CN119082766A - A Fe2Ni5 type crystalline-amorphous heterostructure aerogel catalyst and its preparation method and application - Google Patents
A Fe2Ni5 type crystalline-amorphous heterostructure aerogel catalyst and its preparation method and application Download PDFInfo
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- 239000004964 aerogel Substances 0.000 title claims abstract description 53
- 239000003054 catalyst Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 50
- 238000000034 method Methods 0.000 claims abstract description 21
- 238000004519 manufacturing process Methods 0.000 claims abstract description 12
- 239000000084 colloidal system Substances 0.000 claims abstract description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 9
- 239000001257 hydrogen Substances 0.000 claims abstract description 9
- YTQVNYGLBGECJA-UHFFFAOYSA-L [Fe].[Ni](O)O Chemical compound [Fe].[Ni](O)O YTQVNYGLBGECJA-UHFFFAOYSA-L 0.000 claims abstract description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 60
- 239000000243 solution Substances 0.000 claims description 44
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 30
- 239000000017 hydrogel Substances 0.000 claims description 24
- UGKDIUIOSMUOAW-UHFFFAOYSA-N iron nickel Chemical compound [Fe].[Ni] UGKDIUIOSMUOAW-UHFFFAOYSA-N 0.000 claims description 21
- 229910052751 metal Inorganic materials 0.000 claims description 20
- 239000002184 metal Substances 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 16
- 239000008367 deionised water Substances 0.000 claims description 15
- 229910021641 deionized water Inorganic materials 0.000 claims description 15
- RJTANRZEWTUVMA-UHFFFAOYSA-N boron;n-methylmethanamine Chemical compound [B].CNC RJTANRZEWTUVMA-UHFFFAOYSA-N 0.000 claims description 13
- 239000011259 mixed solution Substances 0.000 claims description 12
- 229910052759 nickel Inorganic materials 0.000 claims description 11
- LAIZPRYFQUWUBN-UHFFFAOYSA-L nickel chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Ni+2] LAIZPRYFQUWUBN-UHFFFAOYSA-L 0.000 claims description 11
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical compound B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 claims description 10
- 238000011534 incubation Methods 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 7
- 229940044631 ferric chloride hexahydrate Drugs 0.000 claims description 7
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 claims description 7
- 150000003839 salts Chemical class 0.000 claims description 7
- 238000004108 freeze drying Methods 0.000 claims description 6
- 229910000085 borane Inorganic materials 0.000 claims description 5
- 238000004140 cleaning Methods 0.000 claims description 5
- 239000012266 salt solution Substances 0.000 claims description 5
- 238000005868 electrolysis reaction Methods 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 2
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 9
- 229910052723 transition metal Inorganic materials 0.000 abstract description 9
- 150000003624 transition metals Chemical class 0.000 abstract description 9
- 239000000463 material Substances 0.000 abstract description 7
- 239000013078 crystal Substances 0.000 abstract description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052760 oxygen Inorganic materials 0.000 abstract description 3
- 239000001301 oxygen Substances 0.000 abstract description 3
- 239000002245 particle Substances 0.000 abstract description 3
- 238000000975 co-precipitation Methods 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- YPTUAQWMBNZZRN-UHFFFAOYSA-N dimethylaminoboron Chemical compound [B]N(C)C YPTUAQWMBNZZRN-UHFFFAOYSA-N 0.000 abstract 1
- 230000001603 reducing effect Effects 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 11
- 230000008569 process Effects 0.000 description 8
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 6
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 6
- 229940032296 ferric chloride Drugs 0.000 description 6
- 229960004887 ferric hydroxide Drugs 0.000 description 6
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 6
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 description 6
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 229910000510 noble metal Inorganic materials 0.000 description 4
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- 229910021389 graphene Inorganic materials 0.000 description 3
- 238000001027 hydrothermal synthesis Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 238000003980 solgel method Methods 0.000 description 3
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 241000282414 Homo sapiens Species 0.000 description 1
- 229910013504 M-O-M Inorganic materials 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000000352 supercritical drying Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
Classifications
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- 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
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/11—Making amorphous alloys
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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
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
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- 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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Abstract
本发明公开了一种Fe2Ni5型晶‑非晶异质结构气凝胶催化剂及其制备方法和应用，属于催化剂技术领域。本发明通过湿化学共沉淀法实现了过渡族金属气凝胶材料的制备，利用二甲氨硼烷温和的还原性质，使得铁镍氢氧化物非晶胶粒内部缓慢生长出FeNi3晶型团簇，产生具有晶体‑非晶(c‑a)异质结构的多相催化活性位点，生成气凝胶三维结构与(c‑a)异质结构混合组织材料。所制备的Fe2Ni5型晶‑非晶异质结构气凝胶催化剂具有优异的电解水析氧性能，能够有效提升电解水制氢效率。
The invention discloses a Fe2Ni5 type crystal-amorphous heterostructure aerogel catalyst and its preparation method and application, belonging to the technical field of catalysts. The invention realizes the preparation of transition metal aerogel materials by wet chemical coprecipitation method, and utilizes the mild reducing property of dimethylaminoborane to slowly grow FeNi3 crystal clusters inside the iron-nickel hydroxide amorphous colloid particles, generate multiphase catalytic active sites with crystal-amorphous (c-a) heterostructure, and generate aerogel three-dimensional structure and (c-a) heterostructure mixed tissue material. The prepared Fe2Ni5 type crystal- amorphous heterostructure aerogel catalyst has excellent electrolytic water oxygen evolution performance, and can effectively improve the electrolytic water hydrogen production efficiency.
Description
Technical Field
The invention belongs to the technical field of catalysts, and particularly relates to an Fe 2Ni5 type crystal-amorphous heterostructure aerogel catalyst, and a preparation method and application thereof.
Background
The energy problem is a great difficulty in obstructing the development of human beings at present, and it is urgent to seek a new energy which is green, environment-friendly, sustainable, efficient and low-cost. The hydrogen energy source is used as a cleanest renewable new energy source and is a substitute for fossil fuel in the future. Electrolysis of water using renewable energy sources such as solar energy is considered to be the most promising method for "green hydrogen" production. However, in the electrolytic water reaction, a large kinetic resistance is required to be overcome, because in actual production, the Oxygen Evolution Reaction (OER) of the anode involves 4 electron transfer processes in the overall water splitting reaction. Therefore, the preparation of the OER catalyst with good catalytic performance is a key for improving the hydrogen production efficiency of water electrolysis.
Early studies found that noble metal materials such as platinum/ruthenium/iridium exhibit superior catalytic properties, but their use in OER was severely hampered by the high price. Transition group metals have been widely studied for their excellent catalytic performance, abundant reserves and low price, but the catalytic effect of simple transition group metals is not ideal. In recent years, researchers have found that synergism between transition metals can effectively reduce the free energy of OER reactions and thereby produce many excellent catalysts such as transition metal alloys, transition metal hydroxides, transition metal oxides.
The existence of a large number of unsaturated sites in the amorphous material structure and the flexible self-driven structure can rapidly reconstruct themselves in the OER reaction process so as to meet the reaction requirement. Research has shown that amorphous catalysts have better catalytic capabilities than crystalline catalysts, but are limited by irregular atomic arrangements, which tend to have lower conductivities. Aerogels provide more active sites for OER reactions due to their unique high porosity and self-supporting three-dimensional framework structure, and their cross-linked three-dimensional network greatly accelerates electron transport, which makes the aerogel exhibit superior catalytic performance in OER field. However, most of researches at present focus on noble metal aerogel or carbon-based aerogel loaded with non-noble metal in a complex synthesis process, and the process for preparing the aerogel is slow and complex, so that the method is not beneficial to industrial hydrogen production. If the amorphous structure is organically combined with the aerogel structure, metal atoms are automatically assembled to form an aerogel framework through a wet chemical reduction method, and the pure transition metal aerogel with controllable components, controllable morphology, controllable performance, high specific surface area and high porosity is prepared. In addition, a great deal of research shows that the compact crystal-amorphous (c-a) heterostructure can provide more reactive sites and more reaction driving force for electron migration, and the characteristics enable the crystal-amorphous (c-a) heterostructure to have unique advantages in the catalyst field. Therefore, if a pure transition metal aerogel having a distinct crystalline and amorphous structure inside could be produced by a simple synthesis process and relatively safe industrial raw materials, a new solution would be provided for the preparation of transition metal catalysts.
In the field of aerogel catalyst preparation, technologies such as a hydrothermal method, a sol-gel method and the like are mainly adopted at present to prepare hydrogel firstly, and then the aerogel is obtained through technologies such as environmental drying, freeze drying or supercritical drying. According to the hydrothermal method, a high-temperature and high-pressure reaction environment is created by heating a reaction container, along with the progress of the reaction, a partially reduced GO sheet layer gradually self-assembles into a three-dimensional network structure through pi-pi interaction and Van der Waals force to form hydrogel, meanwhile, N element and ruthenium element are loaded on the aerogel in the graphene hydrogel generation process, finally, the noble metal loaded graphene hydrogel with a shell-core structure is formed, and the graphene aerogel is prepared through freeze drying. Sol-gel process typically involves dissolving metal organic or inorganic precursors (e.g., metal alkoxides, chlorides, etc.) in a solvent, and forming a metal hydroxy complex by hydrolysis, then forming an M-O-M (M represents a metal) bond by condensation, forming sol particles, and finally drying by supercritical CO 2 to obtain an aerogel. The hydrothermal method is used for preparing the carbon-based aerogel, the preparation process is complex, a plurality of precursors are often required to be synthesized, and metal crystals are required to grow in a heat treatment mode after the aerogel is obtained. By sol gel process, multiple steps are often required to be precisely controlled during the preparation process, and finally repeated washing is often required to remove residual condensing agent during the preparation process. The two methods for preparing the aerogel have more process control links and higher cost, are unfavorable for industrial mass production, have more severe growth environment and are difficult to popularize in actual production.
In the preparation process of transition metal crystallization-amorphous (c-a) heterostructures, more preparation methods at present are to prepare materials with crystal structures firstly, then prepare materials with amorphous structures, finally prepare the crystal-amorphous (c-a) heterostructures by hydrothermal or electrodeposition, the method is complex in process, and metal nano particles with compact crystal-amorphous (c-a) heterostructures are difficult to synthesize, so that the combination of crystal and amorphous interfaces is loose, the resistance of charge transfer is increased, and the OER performance of the catalyst is reduced.
Disclosure of Invention
Aiming at the prior art, the invention provides an Fe 2Ni5 type crystal-amorphous heterostructure aerogel catalyst and a preparation method and application thereof, so as to solve the technical problems of difficult preparation and poor hydrogen evolution catalytic performance of the existing aerogel catalyst.
In order to achieve the above purpose, the technical scheme adopted by the invention is that the preparation method of the Fe 2Ni5 type crystal-amorphous heterostructure aerogel catalyst comprises the following steps:
S1, ferric chloride hexahydrate and nickel chloride hexahydrate are dissolved in water to obtain an iron-nickel metal salt water solution, and dimethylamine borane is dissolved in water to obtain a dimethylamine borane water solution;
S2, adding the water solution of the dimesyl borane into the iron-nickel metal salt solution, and uniformly stirring to obtain a mixed solution;
s3, adding potassium hydroxide into the mixed solution, and uniformly stirring to obtain an iron-nickel hydroxide colloid solution;
S4, incubating the ferric nickel hydroxide colloid solution for 45-50 hours under the dark condition of 20-30 ℃ to obtain Fe 2Ni5 type ferric nickel-based hydrogel;
And S5, cleaning the Fe 2Ni5 type iron-nickel based hydrogel with deionized water for 2-4 times, and then freeze-drying to obtain the Fe 2Ni5 type iron-nickel based hydrogel.
On the basis of the technical scheme, the invention can be improved as follows.
Further, the molar ratio of ferric chloride hexahydrate to nickel chloride hexahydrate in the iron-nickel metal salt aqueous solution is 2:5.
Further, the molar ratio of the dimesyl borane to the nickel chloride hexahydrate in the mixed solution is 1:100.
Further, the molar ratio of the addition of potassium hydroxide to nickel chloride hexahydrate was 1:1.
Further, the incubation temperature in S4 was 25 ℃ and the incubation time was 48h.
Further, the step of washing with deionized water in S5 comprises the steps of immersing Fe 2Ni5 type iron-nickel-based hydrogel in deionized water and centrifuging at 8000rpm for 10-20 min.
And the freeze drying temperature in the step S5 is-40 to-20 ℃ and the drying time is 10-15 h.
The invention also discloses the Fe 2Ni5 type crystal-amorphous heterostructure aerogel catalyst prepared by the preparation method.
The invention also discloses application of the Fe 2Ni5 type crystal-amorphous heterostructure aerogel catalyst in hydrogen production by water electrolysis.
The beneficial effects of the invention are as follows:
According to the preparation method, the transition metal aerogel material is prepared by a wet chemical coprecipitation method, feNi 3 crystal form clusters are slowly grown in the iron-nickel hydroxide amorphous colloidal particles by utilizing the mild reduction property of the dimesyl borane, heterogeneous catalytic active sites with crystal-amorphous (c-a) heterostructure are generated, and the aerogel three-dimensional structure and (c-a) heterostructure mixed tissue material is generated. The prepared Fe 2Ni5 type crystal-amorphous heterostructure aerogel catalyst has excellent electrolytic water oxygen evolution performance, and can effectively improve the hydrogen production efficiency of electrolytic water.
Drawings
FIG. 1 is an SEM photograph of an Fe 2Ni5 -type crystalline-amorphous heterostructure aerogel catalyst;
FIG. 2 is a TEM photograph of an Fe 2Ni5 -type crystalline-amorphous heterostructure aerogel catalyst;
FIG. 3 is an XRD diffraction pattern of an Fe 2Ni5 -type crystalline-amorphous heterostructure aerogel catalyst;
Fig. 4 is an OER performance LSV curve of an Fe 2Ni5 type crystalline-amorphous heterostructure aerogel catalyst.
Detailed Description
The following describes the present invention in detail with reference to examples.
Example 1
An Fe 2Ni5 type crystal-amorphous heterostructure aerogel catalyst is prepared through the following steps:
S1, dissolving 2mmol of ferric chloride hexahydrate in 50mL of water to obtain ferric chloride solution, dissolving 5mmol of nickel chloride hexahydrate in 50mL of water to obtain nickel chloride solution, pouring the ferric chloride solution and the nickel chloride solution into 50mL of deionized water, and uniformly stirring to obtain the iron-nickel metal salt water solution.
S2, stirring and dissolving 0.5mol of dimethylamine borane in 100mL of water under the water bath condition of 30 ℃ to obtain dimethylamine borane solution, and immediately adding the dimethylamine borane solution into the prepared iron-nickel metal salt solution after the stirring is finished to obtain a mixed solution;
s3, dropwise adding 5ml of KOH solution with the concentration of 1M into the mixed solution for five times, wherein 1ml of KOH solution is added each time, and stirring is not needed in the dropwise adding process;
S4, sealing the ferric hydroxide nickel colloid solution, and placing the sealed ferric hydroxide nickel colloid solution in a dark environment for incubation for 48 hours at the incubation temperature of 25 ℃ to obtain Fe 2Ni5 type ferric nickel-based hydrogel;
S5, filling Fe 2Ni5 type iron-nickel-based hydrogel into a 50mL centrifuge tube, adding deionized water to submerge the hydrogel, and centrifuging at 8000rpm for 15min, and cleaning the deionized water after centrifuging is completed;
S6, placing the cleaned Fe 2Ni5 type Fe-Ni-based hydrogel in a freeze dryer, and drying for 12 hours at the temperature of-30 ℃ to obtain the Fe 2Ni5 type crystal-amorphous heterostructure aerogel catalyst.
Example 2
An Fe 2Ni5 type crystal-amorphous heterostructure aerogel catalyst is prepared through the following steps:
S1, dissolving 2mmol of ferric chloride hexahydrate in 50mL of water to obtain ferric chloride solution, dissolving 5mmol of nickel chloride hexahydrate in 50mL of water to obtain nickel chloride solution, pouring the ferric chloride solution and the nickel chloride solution into 50mL of deionized water, and uniformly stirring to obtain the iron-nickel metal salt water solution.
S2, stirring and dissolving 0.5mol of dimethylamine borane in 100mL of water under the water bath condition of 30 ℃ to obtain dimethylamine borane solution, and immediately adding the dimethylamine borane solution into the prepared iron-nickel metal salt solution after the stirring is finished to obtain a mixed solution;
s3, dropwise adding 5ml of KOH solution with the concentration of 1M into the mixed solution for five times, wherein 1ml of KOH solution is added each time, and stirring is not needed in the dropwise adding process;
s4, sealing the ferric hydroxide nickel colloid solution, and placing the sealed ferric hydroxide nickel colloid solution in a dark environment for incubation for 45 hours, wherein the incubation temperature is 30 ℃, so as to obtain Fe 2Ni5 type ferric nickel-based hydrogel;
S5, filling Fe 2Ni5 type iron-nickel-based hydrogel into a 50mL centrifuge tube, adding deionized water to submerge the hydrogel, and centrifuging at 8000rpm for 10min, and cleaning the deionized water after centrifuging is completed;
S6, placing the cleaned Fe 2Ni5 type Fe-Ni-based hydrogel in a freeze dryer, and drying for 10 hours at the temperature of 40 ℃ below zero to obtain the Fe 2Ni5 type crystal-amorphous heterostructure aerogel catalyst.
Example 3
An Fe 2Ni5 type crystal-amorphous heterostructure aerogel catalyst is prepared through the following steps:
S1, dissolving 2mmol of ferric chloride hexahydrate in 50mL of water to obtain ferric chloride solution, dissolving 5mmol of nickel chloride hexahydrate in 50mL of water to obtain nickel chloride solution, pouring the ferric chloride solution and the nickel chloride solution into 50mL of deionized water, and uniformly stirring to obtain the iron-nickel metal salt water solution.
S2, stirring and dissolving 0.5mol of dimethylamine borane in 100mL of water under the water bath condition of 30 ℃ to obtain dimethylamine borane solution, and immediately adding the dimethylamine borane solution into the prepared iron-nickel metal salt solution after the stirring is finished to obtain a mixed solution;
s3, dropwise adding 5ml of KOH solution with the concentration of 1M into the mixed solution for five times, wherein 1ml of KOH solution is added each time, and stirring is not needed in the dropwise adding process;
s4, sealing the ferric hydroxide nickel colloid solution, and placing the sealed ferric hydroxide nickel colloid solution in a dark environment for incubation for 50 hours at an incubation temperature of 20 ℃ to obtain Fe 2Ni5 type ferric nickel-based hydrogel;
s5, filling Fe 2Ni5 type iron-nickel-based hydrogel into a 50mL centrifuge tube, adding deionized water to submerge the hydrogel, and centrifuging at 8000rpm for 20min, and cleaning the deionized water after centrifuging is completed;
S6, placing the cleaned Fe 2Ni5 type Fe-Ni-based hydrogel in a freeze dryer, and drying for 15 hours at the temperature of-20 ℃ to obtain the Fe 2Ni5 type crystal-amorphous heterostructure aerogel catalyst.
Analysis of results
The performance of the Fe 2Ni5 type crystal-amorphous heterostructure aerogel catalyst prepared in the embodiments 1-3 of the present invention is similar, and the performance of the Fe 2Ni5 type crystal-amorphous heterostructure aerogel catalyst in the embodiment 1 is taken as an example to describe the performance.
The morphology of the Fe 2Ni5 type crystal-amorphous heterostructure aerogel catalyst is detected, and the results are shown in figures 1-3, wherein figure 1 shows SEM detection results, figure 2 shows TEM detection results, and figure 3 shows XRD test results. As can be seen from fig. 1 to 3, fig. 1 shows that the Fe 2Ni5 type crystal-amorphous heterostructure aerogel presents a porous three-dimensional structure, fig. 2 shows that the Fe 2Ni5 type crystal-amorphous heterostructure aerogel is air-coagulated into a large amount of amorphous structure and a small amount of crystalline structure, wherein the crystalline structure exists in the form of nanoclusters and is tightly packed by the amorphous structure, and fig. 3 shows that the amorphous structure in the Fe 2Ni5 type crystal-amorphous heterostructure aerogel structure is a main body.
The OER performance of the Fe 2Ni5 type crystalline-amorphous heterostructure aerogel catalysts of the present invention was tested using a typical three electrode test system. As a result, as shown in FIG. 4, the Fe 2Ni5 type crystalline-amorphous heterostructure aerogel was found to have an overpotential of 262mV at a current density of 20mA cm -2. .
While specific embodiments of the invention have been described in detail in connection with the examples, it should not be construed as limiting the scope of protection of the patent. Various modifications and variations which may be made by those skilled in the art without the creative effort are within the scope of the patent described in the claims.
Claims (9)
1. The preparation method of the Fe 2Ni5 type crystal-amorphous heterostructure aerogel catalyst is characterized by comprising the following steps of:
S1, ferric chloride hexahydrate and nickel chloride hexahydrate are dissolved in water to obtain an iron-nickel metal salt water solution, and dimethylamine borane is dissolved in water to obtain a dimethylamine borane water solution;
S2, adding the water solution of the dimesyl borane into the iron-nickel metal salt solution, and uniformly stirring to obtain a mixed solution;
s3, adding potassium hydroxide into the mixed solution, and uniformly stirring to obtain an iron-nickel hydroxide colloid solution;
S4, incubating the ferric nickel hydroxide colloid solution for 45-50 hours under the dark condition of 20-30 ℃ to obtain Fe 2Ni5 type ferric nickel-based hydrogel;
And S5, cleaning the Fe 2Ni5 type iron-nickel based hydrogel with deionized water for 2-4 times, and then freeze-drying to obtain the Fe 2Ni5 type iron-nickel based hydrogel.
2. The method according to claim 1, wherein the molar ratio of ferric chloride hexahydrate to nickel chloride hexahydrate in the aqueous solution of iron-nickel metal salt is 2:5.
3. The method according to claim 1, wherein the molar ratio of the dimesyl borane to the nickel chloride hexahydrate in the mixed solution is 1:100.
4. The method of claim 1, wherein the molar ratio of potassium hydroxide to nickel chloride hexahydrate is 1:1.
5. The method of claim 1, wherein the incubation temperature in S4 is 25℃and the incubation time is 48 hours.
6. The method according to claim 1, wherein the step of washing with deionized water in S5 comprises immersing Fe 2Ni5 type iron-nickel-based hydrogel in deionized water and centrifuging at 8000rpm for 10-20 min.
7. The method of claim 1, wherein the temperature of the freeze-drying in S5 is-40 to-20 ℃ and the drying time is 10-15 hours.
8. The Fe 2Ni5 type crystalline-amorphous heterostructure aerogel catalyst produced by the production process of any one of claims 1 to 7.
9. The use of the Fe 2Ni5 type crystalline-amorphous heterostructure aerogel catalyst of claim 8 in the production of hydrogen by electrolysis of water.
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