CN107262098A - A kind of preparation method of oxygen evolution reaction catalyst - Google Patents
A kind of preparation method of oxygen evolution reaction catalyst Download PDFInfo
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- CN107262098A CN107262098A CN201710579046.7A CN201710579046A CN107262098A CN 107262098 A CN107262098 A CN 107262098A CN 201710579046 A CN201710579046 A CN 201710579046A CN 107262098 A CN107262098 A CN 107262098A
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- peroxide
- oxygen evolution
- evolution reaction
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 239000001301 oxygen Substances 0.000 title claims abstract description 60
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 60
- 239000007809 chemical reaction catalyst Substances 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 38
- 150000002978 peroxides Chemical class 0.000 claims abstract description 28
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 26
- 239000000463 material Substances 0.000 claims abstract description 22
- 150000002736 metal compounds Chemical class 0.000 claims abstract description 20
- 239000000203 mixture Substances 0.000 claims abstract description 18
- 230000000694 effects Effects 0.000 claims abstract description 17
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 12
- 150000001875 compounds Chemical class 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 12
- 238000010438 heat treatment Methods 0.000 claims abstract description 10
- 239000007787 solid Substances 0.000 claims abstract description 8
- 239000007864 aqueous solution Substances 0.000 claims abstract description 7
- 229910052751 metal Inorganic materials 0.000 claims abstract description 6
- 238000001914 filtration Methods 0.000 claims abstract description 4
- 239000002184 metal Substances 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 27
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 20
- 229910052723 transition metal Inorganic materials 0.000 claims description 18
- 150000003624 transition metals Chemical class 0.000 claims description 18
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 10
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 10
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 7
- 229910021645 metal ion Inorganic materials 0.000 claims description 7
- 230000015572 biosynthetic process Effects 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 150000003346 selenoethers Chemical class 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 5
- 239000001273 butane Substances 0.000 claims description 5
- WBZKQQHYRPRKNJ-UHFFFAOYSA-L disulfite Chemical compound [O-]S(=O)S([O-])(=O)=O WBZKQQHYRPRKNJ-UHFFFAOYSA-L 0.000 claims description 5
- 229910052748 manganese Inorganic materials 0.000 claims description 5
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 claims description 5
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- 239000001294 propane Substances 0.000 claims description 5
- 239000011780 sodium chloride Substances 0.000 claims description 5
- 229910000314 transition metal oxide Inorganic materials 0.000 claims description 5
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- SJQITXILEOCXGI-UHFFFAOYSA-N 3,3,6,6-tetramethyl-1,2,4,5-tetraoxane Chemical compound CC1(C)OOC(C)(C)OO1 SJQITXILEOCXGI-UHFFFAOYSA-N 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 150000004767 nitrides Chemical class 0.000 claims description 3
- 230000008859 change Effects 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 claims 2
- ILRLTAZWFOQHRT-UHFFFAOYSA-N potassium;sulfuric acid Chemical compound [K].OS(O)(=O)=O ILRLTAZWFOQHRT-UHFFFAOYSA-N 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 25
- 230000003647 oxidation Effects 0.000 abstract description 15
- 230000008901 benefit Effects 0.000 abstract description 9
- 230000033228 biological regulation Effects 0.000 abstract description 7
- 230000004048 modification Effects 0.000 abstract description 6
- 238000012986 modification Methods 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 231100000252 nontoxic Toxicity 0.000 abstract description 4
- 230000003000 nontoxic effect Effects 0.000 abstract description 4
- 238000006056 electrooxidation reaction Methods 0.000 abstract description 3
- 230000003197 catalytic effect Effects 0.000 description 20
- 239000003054 catalyst Substances 0.000 description 15
- -1 oxo transition metal Compound Chemical class 0.000 description 8
- 229910052742 iron Inorganic materials 0.000 description 7
- 230000006872 improvement Effects 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 229910000765 intermetallic Inorganic materials 0.000 description 4
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 4
- 229910052939 potassium sulfate Inorganic materials 0.000 description 4
- 235000011151 potassium sulphates Nutrition 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 238000007385 chemical modification Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 230000004044 response Effects 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 239000007806 chemical reaction intermediate Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- ZQMIGQNCOMNODD-UHFFFAOYSA-N diacetyl peroxide Chemical compound CC(=O)OOC(C)=O ZQMIGQNCOMNODD-UHFFFAOYSA-N 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 150000002440 hydroxy compounds Chemical class 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 150000003623 transition metal compounds Chemical class 0.000 description 2
- 229910003321 CoFe Inorganic materials 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- NWNCWFWKRQXRGC-UHFFFAOYSA-N acetyl acetate;propan-2-one Chemical compound CC(C)=O.CC(=O)OC(C)=O NWNCWFWKRQXRGC-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
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- 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
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- 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
- B01J23/76—Catalysts 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
- B01J23/78—Catalysts 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
- B01J23/76—Catalysts 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
- B01J23/84—Catalysts 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 arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
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- 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
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- C25B1/04—Hydrogen or oxygen by electrolysis of water
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- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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Abstract
The invention belongs to electrochemical catalysis field, and in particular to a kind of preparation method of oxygen evolution reaction catalyst, comprise the following steps：Compound with two or more transiting metal components is scattered in aqueous solution by S1；S2 adds peroxide；S3 is heated；Mixture after heating is cooled down and centrifuges or be separated by filtration by S4, obtains solid, that is, the oxygen evolution reaction catalyst with high activity is made.The present invention carries out surface modification using chemical oxidation means to transistion metal compound, to manufacture more avtive spots on transistion metal compound surface, improve material oxygen evolution reaction catalysis activity, compared to the electrochemical oxidation method of current more use, chemical oxidation operation is more convenient, it is easier to realize large-scale application and the regulation and control to material surface site.Due to its exist high efficiency, high-quality, high-purity, cost it is low, non-toxic and be easy to manipulation the advantages of, be therefore particularly suitable for the application occasion of large-scale mass production.
Description
Technical field
The invention belongs to electrochemical catalysis field, more particularly to a kind of preparation method of oxygen evolution reaction catalyst.
Background technology
Oxygen evolution reaction (2H2O→4H++4e+O2) coupled as with the reaction such as Hydrogen evolving reaction, carbon dioxide reduction reaction
Half-reaction, it is all significant in terms of acquisition, the fixation of carbon dioxide and the recycling of cleaning Hydrogen Energy, be current clear
One important subject in clean energy research field.However, oxygen evolution reaction is slow in the enterprising retardation of walking of usual electrode interface.Want
Convert the water to oxygen, it is necessary to use catalyst Cheap highly effective.Oxide, sulfide, phosphide, the selenides of transition metal
It is the oxygen evolution reaction catalyst being currently widely studied etc. a series of compounds, has carried out greatly around this series material
Work is measured, but these materials still have reaction overpotential height, a series of problems, such as catalytic efficiency is low, it would be highly desirable to improve.In recent years
The research come shows that transition metal oxide is likely to the avtive spot that transition metal associated materials are catalyzed oxygen evolution reaction,
Therefore a kind of improvement transition metal material oxygen is become to transition metal material progress electrochemical oxidation using current potential or electric current is applied
The method that evolution reaction is catalyzed behavior, but research has shown that, this method poor controllability, and it is difficult to extensive preparation.
On the whole, all kinds of catalyst of the prior art can not reach preferable catalytic effect, correspondingly, this area
Need badly and find more perfect solution, the need for the speed-raising to meet oxygen evolution reaction.
The content of the invention
For the disadvantages described above or Improvement requirement of prior art, the invention provides the preparation side of oxygen evolution reaction catalyst
Method, wherein by being designed to the species and content as the crucial peroxide for participating in thing, is accordingly researched and proposed and fully
Chemical oxidation reaction make use of to carry out the principle of chemical modification to transition metal oxide surface to prepare oxygen evolution reaction catalysis
Agent；Targeted design additionally is carried out to the important technical parameter in course of reaction, can accordingly be realized for material surface
The regulation and control of reaction site, at the same exist high efficiency, high-quality, high-purity, cost it is low, non-toxic and be easy to manipulation the advantages of, because
And the application occasion for the large-scale mass production that is particularly suitable for use in.
To achieve the above object, the invention provides a kind of preparation method of oxygen evolution reaction catalyst, it is characterised in that
This method comprises the following steps：
Compound with two or more transiting metal components is scattered in by S1 with 0.1g/L-5000g/L mass concentration
In aqueous solution, ultrasonic mixing is uniform；
Peroxide is added in the mixture that S2 is obtained in step sl, wherein, the addition of the peroxide is set
It is fixed as follows：The molar ratio range of the peroxide and the metal ion in compound is (1-1000):1；
S3 is heated the mixture obtained in step S2, the table of the peroxide and transistion metal compound
Oxidation reaction occurs for face, and the oxyhydroxide with oxygen evolution reaction catalysis activity is formed on the surface of transition metal oxide；
Mixture cooling after heating and isolated solid are made oxygen evolution reaction catalyst by S4.
Specifically, the present invention using chemical oxidation means come to transistion metal compound progress surface modification, by incited somebody to action
Cross metallic compound and carry out heating response with peroxide, being formed on the surface of transistion metal compound has higher oxygen precipitation anti-
The oxyhydroxide of catalytic activity is answered, so as to prepare the oxygen evolution reaction catalyst with high activity.And the reaction can be with
By controlling the content of peroxide, the regulation and control for material surface site, and then the speed of control oxygen evolution reaction can be achieved,
And generated in preparation process without addition product, improve the purity and catalytic performance of catalyst.
It is further preferred that in step sl, the transition metal is preferably Fe, Co, Ni or Mn.More comparative result
Show, above-mentioned transition metal can react generation transition metal complex from different molecule or group, and to hydroxyl
The oxygen evolution reaction intermediate such as base free radical has suitable adsorption capacity, can be used as catalyst, and above-mentioned metallic element
In chemical oxidation reaction, surface can largely generate hydroxy compounds, be capable of the cracking of effective catalytic water, promote the analysis of oxygen
Go out.Its method of modifying is simple, and the catalyst effect of generation is good, also has the advantages that with low cost.
Preferably, in step sl, the compound of the transition metal formation is preferably one kind or several in following material
Kind：Oxide, sulfide, phosphide, selenides, carbide or nitride.
Preferably, in step sl, the aqueous solution is one kind or its mixture in following material：Pure water, chlorination
Potassium solution, sodium chloride solution, potassium hydroxide solution, sodium hydroxide solution, potassium sulfate solution or metabisulfite solution.
The transistion metal compound of oxide, sulfide, phosphide, the selenides of transition metal etc. can be separated out as oxygen
The catalyst of reaction, but its catalytic activity still has much room for improvement.The transistion metal compound of above-mentioned substance form is scattered in pure
Water, Klorvess Liquid, sodium chloride solution, potassium hydroxide solution, sodium hydroxide solution, potassium sulfate solution or metabisulfite solution etc. contain
In the aqueous solution, after peroxide is added, these materials interact with peroxide, and surface turns in presence of water
Turn to the more oxyhydroxide of defect, it is smooth that the presence of water can make it subsequently produce the chemical oxidation reaction of oxyhydroxide
Carry out, and the oxyhydroxide of this new formation has very high activity to oxygen evolution reaction.And use above-mentioned substance and molten
Liquid carries out peroxidization, can effectively suppress the generation of impurity, improves the purity of catalyst, and then it is final to improve it
Catalytic performance.
Preferably, in step s 2, the peroxide is one kind or its mixture in following material：Hydrogen peroxide,
Diacetone peroxide, 2,2- pairs-(tert-butyl peroxide) propane, 2,2- pairs-(tert-butyl peroxide) butane or Peracetic acid.
Because these peroxide are strong oxidizer, can occur chemical oxidation reaction with metallic compound, using hydrogen peroxide, mistake
Acetyloxide acetone, 2,2- be double-(tert-butyl peroxide) propane, 2,2- be double-(tert-butyl peroxide) butane or Peracetic acid with
Transistion metal compound is reacted, and fast and effeciently can realize chemical modification to transistion metal compound surface.
Preferably, in step s3, the condition of the heating is preferably as follows：Heating-up temperature is 20 DEG C -200 DEG C, plus
The hot time is 1min-48h.Find, the temperature and time of heat treatment will be controlled within the above range, Neng Gouyou after relatively
Compound is carried out surface chemistry oxidation by effect ground, improves the oxygen evolution reaction catalytic performance of compound.
Preferably, separation method in step s 4 is using centrifugation or is separated by filtration.
In general, by the contemplated above technical scheme of the present invention compared with prior art, with advantages below and
Beneficial effect：
(1) the invention provides the preparation method of oxygen evolution reaction catalyst, wherein by being used as crucial participation thing
The species and content of peroxide are designed, and accordingly research and propose and take full advantage of chemical oxidation reaction to oxo transition metal
Compound surface carries out the principle of chemical modification to prepare oxygen evolution reaction catalyst；Additionally to the important process in course of reaction
Parameter carry out targeted design, can accordingly realize the regulation and control of the reaction site for catalyst surface, at the same exist high efficiency,
The advantages of high-quality, high-purity, cost are low, non-toxic and are easy to manipulation, is therefore particularly suitable for the fortune of large-scale mass production
Use occasion.
(2) surface modification is carried out to transistion metal compound using chemical oxidation means, by by transition metal compound
Thing carries out heating response with peroxide, and being formed on the surface of transistion metal compound has higher oxygen evolution reaction catalytic activity
Oxyhydroxide, so as to prepare the oxygen evolution reaction catalyst with high activity.And the reaction can be by controlling
The content of oxide, realizes the regulation and control for material surface site, and then controls the speed of oxygen evolution reaction, and in preparation process
Without addition product generation, the purity and catalytic performance of catalyst are improved.
(3) in the selection of reactant, the transition metal such as Fe, Co, Ni or Mn can be from different molecule or group
React generation transition metal complex, and has suitable energy of adsorption to the oxygen evolution reaction intermediate such as hydroxyl radical free radical
Power, can be used as catalyst, and above-mentioned metallic element, in chemical oxidation reaction, surface can largely generate hydroxy compound
Thing, is capable of the cracking of effective catalytic water, promotes the precipitation of oxygen.Its method of modifying is simple, and the catalyst effect of generation
It is good, also have the advantages that with low cost.
The transistion metal compound of oxide, sulfide, phosphide, the selenides of transition metal etc. can be separated out as oxygen
The catalyst of reaction, but its catalytic activity still has much room for improvement.The transistion metal compound of above-mentioned substance form is scattered in pure
Water, Klorvess Liquid, sodium chloride solution, potassium hydroxide solution, sodium hydroxide solution, potassium sulfate solution or metabisulfite solution etc. contain
In the aqueous solution, after peroxide is added, these materials interact with peroxide, and surface turns in presence of water
Turn to the more oxyhydroxide of defect, it is smooth that the presence of water can make it subsequently produce the chemical oxidation reaction of oxyhydroxide
Carry out, and the oxyhydroxide of this new formation has very high activity to oxygen evolution reaction.And use above-mentioned substance and molten
Liquid carries out peroxidization, can effectively suppress the generation of impurity, improves the purity of catalyst, and then it is final to improve it
Catalytic performance.
Due to hydrogen peroxide, diacetone peroxide, 2,2- it is double-(tert-butyl peroxide) propane, 2,2- be double-(peroxidating
The tert-butyl group) butane or Peracetic acid be strong oxidizer, can occur chemical oxidation reaction with metallic compound, using these mistakes
Oxide is reacted with transistion metal compound, fast and effeciently can realize that chemistry changes to transistion metal compound surface
Property.
(4) present invention carries out surface modification using chemical oxidation means to transistion metal compound, with transition metal
Compound surface manufactures more avtive spots, material oxygen evolution reaction catalysis activity is improved, compared to electrochemical oxidation, chemical oxidation
Operation is more convenient, it is easier to realize large-scale application and the regulation and control to material surface site.Simultaneously because its exist high efficiency,
The advantages of high-quality, high-purity, cost are low, non-toxic and are easy to manipulation, is therefore particularly suitable for the fortune of large-scale mass production
Use occasion.
Brief description of the drawings
Fig. 1 is the flow chart of the preparation method of the oxygen evolution reaction catalyst of the present invention；
Fig. 2 is the scanning electron micrograph for the oxygen evolution reaction catalyst prepared by chemical oxidation；
Fig. 3 is the oxygen evolution reaction catalysis polarization curve by CoFe composite oxides before and after chemical oxidation treatment.
Embodiment
In order to make the purpose , technical scheme and advantage of the present invention be clearer, it is right below in conjunction with drawings and Examples
The present invention is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, and
It is not used in the restriction present invention.As long as in addition, technical characteristic involved in each embodiment of invention described below
Not constituting conflict each other can just be mutually combined.
As shown in figure 1, the preparation method of the oxygen evolution reaction catalyst for the present invention, this method comprises the following steps：
Compound with two or more transiting metal component (is preferably the transition such as Fe, Co, Ni, Mn gold by S1
Oxide, sulfide, phosphide, selenides, carbide or the nitride of category) it is scattered with 0.1g/L-5000g/L mass concentration
In aqueous solution (be preferably pure water, Klorvess Liquid, sodium chloride solution, potassium hydroxide solution, sodium hydroxide solution, potassium sulfate
Solution or metabisulfite solution) in, ultrasonic mixing is uniform；
Peroxide is added in the mixture that S2 is obtained in step sl (is preferably：Hydrogen peroxide, acetyl peroxide third
Ketone, 2,2- pairs-(tert-butyl peroxide) propane, 2,2- pairs-(tert-butyl peroxide) butane or Peracetic acid), wherein, will be described
The addition setting of peroxide is as follows：The molar ratio range of the peroxide and the metal ion in compound is (1-
1000):1；And peroxidization is carried out using above-mentioned substance and solution, it can effectively suppress the generation of impurity, improve catalysis
The purity of agent, and then improve its final catalytic performance；
The mixture obtained in step S2 is handled 1min-48h by S3 in the range of 20 DEG C -200 DEG C, the peroxide with
Oxidation reaction occurs for the surface of transistion metal compound, and being formed on the surface of transition metal oxide has higher oxygen evolution reaction
The oxyhydroxide of catalytic activity；
Mixture after heating is cooled down and centrifuges or be separated by filtration by S4, obtains solid, that is, being made has high activity
Oxygen evolution reaction catalyst.
Specifically, the present invention using chemical oxidation means come to transistion metal compound progress surface modification, by incited somebody to action
Cross metallic compound and carry out heating response with peroxide, being formed on the surface of transistion metal compound has higher oxygen precipitation anti-
The oxyhydroxide of catalytic activity is answered, so as to prepare the oxygen evolution reaction catalyst with high activity.And the reaction can be with
By controlling the content of peroxide, the regulation and control for material surface site, and then the speed of control oxygen evolution reaction can be achieved,
And generated in preparation process without addition product, improve the purity and catalytic performance of catalyst.
Preferably to explain the present invention, several specific embodiments given below：
Embodiment 1
Two kinds of transition metals of Co, Fe will be contained, and (Co/Fe mol ratios are 1：99-99:1) composite oxides with
100g/L mass concentration is scattered in 0.005-0.5M NaOH solutions, ultrasonic 1h, hydrogen peroxide is subsequently added, according to peroxide
Compound：Metal ion mol ratio is 50:1 ratio adds hydrogen peroxide, is heated to 100 DEG C, is incubated 5h, cooling, by what is obtained
Mixture is centrifuged, and gained solid is efficient oxygen evolution reaction catalyst (such as Fig. 2).This chemical oxidation treatment can be
Oxyhydroxide of the material surface formation with higher oxygen evolution reaction catalytic activity, although be progress oxygen by substrate of oxide
Change is handled, and its oxygen evolution reaction catalysis activity can also be significantly improved, and oxygen evolution reaction overpotential is obviously reduced, initial action
Current potential is substantially negative compared to before oxidation processes to be moved, and the kinetic current under 1.5V improves decades of times (such as Fig. 3).
Embodiment 2
Two kinds of transition metals of Ni, Fe will be contained, and (Ni/Fe mol ratios are 1：99-99:1) sulfide is with 10g/L's
Mass concentration is dispersed in water, and is stirred, and is subsequently added Peracetic acid, by peroxide：Metal ion mol ratio is 5:1
Ratio is added, and heated sealed is incubated 1h, after cooling filters mixture to 160 DEG C, and the solid of gained is that efficient oxygen is separated out
Catalysts.
Embodiment 3
Two kinds of transition metals of Mn, Fe will be contained, and (Mn/Fe mol ratios are 1：99-99:1) composite oxides with
5000g/L mass concentration is scattered in 0.005-0.5M NaOH solutions, ultrasonic 1h, hydrogen peroxide is subsequently added, according to peroxide
Compound：Metal ion mol ratio is 1:1 ratio adds at hydrogen peroxide, 20 DEG C and places 5h, by the centrifugation point of obtained mixture
From gained solid is efficient oxygen evolution reaction catalyst.This chemical oxidation treatment can material surface formation have compared with
The oxyhydroxide of high oxygen evolution reaction catalysis activity, although be progress oxidation processes by substrate of oxide, its oxygen separates out anti-
Catalytic activity is answered also to be significantly improved.
Embodiment 4
Two kinds of transition metals of Co, Fe will be contained, and (Co/Fe mol ratios are 1：99-99:1) composite oxides with
0.1g/L mass concentration is scattered in 0.005-0.5M NaOH solutions, ultrasonic 1h, Peracetic acid is subsequently added, according to peroxide
Compound：Metal ion mol ratio is 1000:1 ratio adds hydrogen peroxide, is heated to 200 DEG C, is incubated 1min, cools down, will
The mixture arrived is centrifuged, and gained solid is efficient oxygen evolution reaction catalyst.This chemical oxidation treatment can be in material
Expect that surface forms the oxyhydroxide with higher oxygen evolution reaction catalytic activity, although aoxidized by substrate of oxide
Processing, its oxygen evolution reaction catalysis activity can also be significantly improved.
As it will be easily appreciated by one skilled in the art that the foregoing is merely illustrative of the preferred embodiments of the present invention, it is not used to
The limitation present invention, any modifications, equivalent substitutions and improvements made within the spirit and principles of the invention etc., it all should include
Within protection scope of the present invention.
Claims (7)
1. a kind of preparation method of oxygen evolution reaction catalyst, it is characterised in that this method comprises the following steps：
Compound with two or more transiting metal components is scattered in aqueous by S1 with 0.1g/L-5000g/L mass concentration
In solution, ultrasonic mixing is uniform；
Peroxide is added in the mixture that S2 is obtained in step sl, wherein, by the addition setting of the peroxide such as
Under：The molar ratio range of the peroxide and the metal ion in compound is (1-1000):1；
S3 is heated the mixture obtained in step S2, the surface hair of the peroxide and transistion metal compound
Raw oxidation reaction, the oxyhydroxide with oxygen evolution reaction catalysis activity is formed on the surface of transition metal oxide；
Mixture cooling after heating and isolated solid are made oxygen evolution reaction catalyst by S4.
2. preparation method as claimed in claim 1, it is characterised in that in step sl, the transition metal be preferably Fe,
Co, Ni or Mn.
3. preparation method as claimed in claim 1 or 2, it is characterised in that in step sl, the change of the transition metal formation
Compound is preferably the one or more in following material：Oxide, sulfide, phosphide, selenides, carbide or nitride.
4. preparation method as claimed in claim 3, it is characterised in that in step sl, the aqueous solution is following material
In one kind or its mixture：Pure water, Klorvess Liquid, sodium chloride solution, potassium hydroxide solution, sodium hydroxide solution, sulfuric acid
Potassium solution or metabisulfite solution.
5. preparation method as claimed in claim 4, it is characterised in that in step s 2, the peroxide is following material
In one kind or its mixture：Hydrogen peroxide, diacetone peroxide, 2,2- be double-and (tert-butyl peroxide) propane, 2,2- be double-
(tert-butyl peroxide) butane or Peracetic acid.
6. preparation method as claimed in claim 5, it is characterised in that in step s3, the condition of the heating is preferred
It is as follows：Heating-up temperature is 20 DEG C -200 DEG C, and the heat time is 1min-48h.
7. preparation method as claimed in claim 6, it is characterised in that separation method in step s 4 using centrifuging or
It is separated by filtration.
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| CN110947374A (en) * | 2019-12-16 | 2020-04-03 | 佛山职业技术学院 | Hydroxyl metal oxide nano catalyst and preparation method thereof |
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