CN111167456B - Catalyst, preparation method and application of catalyst in hydrogen production by water electrolysis - Google Patents
Catalyst, preparation method and application of catalyst in hydrogen production by water electrolysis Download PDFInfo
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- CN111167456B CN111167456B CN202010047605.1A CN202010047605A CN111167456B CN 111167456 B CN111167456 B CN 111167456B CN 202010047605 A CN202010047605 A CN 202010047605A CN 111167456 B CN111167456 B CN 111167456B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 69
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 21
- 239000001257 hydrogen Substances 0.000 title claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 13
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 238000005868 electrolysis reaction Methods 0.000 title abstract description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 89
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 59
- 229910052802 copper Inorganic materials 0.000 claims abstract description 46
- 239000010949 copper Substances 0.000 claims abstract description 46
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 40
- 239000004280 Sodium formate Substances 0.000 claims abstract description 35
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 claims abstract description 35
- 235000019254 sodium formate Nutrition 0.000 claims abstract description 35
- 229910052751 metal Inorganic materials 0.000 claims abstract description 24
- 239000002184 metal Substances 0.000 claims abstract description 24
- 239000000463 material Substances 0.000 claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 5
- 239000000758 substrate Substances 0.000 claims abstract description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 23
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 19
- 239000012498 ultrapure water Substances 0.000 claims description 19
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 14
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 14
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- 238000004140 cleaning Methods 0.000 claims description 11
- 238000005238 degreasing Methods 0.000 claims description 11
- SHWZFQPXYGHRKT-FDGPNNRMSA-N (z)-4-hydroxypent-3-en-2-one;nickel Chemical compound [Ni].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O SHWZFQPXYGHRKT-FDGPNNRMSA-N 0.000 claims description 10
- 238000007789 sealing Methods 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 8
- 239000011889 copper foil Substances 0.000 claims description 7
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 6
- 239000006260 foam Substances 0.000 claims description 6
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 4
- 238000011049 filling Methods 0.000 claims description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims 1
- 229910000510 noble metal Inorganic materials 0.000 abstract description 6
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 40
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 18
- 238000012360 testing method Methods 0.000 description 13
- 239000000203 mixture Substances 0.000 description 8
- 238000001291 vacuum drying Methods 0.000 description 8
- 238000005303 weighing Methods 0.000 description 8
- 238000004090 dissolution Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 239000003792 electrolyte Substances 0.000 description 7
- 235000019441 ethanol Nutrition 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 230000010287 polarization Effects 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 238000005520 cutting process Methods 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 230000010355 oscillation Effects 0.000 description 3
- 230000000630 rising effect Effects 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000012937 correction Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000011010 flushing procedure Methods 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 238000001075 voltammogram Methods 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000004969 ion scattering spectroscopy Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000000047 product Substances 0.000 description 1
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- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 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
- 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
- B01J35/39—Photocatalytic properties
-
- 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
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/055—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
- C25B11/057—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material consisting of a single element or compound
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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
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
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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
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
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Abstract
A catalyst, a preparation method and application thereof in hydrogen production by water electrolysis. The invention belongs to the technical field of catalysts, and relates to a catalyst, wherein a substrate of the catalyst is made of a copper material, the surface of the copper material is coated with cubic phase structure metal nickel, and the surface of the cubic phase structure metal nickel is coated with hexagonal phase structure metal nickel; the thickness of the cubic phase structure metal nickel is 10-200 nm, and the thickness of the hexagonal phase structure metal nickel is 1-20 nm; the catalyst provided by the invention adopts sodium formate and nickel source, takes copper material as substrate, is directly prepared through simple hydrothermal reaction, has the characteristics of simple reaction steps, no use of noble metal, low cost, high catalytic efficiency and good stability, and has great application value in electrocatalytic decomposition of water to produce hydrogen.
Description
Technical Field
The invention belongs to the technical field of catalysts, and relates to a catalyst, a preparation method and application thereof in hydrogen production by water electrolysis.
Background
Hydrogen energy is regarded as the clean energy with the most development potential in the 21 st century, and electrolytic water hydrogen production is a research hotspot of hydrogen production methods due to the advantages of renewable energy and environmental friendliness. However, in order to produce hydrogen in large quantities in practical devices, a catalyst capable of operating efficiently and stably in an industrial hydrogen production environment (high current, high electrolyte concentration, etc.) is required. Platinum-based noble metal catalysts are better electrolyzed water catalysts, but are difficult to apply in large scale due to the scarce reserves and the high price. The non-noble metal catalyst with the theoretical hydrogen evolution activity closest to that of noble metal has rich reserves, low price and rich application prospect in industrial production.
However, non-noble metal catalysts suffer from several problems in practical applications: (1) The transition metal catalyst with high activity is easy to oxidize in air, so that the catalytic activity is lost; (2) The common catalyst is difficult to stably work for a long time under the actual hydrogen production working environment; (3) The method for preparing the efficient and stable catalyst by using the simple and low-cost synthesis method is lacking.
Disclosure of Invention
The invention aims to provide a catalyst which has an original multilayer coating structure with different nickel crystal forms, has good structural stability, does not use noble metal and has low cost.
The invention also aims to provide a preparation method of the catalyst, which has the advantages of simple raw materials, low price, simple preparation method, low cost and mass production.
The invention also aims to provide an application of the catalyst in hydrogen production by water electrolysis, and the catalyst has the characteristics of high catalytic activity and good stability.
The invention adopts the following technical proposal,
the base of the catalyst is a copper material, the surface of the copper material is coated with cubic phase structure metal nickel, and the surface of the cubic phase structure metal nickel is coated with hexagonal phase structure metal nickel; the thickness of the cubic phase structure metal nickel is 10-200 nm, and the thickness of the hexagonal phase structure metal nickel is 1-20 nm.
Preferably, the thickness of the cubic phase structure metal nickel is 30-180 nm.
More preferably, the thickness of the cubic phase structure metallic nickel is 50-130 nm.
Preferably, the thickness of the hexagonal phase structure metallic nickel is 2-15 nm.
More preferably, the thickness of the hexagonal phase structure metallic nickel is 3-10 nm.
Preferably, the copper material is selected from at least one of copper foam, copper powder, copper mesh and copper foil.
A method for preparing the catalyst according to any one of the above embodiments, comprising the steps of,
s1, carrying out ultrasonic degreasing and degreasing on the copper material in acetone or absolute ethyl alcohol, washing with ultrapure water, placing into hydrochloric acid to ultrasonically remove surface oxides, and washing with ultrapure water to obtain a pretreated copper material;
s2, adding 1 part of sodium formate into 4-200 parts of water according to parts by weight to obtain a sodium formate solution;
s3, adding 1 part of nickel source into 15-600 parts of N, N-Dimethylformamide (DMF) according to parts by weight to obtain nickel source solution;
s4, adding the pretreated copper material obtained in the step S1, the sodium formate solution obtained in the step S2 and the nickel source solution obtained in the step S3 into a reaction kettle, sealing, placing the reaction kettle in the environment of 150-180 ℃ for reacting for 12-24 hours, cooling, taking out the copper material, cleaning and vacuum drying to obtain the catalyst.
Preferably, the nickel source in step S3 is selected from at least one of nickel chloride, nickel acetylacetonate, nickel sulfate and nickel nitrate.
Preferably, in step S4, the sodium formate solution and the nickel solution are added to the reaction kettle, and then the liquid level is immersed through the copper material.
Preferably, in the step S4, after the copper material, the sodium formate solution and the nickel source solution are added into the reaction kettle, the reaction filling ratio is 45-75%.
Preferably, after the copper material, the sodium formate solution and the nickel source solution are added into the reaction kettle in the step S4, the reaction kettle is placed in an ultrasonic generator for ultrasonic vibration for 5-15 minutes before sealing.
Use of a catalyst according to any one of the embodiments above for electrocatalytic decomposition of aqueous hydrogen.
The invention has the beneficial effects that:
(1) The preparation method adopts one-step hydrothermal reaction to directly synthesize the final product, has the advantages of mild synthesis conditions, simple method, easy operation, cheap and easily obtained raw materials, simple post-treatment of the product, environmental friendliness, suitability for large-scale production and good practical application prospect.
(2) The catalyst has more catalytic active sites, the exposed surface of the catalyst is hexagonal phase structure metal nickel, and the hexagonal phase structure metal nickel and the cubic phase metal nickel of the inner layer form a crystalline phase heterojunction, so that the catalyst has better electrocatalytic activity and stability.
(3) The catalyst can be directly used as an electrode material for electrocatalytic reaction, and a tightly combined heterojunction can be formed between nickel metal and a copper material substrate without an external binder, so that the structural stability of the electrocatalytic electrode is greatly improved.
Drawings
FIG. 1 is a schematic structural view of a catalyst of the present invention,
wherein, the 1-copper material is 2-cubic phase structure metal nickel and 3-hexagonal phase structure metal nickel.
Fig. 2 is an SEM image of the surface morphology of the catalyst 1 of example 1.
Fig. 3 is a TEM image of a section of the catalyst 1 of example 1 and a fourier transform image of the corresponding region.
Fig. 4 is an XRD pattern of catalyst 1 of example 1.
FIG. 5 is a high resolution low energy ion scattering (HS-LEISS) spectrum of catalyst 3 of example 3.
Fig. 6 is a SEM image of the surface morphology of catalyst 5 of example 5.
Fig. 7 is a SEM image of the surface morphology of catalyst 6 of example 6.
Fig. 8 is a SEM image of the surface morphology of the catalyst 7 of example 7.
FIG. 9 is a graph of polarization curve (LSV) of catalyst 1 in 1M KOH electrolyte,
wherein, 1-catalyst is 1, 2-foam nickel and 3-foam copper.
FIG. 10 is a graph of polarization curve (LSV) of catalyst 2 in 6M KOH electrolyte at 80 ℃.
Detailed Description
Further advantages and effects of the present invention will become apparent to those skilled in the art from the present disclosure, by describing embodiments of the present invention with specific examples.
It should be understood that the structures, proportions, sizes, etc. shown in the drawings are for the purpose of understanding and reading the contents disclosed in the specification, and are not intended to limit the applicable scope of the present invention, so that any structural modifications, proportional changes, or dimensional adjustments should fall within the scope of the present invention without affecting the efficacy and achievement of the present invention. In the meantime, the terms such as "above", "inside", "outside", "bottom", "one", "in" and the like cited in the present specification are also for convenience of description and are not intended to limit the scope of the present invention, and the changes or modifications of the relative relationship are described in advance without substantial modification of the technical content, when they are considered as the scope of the present invention.
Example 1
Cutting foamy copper into small blocks with the length of 1 multiplied by 2cm, degreasing and degreasing the small blocks in acetone by ultrasonic for 10min, flushing the small blocks with ultrapure water for 3 times, putting the small blocks into 1mol/L hydrochloric acid for ultrasonic for 10min to remove surface oxides, and cleaning the small blocks with the ultrapure water for 3 times to obtain pretreated foamy copper;
0.33g of sodium formate was weighed and added to 1.5ml of ultrapure water to obtain a sodium formate solution; weigh 0.05g NiCl 2 ·6H 2 Adding O into 13ml of DMF for ultrasonic dissolution to obtain nickel chloride solution;
and (3) uniformly mixing the sodium formate solution and the nickel chloride solution, adding the mixture into a 25ml reaction kettle, adding pretreated foamy copper, sealing, placing the mixture into a temperature programming oven, reacting at a temperature of 160 ℃ for 18 hours at a temperature of 3 ℃/min, cooling to room temperature, taking out foamy copper, alternately cleaning the foamy copper with water and ethanol for 3 times, and vacuum drying at 60 ℃ for 12 hours to obtain the catalyst 1.
As can be seen from fig. 2, the three-dimensional skeleton surface of the catalyst 1 is rough, has a honeycomb-like structure and a large specific surface area, can provide more catalytic sites, and is beneficial to promoting the catalytic reaction. As can be seen from fig. 3 and 4, the thickness of the surface hexagonal phase structure metal nickel in the catalyst 1 is about 5nm, and the thickness of the internal cubic phase structure metal nickel is about 100nm.
Example 2
Weighing 0.2g of sodium formate and adding the sodium formate to 1.5ml of ultrapure water to obtain a sodium formate solution; weigh 0.2g NiCl 2 ·6H 2 Adding O into 13ml of DMF for ultrasonic dissolution to obtain nickel chloride solution;
mixing sodium formate solution and nickel chloride solution, adding into a 25ml reaction kettle after ultrasonic oscillation, adding the pretreated foamy copper in the example 1, sealing, placing into a temperature programming oven, reacting for 24 hours at 150 ℃ at a temperature rising rate of 3 ℃/min, cooling to room temperature, taking out the foamy copper, alternately cleaning with water and ethanol for 3 times, and vacuum drying at 60 ℃ for 12 hours to obtain the catalyst 2.
Example 3
Weighing 0.1g of sodium formate and adding the sodium formate to 1.5ml of ultrapure water to obtain a sodium formate solution; weighing 0.4g of nickel acetylacetonate, and adding the nickel acetylacetonate into 13ml of DMF for ultrasonic dissolution to obtain a nickel acetylacetonate solution;
mixing sodium formate solution and nickel acetylacetonate solution, adding into a 25ml reaction kettle after ultrasonic oscillation, adding the pretreated foamy copper in the example 1, sealing, placing into a temperature programming oven, reacting for 20 hours at 160 ℃ at a temperature rising rate of 3 ℃/min, cooling to room temperature, taking out the foamy copper, alternately cleaning with water and ethanol for 3 times, and vacuum drying at 60 ℃ for 12 hours to obtain the catalyst 3. As shown in fig. 3, the catalyst 3 is coated with about 50nm of metallic nickel on the surface of a copper substrate, and the thickness of the hexagonal phase metallic nickel exposed on the surface is about 5nm.
Example 4
0.15g of sodium formate was weighed and added to 1.5ml of ultrapure water to obtain a sodium formate solution; weighing 0.7g of nickel nitrate, adding the nickel nitrate into 13ml of DMF, and performing ultrasonic dissolution to obtain a nickel nitrate solution;
mixing sodium formate solution and nickel nitrate solution, adding into a 25ml reaction kettle after ultrasonic oscillation, adding the pretreated foamy copper in the embodiment 1, sealing, placing into a temperature programming oven, reacting for 20 hours at 160 ℃ at a temperature rising rate of 3 ℃/min, cooling to room temperature, taking out the foamy copper, alternately cleaning with water and ethanol for 3 times, and vacuum drying at 60 ℃ for 12 hours to obtain the catalyst 4.
Example 5
Ultrasonic degreasing and degreasing copper powder in acetone for 10min, flushing with ultrapure water for 3 times, ultrasonic treating in 2mol/L hydrochloric acid for 10min to remove surface oxides, and cleaning with ultrapure water for 3 times to obtain pretreated copper powder;
0.06g of sodium formate was weighed and added to 1.5ml of ultrapure water to obtain a sodium formate solution; weighing 0.1g of nickel acetylacetonate, and adding the nickel acetylacetonate into 13ml of DMF for ultrasonic dissolution to obtain a nickel acetylacetonate solution;
and (3) uniformly mixing the sodium formate solution and the nickel acetylacetonate solution, adding the mixture into a 25ml reaction kettle, adding the pretreated copper powder, sealing, placing the mixture into a temperature programming oven, reacting at a temperature of 180 ℃ for 12 hours at a heating rate of 4 ℃/min, cooling to room temperature, taking out the copper powder, alternately cleaning the copper powder with water and ethanol for 3 times, and vacuum drying at 60 ℃ for 10 hours to obtain the catalyst 5.
Example 6
Cutting copper mesh into small pieces of 0.5X3 cm, degreasing with ultrasonic in acetone for 10min, washing with ultrapure water for 3 times, placing into 1mol/L hydrochloric acid for ultrasonic for 10min to remove surface oxide, and washing with ultrapure water for 3 times to obtain pretreated copper mesh;
0.25g of sodium formate was weighed and added to 1.5ml of ultrapure water to obtain a sodium formate solution; weighing 0.3g of nickel nitrate, adding the nickel nitrate into 13ml of DMF, and performing ultrasonic dissolution to obtain a nickel nitrate solution;
and (3) uniformly mixing the sodium formate solution and the nickel nitrate solution, adding the mixture into a 25ml reaction kettle, adding a pretreated copper mesh, sealing, placing the mixture into a temperature programming oven, reacting at a temperature of 170 ℃ for 15 hours at a temperature of 3 ℃/min, cooling to room temperature, taking out the copper mesh, alternately cleaning the copper mesh with water and ethanol for 3 times, and vacuum drying at 50 ℃ for 20 hours to obtain the catalyst 6.
Example 7
Cutting copper foil into small pieces of 0.5X3 cm, degreasing and degreasing in acetone for 10min, washing with ultrapure water for 3 times, placing into 1mol/L hydrochloric acid for ultrasonic treatment for 10min to remove surface oxides, and washing with ultrapure water for 3 times to obtain pretreated copper foil;
weighing 0.12g of sodium formate and adding the sodium formate to 1.5ml of ultrapure water to obtain a sodium formate solution; weighing 0.25g of nickel nitrate, adding the nickel nitrate into 13ml of DMF, and performing ultrasonic dissolution to obtain a nickel nitrate solution;
and (3) uniformly mixing the sodium formate solution and the nickel nitrate solution, adding the mixture into a 25ml reaction kettle, adding the pretreated copper foil, sealing, placing the mixture into a temperature programming oven, reacting at a temperature of 170 ℃ for 15 hours at a temperature of 3 ℃/min, cooling to room temperature, taking out the copper foil, alternately cleaning the copper foil with water and ethanol for 3 times, and vacuum drying at 50 ℃ for 20 hours to obtain the catalyst 7.
Electrocatalytic water decomposition hydrogen production test 1: a three electrode test system was used on electrochemical workstation CHI660E, the working electrode was the catalyst 1 electrode of example 1, the counter electrode was a graphite carbon sheet, and the reference electrode was a mercury-oxidized mercury electrode. The test electrolyte is a potassium hydroxide aqueous solution with the concentration of 1mol/L at the temperature of 25 ℃, high-purity nitrogen is introduced into the test to carry out saturation treatment, and the test temperature is room temperature. In the linear sweep voltammogram test, the sweep rate was 1mV/s and the solution ohm-drop iR compensation correction was performed and converted to the electrode potential of the Reversible Hydrogen Electrode (RHE).
FIG. 9 is a polarization curve (LSV) of the catalyst 1 obtained in the present invention in a 1M KOH electrolyte, showing that the catalyst 1 electrode exhibits high hydrogen evolution activity in alkaline medium and current density of-10 mA cm -2 And-100 mA cm -2 The overpotential for catalyst 1 was 87mV and 157mV, respectively. The activity of the catalyst prepared by the invention is obviously higher than that of blank foam nickel and foam copper.
Electrocatalytic water decomposition hydrogen production test 2: a three electrode test system was used on electrochemical workstation CHI660E, the working electrode was the catalyst 2 electrode of example 2, the counter electrode was a graphite carbon sheet, and the reference electrode was a mercury-oxidized mercury electrode. The test electrolyte is a 6mol/L potassium hydroxide aqueous solution at 80 ℃, high-purity nitrogen is introduced into the test to carry out saturation treatment, and the test temperature is room temperature. In the linear sweep voltammogram test, the sweep rate was 1mV/s and the solution ohm-drop iR compensation correction was performed and converted to the electrode potential of the Reversible Hydrogen Electrode (RHE).
FIG. 10 is a graph of polarization curve (LSV) of the present test in a 6M KOH electrolyte at 80℃and shows that the catalyst 2 electrode of the present invention can still exhibit high hydrogen evolution activity in a strong and harsh alkaline medium.
Claims (10)
1. The catalyst is characterized in that a substrate of the catalyst is made of a copper material, the surface of the copper material is coated with cubic phase structure metal nickel, and the surface of the cubic phase structure metal nickel is coated with hexagonal phase structure metal nickel; the thickness of the cubic phase structure metal nickel is 10-200 nm, and the thickness of the hexagonal phase structure metal nickel is 1-20 nm.
2. The catalyst of claim 1, wherein the cubic phase structure metallic nickel has a thickness of 30-180 nm.
3. The catalyst of claim 2, wherein the cubic phase structure metallic nickel has a thickness of 50-130 nm.
4. The catalyst of claim 1, wherein the hexagonal phase structured metallic nickel has a thickness of 2-15 nm.
5. The catalyst of claim 4, wherein the hexagonal phase structured metallic nickel has a thickness of 3-10 nm.
6. The catalyst of any one of claims 1-5, wherein the copper material is selected from at least one of copper foam, copper powder, copper mesh, and copper foil.
7. A process for preparing a catalyst as claimed in any one of claims 1 to 6, comprising the steps of,
s1, carrying out ultrasonic degreasing and degreasing on the copper material in acetone or absolute ethyl alcohol, washing with ultrapure water, placing into hydrochloric acid to ultrasonically remove surface oxides, and washing with ultrapure water to obtain a pretreated copper material;
s2, adding 1 part of sodium formate into 4-200 parts of water according to parts by weight to obtain a sodium formate solution;
s3, adding 1 part of nickel source into 15-600 parts of N, N-dimethylformamide according to parts by weight to obtain a nickel source solution;
and S4, adding the pretreated copper material obtained in the step S1, the sodium formate solution obtained in the step S2 and the nickel source solution obtained in the step S3 into a reaction kettle, sealing, placing the reaction kettle in an environment of 150-180 ℃ for reacting for 12-24 hours, cooling, taking out the copper material, cleaning, and drying in vacuum to obtain the catalyst.
8. The method of claim 7, wherein the nickel source in step S3 is selected from at least one of nickel chloride, nickel acetylacetonate, nickel sulfate, and nickel nitrate.
9. The preparation method of claim 7, wherein after the copper material, the sodium formate solution and the nickel source solution are added into the reaction kettle in the step S4, the volume ratio of the reaction filling is 45-75%.
10. Use of a catalyst according to any one of claims 1 to 6 for the electrocatalytic decomposition of aqueous hydrogen.
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