A kind of AlOOH-CoSe2O compoiste material and its preparation method are analysed in electro-catalysis
阅读说明：本技术 一种AlOOH-CoSe2电催化析氧复合材料及其制法 (A kind of AlOOH-CoSe2O compoiste material and its preparation method are analysed in electro-catalysis ) 是由 周丽丽 于 2019-09-04 设计创作，主要内容包括：本发明涉及电催化析氧材料技术领域,且公开了一种AlOOH-CoSe_2电催化剂析氧复合材料及其制法,配方包括以下实验原料：无水氯化铝、无水乙二醇、六水合氯化钴、硒粉、催化剂。该AlOOH-CoSe_2电催化析氧复合材料及其制法,材料中的AlOOH和CoSe_2之间具有强电子相互作用,有效地提高了材料的电导性,促进了电荷在电解液和电极之间的转移,进而增强了析氧材料的电催化性能,微米级CoSe_2提供了巨大的比表面积,通过电解法使AlOOH完全均匀地附着在新生成的CoSe_2的表面,大幅增加了电催化活性面积,达到了增强电催化材料的析氧性能的效果,同时AlOOH在电解过程中释放的大量-OH基团在材料的表面形成网状保护膜,使析氧材料在碱性的电解液中不被分解,增强了析氧材料的化学稳定性。(The present invention relates to electro-catalysis to analyse oxygen field of material technology, and discloses a kind of AlOOH-CoSe 2 Elctro-catalyst analyses O compoiste material and its preparation method, and formula includes following experimental raw: anhydrous aluminum chloride, without water glycol, cobalt chloride hexahydrate, selenium powder, catalyst.The AlOOH-CoSe 2 O compoiste material and its preparation method, AlOOH and CoSe in material are analysed in electro-catalysis 2 Between have strong electron interaction, effectively improve the electrical conductance of material, promote transfer of the charge between electrolyte and electrode, so enhance analysis oxygen material electrocatalysis characteristic, micron order CoSe 2 Huge specific surface area is provided, so that AlOOH is completely homogeneously attached to newly-generated CoSe by electrolysis method 2 Surface; it is added significantly to electro catalytic activity area; the analysis oxygen performance for enhancing electrocatalysis material is achieved the effect that; a large amount of-OH groups that AlOOH discharges in electrolytic process simultaneously form reticular protection film on the surface of material; so that analysis oxygen material is not decomposed in the electrolyte of alkalinity, enhances the chemical stability of analysis oxygen material.)
1. a kind of AlOOH-CoSe2O compoiste material and its preparation method are analysed in electro-catalysis, the raw material including following parts by weight proportion, Be characterized in that: 13-18 parts of anhydrous aluminum chlorides, 55-68 parts without water glycol, 15-20 parts of cobalt chloride hexahydrates, 3.5-6 parts of selenium powders, 0.5-1 parts of catalyst.
2. a kind of AlOOH-CoSe according to claim 12O compoiste material and its preparation method are analysed in electro-catalysis, it is characterised in that: institute Stating AlCl3 mass fraction in anhydrous aluminum chloride is 96.8-98.3%.
3. a kind of AlOOH-CoSe according to claim 12O compoiste material and its preparation method are analysed in electro-catalysis, it is characterised in that: institute Stating OH-CH2CH2-OH content in no water glycol is 98.5-99.2%.
4. a kind of AlOOH-CoSe according to claim 12O compoiste material and its preparation method are analysed in electro-catalysis, it is characterised in that: institute Stating cobalt chloride hexahydrate is CoCl3·6H2O, wherein CoCl3Mass fraction is 51.8-53.6%.
5. a kind of AlOOH-CoSe according to claim 12O compoiste material and its preparation method are analysed in electro-catalysis, it is characterised in that: institute Stating selenium powder is elemental selenium, and wherein Se content is 98.3-99.5%.
6. a kind of AlOOH-CoSe according to claim 12O compoiste material and its preparation method are analysed in electro-catalysis, it is characterised in that: institute Stating catalyst is N2H4·H2O mass fraction is 96.8.5-98.4%.
7. a kind of AlOOH-CoSe according to claim 12O compoiste material and its preparation method are analysed in electro-catalysis, it is characterised in that: institute State AlOOH-CoSe2Electro-catalysis analyse O compoiste material, preparation method the following steps are included:
(1) it prepares aluminum oxyhydroxide AlOOH micelle: 55-68 parts being successively added into 1000mL beaker without water glycol and 13-18 Part anhydrous aluminum chloride simultaneously stirs evenly, and then places the beaker in ultrasonic treatment instrument, is heated to 70-75 DEG C, supersonic frequency is 25KHz carries out ultrasonic treatment 6-8h, is dispersed in material in ethylene glycol solvent and forms colloidal sol, and material in beaker is shifted Into high-pressure hydrothermal reaction kettle, and reaction kettle is placed in reaction kettle heater and is heated to 280-285 DEG C, it will after reaction 24-28h High-pressure hydrothermal reaction kettle is cooled to room temperature, and material in reactor is filtered by Buchner funnel, is removed solvent, is reused 500- 600mL ethyl alcohol and 3000-4000mL distilled water successively replace cleaning product, remove remaining ethylene glycol and byproduct of reaction, most The product of washes clean is placed in baking oven afterwards and is heated to 65-70 DEG C, moisture 6-8h is dried, white gum object hydroxyl is prepared Aluminium oxide Al OOH micelle.
(2) prepare micron order CoSe: into beaker be added 600mL distilled water, then successively weigh 15-20 parts of cobalt chloride hexahydrates, 3.5-6 parts of selenium powders and 0.5-1 parts of catalyst ns2H4·H2O is added into beaker, is after mixing evenly transferred into the material in beaker In high-pressure hydrothermal reaction kettle, reaction kettle is placed in reaction kettle heater box, 220-230 DEG C of reaction 12-15h is heated to, has reacted Reaction kettle is cooled to room temperature after complete and material is fully transferred in planetary ball mill, and 800mL ethyl alcohol is added, ball milling 10- 12h, until then the good material filtering of ball milling is gone out liquid and obtain two selenizing cobalt precursors by all materials by 1340 mesh mesh screens Body, and successively washed using the dilute hydrochloric acid and 4000-5000mL distilled water that substance withdrawl syndrome is 1.5-1.8mol/L, it will wash Two clean cobaltous selenides, which are placed in baking oven, is heated to 80-85 DEG C, and dry moisture 6-7h obtains the solid powder that partial size is 10-12um Last micron order CoSe.
(3) AlOOH-CoSe is prepared2O compoiste material is analysed in electro-catalysis: 1000mL distilled water being added into 2000mL beaker, and successively 15g anhydrous Na is added2CO3, 20g anhydrous NaCl and the anhydrous Fe (NH of 35g4)2(SO4)2·6H2O, and sequentially add above-mentioned steps (1) obtained to prepare micron order CoSe made from aluminum oxyhydroxide AlOOH micelle and step (2), at the uniform velocity stirring keeps solid whole Electrolyte is prepared in dissolution, and glassy carbon electrode is working electrode, and as reference electrode, platinized platinum is used as to electrode, electricity Ag/AgCl The current density of solution is 0.15mAcm2-It is electrolysed 2-3h, then takes out glassy carbon electrode, and with 2000-3000mL distilled water The product of cleaning glass carbon electrodes, and solid product is extracted to be placed in baking oven and is heated to 70-75 DEG C, dry moisture 7-8h obtains AlOOH-CoSe2O compoiste material is analysed in electro-catalysis.
Technical field
The present invention relates to electro-catalysis analysis oxygen field of material technology, specially a kind of AlOOH-CoSe2Oxygen composite wood is analysed in electro-catalysis Material and its preparation method.
Background technique
With fossil energy gradually decrease with fossil energy burning after caused by environmental problem become increasingly conspicuous, social development Demand to renewable and clean energy resource becomes more more and more urgent, therefore develops clean energy technology as the hot spot studied both at home and abroad One of, wherein water electrolysis hydrogen production is one of the most effective means for obtaining renewable hydrogen energy, and water electrolysis hydrogen production process relates generally to To hydrogen and oxygen, skill is converted and stored to the evolution reaction on anode and cathode, Electrochemical oxygen evolution reaction in various energy respectively Play an important role in terms of art, for electrolysis water, its reaction speed mainly by complexity and dynamics is slow Oxygen evolution reaction is determined, then can solve the slow process of its dynamics using efficient Electrochemical oxygen evolution catalysts.
Currently used in the catalysis material of Electrochemical oxygen evolution, it is most useful that platinum, ruthenium noble metal catalyst.However due to Precious Metals Resources are rare, expensive, therefore the industrialized production of such catalyst is extremely restricted, and is urged compared to noble metal Agent, base metal (such as: iron, cobalt, nickel, manganese) sill are used to develop high work due to resourceful, cheap The material of property is with catalytic electrochemical oxygen evolution reaction, but these materials are lower in conductivity, electro catalytic activity area very little, simultaneously The chemical stability of these materials is poor in electrolytic process, reduces the practicability and durability of electro-catalysis analysis oxygen material.
Summary of the invention
(1) the technical issues of solving
In view of the deficiencies of the prior art, the present invention provides a kind of AlOOH-CoSe2Electro-catalysis analyse O compoiste material and its The problem of preparation method, it is lower in conductivity to solve existing material, electro catalytic activity area very little, while solving electro-catalysis again It is poor to analyse chemical stability in oxygen material electrolytic process, the problem for causing durability not high.
(2) technical solution
To achieve the above object, the invention provides the following technical scheme: a kind of AlOOH-CoSe2Oxygen composite wood is analysed in electro-catalysis Material and its preparation method, including following parts by weight proportion raw material: 13-18 parts of anhydrous aluminum chlorides, 55-68 parts without water glycol, 15-20 parts of cobalt chloride hexahydrates, 3.5-6 parts of selenium powders, 0.5-1 parts of catalyst.
Preferably, AlCl3 mass fraction is 96.8-98.3% in the anhydrous aluminum chloride.
Preferably, OH-CH2CH2-OH content is 98.5-99.2% in the no water glycol.
Preferably, the cobalt chloride hexahydrate is CoCl3·6H2O, wherein CoCl3Mass fraction is 51.8-53.6%.
Preferably, the selenium powder is elemental selenium, and wherein Se content is 98.3-99.5%.
Preferably, the catalyst is N2H4·H2O mass fraction is 96.8.5-98.4%.
Preferably, the AlOOH-CoSe2Electro-catalysis analyse O compoiste material, preparation method the following steps are included:
(1) prepare aluminum oxyhydroxide AlOOH micelle: successively into 1000mL beaker be added 55-68 part without water glycol with 13-18 parts of anhydrous aluminum chlorides simultaneously stir evenly, and then place the beaker in ultrasonic treatment instrument, are heated to 70-75 DEG C, supersonic frequency For 25KHz, ultrasonic treatment 6-8h is carried out, material is dispersed in ethylene glycol solvent and forms colloidal sol, material in beaker is turned It moves in high-pressure hydrothermal reaction kettle, and reaction kettle is placed in reaction kettle heater and is heated to 280-285 DEG C, after reacting 24-28h High-pressure hydrothermal reaction kettle is cooled to room temperature, and material in reactor is filtered by Buchner funnel, solvent is removed, reuses 500-600mL ethyl alcohol and 3000-4000mL distilled water successively replace cleaning product, remove remaining ethylene glycol and reaction by-product The product of washes clean is finally placed in baking oven and is heated to 65-70 DEG C by object, dries moisture 6-8h, white gum is prepared Object aluminum oxyhydroxide AlOOH micelle.
(2) it prepares micron order CoSe: 600mL distilled water being added into beaker, then successively weigh 15-20 part six and be hydrated chlorine Change cobalt, 3.5-6 parts of selenium powders and 0.5-1 parts of catalyst ns2H4·H2O is added into beaker, after mixing evenly by the material in beaker It is transferred into high-pressure hydrothermal reaction kettle, reaction kettle is placed in reaction kettle heater box, be heated to 220-230 DEG C of reaction 12-15h, Reaction kettle is cooled to room temperature after fully reacting and material is fully transferred in planetary ball mill, and 800mL ethyl alcohol, ball is added 10-12h is ground, until then the good material filtering of ball milling is gone out liquid and obtain two cobaltous selenides by all materials by 1340 mesh mesh screens Presoma, and successively washed using the dilute hydrochloric acid and 4000-5000mL distilled water that substance withdrawl syndrome is 1.5-1.8mol/L, it will Two cobaltous selenides of washes clean, which are placed in baking oven, is heated to 80-85 DEG C, and dry moisture 6-7 h, obtaining partial size is consolidating for 10-12um Body powder micron order CoSe.
(3) AlOOH-CoSe is prepared2O compoiste material is analysed in electro-catalysis: 1000mL distilled water is added into 2000mL beaker, And sequentially add 15g anhydrous Na2CO3, 20g anhydrous NaCl and the anhydrous Fe (NH of 35g4)2(SO4)2·6H2O, and sequentially add Micron order CoSe made from step (1) preparation aluminum oxyhydroxide AlOOH micelle obtained and step (2) is stated, at the uniform velocity stirring makes solid Electrolyte is prepared in the whole dissolutions of body, and glassy carbon electrode is working electrode, and Ag/AgCl is as reference electrode, platinized platinum conduct pair Electrode, the current density of electrolysis are 0.15mAcm2-It is electrolysed 2-3h, is then taken out glassy carbon electrode, and use 2000- The product of 3000mL distilled water cleaning glass carbon electrodes, and solid product is extracted to be placed in baking oven and is heated to 70- 75 DEG C, dry moisture 7-8h obtains AlOOH-CoSe2O compoiste material is analysed in electro-catalysis.
(3) beneficial technical effect
Compared with prior art, the present invention has following beneficial technical effect:
1, the AlOOH-CoSe2O compoiste material and its preparation method, AlOOH and CoSe in material are analysed in electro-catalysis2Between have There is strong electron interaction, effectively improve the electrical conductance of material, promotes transfer of the charge between electrolyte and electrode, And then the electrocatalysis characteristic of analysis oxygen material is enhanced, meanwhile, micron order CoSe2Huge specific surface area is provided, electrolysis is passed through Method increases the electrode surface roughness and porosity of material, AlOOH is made completely homogeneously to be attached to newly-generated CoSe2's Surface, greatly improved the contact area of electrocatalysis material and electrolyte, to increase electro catalytic activity area, reach increasing The effect of the analysis oxygen performance of forceful electric power catalysis material.
2, the AlOOH-CoSe2Electro-catalysis analysis O compoiste material and its preparation method, AlOOH discharge a large amount of in electrolytic process Hydroxyl-OH and CoSe2Synergistic effect is formed, the transmitting resistance of interface charge is reduced, to improve electron transfer rate, is dropped The oxygen evolution potential of low electrolysis and and overpotential, to improve the efficiency of electrolysis analysis oxygen, while AlOOH is released in electrolytic process A large amount of-OH the groups put form reticular protection film on the surface of material, and analysis oxygen material is made not to be decomposed in the electrolyte of alkalinity, Its chemical stability is enhanced, the practicability and durability of electrocatalysis material are improved.
Specific embodiment
To achieve the above object, the invention provides the following technical scheme: a kind of AlOOH-CoSe2Oxygen composite wood is analysed in electro-catalysis Material and its preparation method, the raw material including following parts by weight proportion, 13-18 parts of anhydrous aluminum chlorides, 55-68 parts without water glycol, 15- 20 parts of cobalt chloride hexahydrates, 3.5-6 parts of selenium powders, 0.5-1 parts of catalyst, AlCl3 mass fraction is 96.8- in anhydrous aluminum chloride 98.3%, OH-CH2CH2-OH content is 98.5-99.2%, cobalt chloride hexahydrate CoCl in no water glycol3·6H2O, Middle CoCl3Mass fraction is 51.8-53.6%, and selenium powder is elemental selenium, and wherein Se content is 98.3-99.5%, and catalyst is N2H4·H2O mass fraction is 96.8.5-98.4%, AlOOH-CoSe2Electro-catalysis analyse O compoiste material, preparation method include with Lower step:
(1) prepare aluminum oxyhydroxide AlOOH micelle: successively into 1000mL beaker be added 55-68 part without water glycol with 13-18 parts of anhydrous aluminum chlorides simultaneously stir evenly, and then place the beaker in ultrasonic treatment instrument, are heated to 70-75 DEG C, supersonic frequency For 25KHz, ultrasonic treatment 6-8h is carried out, material is dispersed in ethylene glycol solvent and forms colloidal sol, material in beaker is turned It moves in high-pressure hydrothermal reaction kettle, and reaction kettle is placed in reaction kettle heater and is heated to 280-285 DEG C, after reacting 24-28h High-pressure hydrothermal reaction kettle is cooled to room temperature, and material in reactor is filtered by Buchner funnel, solvent is removed, reuses 500-600mL ethyl alcohol and 3000-4000mL distilled water successively replace cleaning product, remove remaining ethylene glycol and reaction by-product The product of washes clean is finally placed in baking oven and is heated to 65-70 DEG C by object, dries moisture 6-8h, white gum is prepared Object aluminum oxyhydroxide AlOOH micelle.
(2) it prepares micron order CoSe: 600mL distilled water being added into beaker, then successively weigh 15-20 part six and be hydrated chlorine Change cobalt, 3.5-6 parts of selenium powders and 0.5-1 parts of catalyst ns2H4·H2O is added into beaker, after mixing evenly by the material in beaker It is transferred into high-pressure hydrothermal reaction kettle, reaction kettle is placed in reaction kettle heater box, be heated to 220-230 DEG C of reaction 12-15h, Reaction kettle is cooled to room temperature after fully reacting and material is fully transferred in planetary ball mill, and 800mL ethyl alcohol, ball is added 10-12h is ground, until then the good material filtering of ball milling is gone out liquid and obtain two cobaltous selenides by all materials by 1340 mesh mesh screens Presoma, and successively washed using the dilute hydrochloric acid and 4000-5000mL distilled water that substance withdrawl syndrome is 1.5-1.8mol/L, it will Two cobaltous selenides of washes clean, which are placed in baking oven, is heated to 80-85 DEG C, and dry moisture 6-7 h, obtaining partial size is consolidating for 10-12um Body powder micron order CoSe.
(3) AlOOH-CoSe is prepared2O compoiste material is analysed in electro-catalysis: 1000mL distilled water is added into 2000mL beaker, And sequentially add 15g anhydrous Na2CO3, 20g anhydrous NaCl and the anhydrous Fe (NH of 35g4)2(SO4)2·6H2O, and sequentially add Micron order CoSe made from step (1) preparation aluminum oxyhydroxide AlOOH micelle obtained and step (2) is stated, at the uniform velocity stirring makes solid Electrolyte is prepared in the whole dissolutions of body, and glassy carbon electrode is working electrode, and Ag/AgCl is as reference electrode, platinized platinum conduct pair Electrode, the current density of electrolysis are 0.15mAcm2-It is electrolysed 2-3h, is then taken out glassy carbon electrode, and use 2000- The product of 3000mL distilled water cleaning glass carbon electrodes, and solid product is extracted to be placed in baking oven and is heated to 70- 75 DEG C, dry moisture 7-8h obtains AlOOH-CoSe2O compoiste material is analysed in electro-catalysis.