technology of preparing and electro-catalysis energy and material application field of nano material.
Background technique
With the rapid development of industry, the demand of the energy is increasingly sharpened.Three macrofossil fuel (coal, petroleum, natural gas) Excessive exploitation not only cause serious environmental pollution, while also threaten national energy security.In order to solve this sternness Problem, in recent years, various countries worldwide invest considerable capital to research and develop clean renewable energy, such as metal electricity Pond, polymer electrolyte fuel cells and electrolysis water, wherein electrolysis water is considered as one of technology most with prospects.Moisture The hydrogen and oxygen that solution reaction generates can convert chemical energy for solar energy or electric energy and store, and generated hydrogen is firing The high and unique combustion product of energy density is water when burning releases energy, to zero environmental.Water splitting processes can be divided into two A reaction: anode part oxygen evolution reaction (OER) and cathode portion evolving hydrogen reaction (HER).Wherein oxygen evolution reaction dynamic process is slow Slowly, hydrogen production rate is low, is not able to satisfy actual demand, therefore the oxygen evolution reaction elctro-catalyst for developing efficient stable is studied at present One hot spot.
In oxygen evolution reaction catalysts, noble metal Ru, Ir and its oxide show very excellent catalytic performance, but by It is low in reserves, it is expensive, limit its extensive use.Therefore, research has stable non-expensive of low cost, high activity, performance Metallic catalyst becomes the very important project in electro-catalysis field, wherein studying most commonly used is the oxidation based on transition metal Object or hydroxide.Such catalyst manufacturing cost is low, toxicity is low, and structure and form are easily controllable, the corrosion resistant in alkaline solution Corrosion is good, and the extensive concern of people has just been received since proposition.Ming Gong et al. (J Am Chem Soc, 135 (2013) Excellent properties of the iron nickel hydrotalcite structure material as oxygen evolution reaction catalysts 8452-8455) are reported, this is because hydrotalcite Structural material has the characteristic of layer structure.Develop hydroxide materials, class water with excellent properties again on this basis The catalyst such as talc materials.
Oxygen evolution reaction is the committed step for restricting water splitting processes, and the research of oxygen evolution reaction catalysts has highly important Meaning.On the basis of many researchs, the invention proposes one kind to be surface modified by anion exchange for promoting hydrogen The method of oxide oxygen evolution reaction performance, this method can be further improved the performance of catalyst, and it is anti-to solve existing catalyst Answer dynamic stability poor, the problems such as current density is low under low overpotential.
Summary of the invention
The purpose of the present invention is to propose to a kind of are surface modified by anion exchange to analyse oxygen for promoting hydroxide The method of reactivity worth solves existing poor catalyst stability to improve the performance of oxygen evolution reaction catalysts, and current density is low The problems such as.
The technical solution adopted by the present invention to solve the technical problems are as follows: one kind is surface modified by anion exchange Method for promoting hydroxide oxygen evolution reaction performance, it is characterised in that comprise the steps of:
(1) one or more salt are dissolved in hydrophilic solution (single solution or mixed solution), wherein in solution The concentration of cation is 0.0001~10mol/mL, and the concentration of anion is 0.0001~10mol/mL.
(2) a certain amount of known hydroxide materials are weighed, are dispersed in step (1) resulting inorganic salt solution, Concentration is 0.0001~10mg/mL.
(3) step (2) resulting solution is put into shaking table, 1 is rocked with even speed~for 24 hours.
(4) after the material that step (3) obtains successively being used deionized water and dehydrated alcohol centrifuge washing, it is put into vacuum drying Case, drying duration 10~for 24 hours.
Above-described salting liquid cation is Li+、Na+、K+And NH4+One of ion is a variety of;Salting liquid anion For Cl-、F-、I-、S2-、CH3COO-、ClO-、CO3 2-、C2O4 2-、HCO3 -、HS-、HSO3 -、MnO4 -、NO2 -、NO3 -、PO4 3-、SO3 2-、 SO4 2-And S2O3 2-One of or it is a variety of;Hydrophilic solution is deionized water, ethyl alcohol, ethylene glycol, glycerine, isopropanol, isobutyl Alcohol, one or more of decyl alcohol mixed solution;
(5) step (4) resulting material is used for electrolysis water (oxygen evolution reaction) catalysis material, it is molten that material is dispersed in mixing In liquid (ethyl alcohol: deionized water ratio is 1:1) and 5% nafion aqueous solution, mixed solution and nafion water in mixed solution The ratio of solution is (90~95): (10~5).Configured solution is coated in glassy carbon electrode surface, room temperature is dried.Using three Electrode system is tested with linear sweep voltammetry, and electrolyte is 1M KOH.
Beneficial effect
1. the present invention is surface modified by anion exchange to promote hydroxide materials oxygen evolution reaction performance, In The chemical structure of material itself is not changed in synthesis process.
2. method of modifying of the invention, easy to operate, low in cost, mild condition, product morphology and structure and original conjunction It is consistent at method.Catalytic performance is further promoted on the basis of original catalyst catalytic performance.
3. the present invention is surface modified by anion exchange to promote hydroxide materials oxygen evolution reaction performance, it is The good catalyst of oxygen evolution reaction is that sweeping for 10mV/s measures under speed in sweep speed, current density reaches in 1M KOH solution To 50mA cm-2Overpotential fall below 0.293mV from 0.412mV.
Detailed description of the invention
Fig. 1 is the Fourier transform infrared map of cobalt hydroxide sample 1 and 2 prepared by embodiment 1;
Fig. 2 is the X-ray diffracting spectrum of three hydroxide sample 1 and 2 of cobalt magnesium nickel prepared by embodiment 3;
Fig. 3 is linear voltammetry scanning of the nickel hydroxide sample 1 and 2 prepared by embodiment 5 in 1M KOH electrolyte Performance;
Fig. 4 is linear volt of the iron nickel hydrotalcite structure sample 1,2 and 3 in 1M KOH electrolyte prepared by embodiment 7 Peace method scan performance;
Specific embodiment
Hereinafter, the present invention will be described in detail with reference to the accompanying drawings, helps to understand the present invention, but the present invention is not limited merely to Following embodiment.
Embodiment 1
Sample 1
For cobalt hydroxide sample.
Sample 1 is used for electrolysis water (oxygen evolution reaction) catalysis material, material is dispersed in mixed solution and nafion, is mixed Closing mixed solution and nafion ratio in solution is 94:6.Configured solution is coated in glassy carbon electrode surface, room temperature is dried. It is tested using three-electrode system with linear sweep voltammetry, electrolyte is 1M KOH.It is sweeping for 10mV/s in sweep speed The lower measurement of speed, overpotential 0.37V, current density can reach 10mA cm-2
Sample 2
(1) 10g sodium sulphate is dissolved in 100mL deionized water, is made it completely dissolved.
(2) sample 1 (cobalt hydroxide) for weighing 10mg is dispersed in step (1) resulting inorganic salt solution.
(3) step (2) resulting solution is put into shaking table, 10h is rocked with even speed.
(4) after the material that step (3) obtains successively being used deionized water and dehydrated alcohol centrifuge washing, it is put into vacuum drying Case dries the cobalt hydroxide sample that can be modified after 20h.
(5) step (4) resulting material is used for electrolysis water (oxygen evolution reaction) catalysis material, it is molten that material is dispersed in mixing In liquid and nafion, mixed solution and nafion ratio are 94:6 in mixed solution.By configured solution coated in glass carbon electricity Pole surface, room temperature are dried.It is tested using three-electrode system with linear sweep voltammetry, electrolyte is 1M KOH.It is scanning Rate is that sweeping for 30mV/s measures under speed, and overpotential 0.36V, current density can reach 10mA cm-2
Fig. 1 is the infrared transformation map of Fourier of the cobalt hydroxide sample 1 and 2 of modified obtained by the implementation case, As can be seen from the figure material obtained has a good infrared signature absorption peak, sample 2 since anion replaces exchange reaction, In 1100cm-1There is the characteristic absorption peak of sulfate radical at place, and there are apparent difference with sample 1 for this.
Embodiment 2
Sample 1
For iron nickel hydrotalcite structure sample.
Sample 1 is used for electrolysis water (oxygen evolution reaction) catalysis material, material is dispersed in mixed solution and nafion, is mixed Closing mixed solution and nafion ratio in solution is 95:5.Configured solution is coated in glassy carbon electrode surface, room temperature is dried. It is tested using three-electrode system with linear sweep voltammetry, electrolyte is 1M KOH.It is sweeping for 10mV/s in sweep speed The lower measurement of speed, overpotential 0.37V, current density can reach 10mA cm-2
Sample 2
(1) 6.5g potassium chloride is dissolved in 100mL hydrophilic solution (deionized water is 1:1 with proportion of ethanol), keeps its complete Fully dissolved.
(2) sample 1 (iron nickel hydrotalcite structure sample) for weighing 10mg, is dispersed in step (1) resulting inorganic salts In solution.
(3) step (2) resulting solution is put into shaking table, 12h is rocked with even speed.
(4) after the material that step (3) obtains successively being used deionized water and dehydrated alcohol centrifuge washing, it is put into vacuum drying Case dries the iron nickel hydrotalcite structure sample that can be modified after 18h.
(5) step (4) resulting material is used for electrolysis water (oxygen evolution reaction) catalysis material, it is molten that material is dispersed in mixing In liquid and nafion, mixed solution and nafion ratio are 95:5 in mixed solution.By configured solution coated in glass carbon electricity Pole surface, room temperature are dried.It is tested using three-electrode system with linear sweep voltammetry, electrolyte is 1M KOH.It is scanning Rate is that sweeping for 30mV/s measures under speed, and overpotential 0.34V, current density can reach 10mA cm-2
Embodiment 3
Sample 1
For cobalt magnesium nickel hydroxide sample.
Sample 1 is used for electrolysis water (oxygen evolution reaction) catalysis material, material is dispersed in mixed solution and nafion, is mixed Closing mixed solution and nafion ratio in solution is 93:7.Configured solution is coated in glassy carbon electrode surface, room temperature is dried. It is tested using three-electrode system with linear sweep voltammetry, electrolyte is 1M KOH.It is sweeping for 10mV/s in sweep speed The lower measurement of speed, overpotential 0.33V, current density can reach 10mA cm-2
Sample 2
(1) 8g sodium sulphate is dissolved in 100mL deionized water, is made it completely dissolved.
(2) sample 1 (cobalt magnesium nickel hydroxide) for weighing 5mg, is dispersed in step (1) resulting inorganic salt solution In.
(3) step (2) resulting solution is put into shaking table, 12h is rocked with even speed.
(4) after the material that step (3) obtains successively being used deionized water and dehydrated alcohol centrifuge washing, it is put into vacuum drying Case dries the cobalt magnesium nickel hydroxide sample that can be modified after 20h.
(5) step (4) resulting material is used for electrolysis water (oxygen evolution reaction) catalysis material, it is molten that material is dispersed in mixing In liquid and nafion, mixed solution and nafion ratio are 93:7 in mixed solution.By configured solution coated in glass carbon electricity Pole surface, room temperature are dried.It is tested using three-electrode system with linear sweep voltammetry, electrolyte is 1M KOH.It is scanning Rate is that sweeping for 10mV/s measures under speed, and overpotential presses 0.3V, and current density is up to 10mA cm-2
Fig. 2 is the X ray diffracting spectrum of the three hydroxide sample 1 and 2 of cobalt magnesium nickel of the resulting modification of the present embodiment, from figure In it can be seen that gained sample has preferable structural characteristic peak, well-crystallized, and anion exchange reaction is not to material Structure impacts.
Embodiment 4
Sample 1
For cobalt hydroxide sample.
Sample 1 is used for electrolysis water (oxygen evolution reaction) catalysis material, material is dispersed in mixed solution and nafion, is mixed Closing mixed solution and nafion ratio in solution is 94:6.Configured solution is coated in glassy carbon electrode surface, room temperature is dried. It is tested using three-electrode system with linear sweep voltammetry, electrolyte is 1M KOH.It is sweeping for 10mV/s in sweep speed The lower measurement of speed, overpotential 0.37V, current density can reach 10mA cm-2
Sample 2
(1) 10g sodium carbonate is dissolved in 100mL hydrophilic solution (ethyl alcohol and ethylene glycol ratio be 1:2), keeps it completely molten Solution.
(2) sample 1 (cobalt hydroxide) for weighing 5mg is dispersed in step (1) resulting inorganic salt solution.
(3) step (2) resulting solution is put into shaking table, 10h is rocked with even speed.
(4) after the material that step (3) obtains successively being used deionized water and dehydrated alcohol centrifuge washing, it is put into vacuum drying Case dries the cobalt hydroxide sample that can be modified after 16h.
(5) step (4) resulting material is used for electrolysis water (oxygen evolution reaction) catalysis material, it is molten that material is dispersed in mixing In liquid and nafion, mixed solution and nafion ratio are 93:7 in mixed solution.By configured solution coated in glass carbon electricity Pole surface, room temperature are dried.It is tested using three-electrode system with linear sweep voltammetry, electrolyte is 1M KOH.It is scanning Rate is that sweeping for 10mV/s measures under speed, and overpotential presses 0.32V, and current density is up to 10mA cm-2
Embodiment 5
Sample 1
For nickel hydroxide sample.
Sample 1 is used for electrolysis water (oxygen evolution reaction) catalysis material, material is dispersed in mixed solution and nafion, is mixed Closing mixed solution and nafion ratio in solution is 95:5.Configured solution is coated in glassy carbon electrode surface, room temperature is dried. It is tested using three-electrode system with linear sweep voltammetry, electrolyte is 1M KOH.It is sweeping for 10mV/s in sweep speed The lower measurement of speed, overpotential 0.415V, current density can reach 10mA cm-2
Sample 2
(1) 12g sodium sulphate is dissolved in 100mL hydrophilic solution (deionized water and ethylene glycol ratio be 1:2), makes it completely Dissolution.
(2) sample 1 (nickel hydroxide) for weighing 8mg is dispersed in step (1) resulting inorganic salt solution.
(3) step (2) resulting solution is put into shaking table, 14h is rocked with even speed.
(4) after the material that step (3) obtains successively being used deionized water and dehydrated alcohol centrifuge washing, it is put into vacuum drying Case, the nickel hydroxide sample that can be modified after drying for 24 hours.
(5) step (4) resulting material is used for electrolysis water (oxygen evolution reaction) catalysis material, it is molten that material is dispersed in mixing In liquid and nafion, mixed solution and nafion ratio are 94:6 in mixed solution.By configured solution coated in glass carbon electricity Pole surface, room temperature are dried.It is tested using three-electrode system with linear sweep voltammetry, electrolyte is 1M KOH.It is scanning Rate is that sweeping for 10mV/s measures under speed, and overpotential presses 0.372V, and current density is up to 10mA cm-2
Fig. 3 is the oxygen evolution reaction performance map of the nickel hydroxide sample 1 and 2 of the resulting modification of the present embodiment, and abscissa is electricity Position, ordinate are the current density that oxygen evolution reaction generates.It is shown in figure, the electric current of the material in overpotential 0.415V of sample 1 is close Degree reaches 10mA cm-2.And the current density of material in overpotential 0.372V of sample 2 can reach 10mA cm-2
Embodiment 6
Sample 1
For magnesium cobalt hydroxide structure sample.
Sample 1 is used for electrolysis water (oxygen evolution reaction) catalysis material, material is dispersed in mixed solution and nafion, is mixed Closing mixed solution and nafion ratio in solution is 94:6.Configured solution is coated in glassy carbon electrode surface, room temperature is dried. It is tested using three-electrode system with linear sweep voltammetry, electrolyte is 1M KOH.It is sweeping for 10mV/s in sweep speed The lower measurement of speed, overpotential 0.37V, current density can reach 10mA cm-2
Sample 2
(1) 9g potassium nitrate is dissolved in 100mL hydrophilic solution (deionized water and glycerine ratio be 1:2), makes it completely Dissolution.
(2) sample 1 (magnesium cobalt hydroxide) for weighing 6mg is dispersed in step (1) resulting inorganic salt solution.
(3) step (2) resulting solution is put into shaking table, 12h is rocked with even speed.
(4) after the material that step (3) obtains successively being used deionized water and dehydrated alcohol centrifuge washing, it is put into vacuum drying Case, the magnesium cobalt hydroxide sample that can be modified after drying for 24 hours.
(5) step (4) resulting material is used for electrolysis water (oxygen evolution reaction) catalysis material, it is molten that material is dispersed in mixing In liquid and nafion, mixed solution and nafion ratio are 94:6 in mixed solution.By configured solution coated in glass carbon electricity Pole surface, room temperature are dried.It is tested using three-electrode system with linear sweep voltammetry, electrolyte is 1M KOH.It is scanning Rate is that sweeping for 10mV/s measures under speed, and overpotential presses 0.36V, and current density is up to 10mA cm-2
Embodiment 7
Sample 1
For iron nickel hydrotalcite structure sample.
Sample 1 is used for electrolysis water (oxygen evolution reaction) catalysis material, material is dispersed in mixed solution and nafion, is mixed Closing mixed solution and nafion ratio in solution is 95:5.Configured solution is coated in glassy carbon electrode surface, room temperature is dried. It is tested using three-electrode system with linear sweep voltammetry, electrolyte is 1M KOH.It is sweeping for 10mV/s in sweep speed The lower measurement of speed, overpotential 0.412V, current density can reach 50mA cm-2
Sample 2
(1) 9g sodium sulphate is dissolved in 100mL deionized water, is made it completely dissolved.
(2) sample 1 (iron nickel hydrotalcite structure) for weighing 12mg, is dispersed in step (1) resulting inorganic salt solution In.
(3) step (2) resulting solution is put into shaking table, 18h is rocked with even speed.
(4) after the material that step (3) obtains successively being used deionized water and dehydrated alcohol centrifuge washing, it is put into vacuum drying Case dries the iron nickel hydrotalcite structure sample that can be modified after 20h.
(5) step (4) resulting material is used for electrolysis water (oxygen evolution reaction) catalysis material, it is molten that material is dispersed in mixing In liquid and nafion, mixed solution and nafion ratio are 94:6 in mixed solution.By configured solution coated in glass carbon electricity Pole surface, room temperature are dried.It is tested using three-electrode system with linear sweep voltammetry, electrolyte is 1M KOH.It is scanning Rate is that sweeping for 10mV/s measures under speed, and overpotential presses 0.354V, and current density is up to 50mA cm-2
Sample 3
For step 4 gained sample in sample 2.
Sample 3 is used for electrolysis water (oxygen evolution reaction) catalysis material, material is dispersed in mixed solution and nafion, is mixed Closing mixed solution and nafion ratio in solution is 93:7.Configured solution is coated in glassy carbon electrode surface, room temperature is dried. It is tested using three-electrode system with linear sweep voltammetry, electrolyte is 1M KOH.It is sweeping for 10mV/s in sweep speed The lower measurement of speed, overpotential 0.293V, current density can reach 50mA cm-2
Fig. 4 is the oxygen evolution reaction performance map of the iron nickel hydrotalcite structure sample 1,2 and 3 of the resulting modification of the present embodiment, horizontal Coordinate is current potential, and ordinate is the current density that oxygen evolution reaction generates.It is shown in figure, the material in overpotential 0.412V of sample 1 Current density reach 50mA cm-2.The current density of material in overpotential 0.354V of sample 2 reaches 50mA cm-2.And sample The current density of material in overpotential 0.293V of product 3 can reach 50mA cm-2

Claims (4)

1. a kind of method being surface modified by anion exchange for promoting hydroxide oxygen evolution reaction performance, including such as Lower step:
(1) one or more salt are dissolved in hydrophilic solution (single solution or mixed solution), wherein solution middle-jiao yang, function of the spleen and stomach from The concentration of son is 0.0001~10mol/ml, and the concentration of anion is 0.0001~10mol/mL.
(2) a certain amount of known hydroxide materials are weighed, are dispersed in step (1) resulting inorganic salt solution, concentration is 0.0001~10mg/mL.
(3) step (2) resulting solution is put into shaking table, 1 is rocked with even speed~for 24 hours.
(4) after the material that step (3) obtains successively being used deionized water and dehydrated alcohol centrifuge washing, it is put into vacuum oven, Drying duration 10~for 24 hours.
(5) step (4) resulting material is used for electrolysis water (oxygen evolution reaction) catalysis material, material is dispersed in mixed solution (ethyl alcohol: deionized water ratio is 1:1) with nafion, mixed solution and nafion ratio are (90~95) in mixed solution: (10~5).Configured solution is coated in glassy carbon electrode surface, room temperature is dried.It is lied prostrate using three-electrode system with linear scan Peace method is tested, and electrolyte is 1M KOH.
2. preparation method as described in claim 1, it is characterised in that: the salting liquid cation is Li+、Na+、K+And NH4+From One of son is a variety of.
3. preparation method as described in claim 1, it is characterised in that: the salting liquid anion is Cl-、F-、I-、S2-、 CH3COO-、ClO-、CO3 2-、C2O4 2-、HCO3 -、HS-、HSO3 -、MnO4 -、NO2 -、NO3 -、PO4 3-、SO3 2-、SO4 2-And S2O3 2-In It is one or more.
4. preparation method as described in claim 1, it is characterised in that: hydrophilic solution is deionized water, ethyl alcohol, ethylene glycol, Glycerine, isopropanol, isobutanol, one or more of decyl alcohol mixed solution.
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