CN111167456A - Catalyst, preparation method and application in hydrogen production by water electrolysis - Google Patents
Catalyst, preparation method and application in hydrogen production by water electrolysis Download PDFInfo
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- CN111167456A CN111167456A CN202010047605.1A CN202010047605A CN111167456A CN 111167456 A CN111167456 A CN 111167456A CN 202010047605 A CN202010047605 A CN 202010047605A CN 111167456 A CN111167456 A CN 111167456A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 65
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 239000001257 hydrogen Substances 0.000 title claims abstract description 20
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 238000004519 manufacturing process Methods 0.000 title abstract description 12
- 238000005868 electrolysis reaction Methods 0.000 title description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 95
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 56
- 229910052802 copper Inorganic materials 0.000 claims abstract description 44
- 239000010949 copper Substances 0.000 claims abstract description 44
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 43
- 239000004280 Sodium formate Substances 0.000 claims abstract description 39
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 claims abstract description 39
- 235000019254 sodium formate Nutrition 0.000 claims abstract description 39
- 229910052751 metal Inorganic materials 0.000 claims abstract description 27
- 239000002184 metal Substances 0.000 claims abstract description 27
- 239000000463 material Substances 0.000 claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- 239000000758 substrate Substances 0.000 claims abstract description 6
- 238000000354 decomposition reaction Methods 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
- 238000004140 cleaning Methods 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
- 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
- 238000001035 drying Methods 0.000 claims description 9
- 238000005238 degreasing Methods 0.000 claims description 7
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 6
- 239000011889 copper foil Substances 0.000 claims description 6
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 5
- 239000006260 foam Substances 0.000 claims description 4
- 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
- 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 41
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 18
- 239000000203 mixture Substances 0.000 description 14
- 238000005303 weighing Methods 0.000 description 12
- 238000012360 testing method Methods 0.000 description 10
- 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
- 238000010438 heat treatment Methods 0.000 description 6
- 238000004090 dissolution Methods 0.000 description 5
- 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
- 239000007864 aqueous solution Substances 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
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- RPZHFKHTXCZXQV-UHFFFAOYSA-N mercury(i) oxide Chemical compound O1[Hg][Hg]1 RPZHFKHTXCZXQV-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 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
- 230000009286 beneficial effect Effects 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
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- 239000013078 crystal Substances 0.000 description 1
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- 230000002349 favourable effect Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000004969 ion scattering spectroscopy Methods 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001737 promoting effect Effects 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
- 238000002604 ultrasonography Methods 0.000 description 1
Images
Classifications
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- B01J35/39—
-
- 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
-
- B01J35/40—
-
- 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
-
- 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
-
- 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
-
- 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
Abstract
A catalyst, a preparation method and application in hydrogen production by electrolyzing water. The invention belongs to the technical field of catalysts, and relates to a catalyst, wherein a substrate 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; the catalyst provided by the invention is prepared directly by adopting sodium formate and nickel sources and a copper material as a substrate 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 a huge application value in hydrogen production through electrocatalytic decomposition of water.
Description
Technical Field
The invention belongs to the technical field of catalysts, and relates to a catalyst, a preparation method and application in hydrogen production by water electrolysis.
Background
The hydrogen energy is regarded as the clean energy with the most development potential in the 21 st century, and the hydrogen production by electrolyzing water becomes a research hotspot of the hydrogen production method due to the advantages of renewable energy and environmental friendliness. However, in order to mass-produce hydrogen gas in an actual apparatus, a catalyst capable of operating stably and efficiently in an industrial hydrogen production environment (high current, high electrolyte concentration, etc.) is required. The platinum-based noble metal catalyst is a better water electrolysis catalyst, but is difficult to be applied in a large scale due to rare reserves and high price. The metal nickel is rich in reserves, low in price and the theoretical hydrogen evolution activity of the metal nickel is closest to that of a noble metal non-noble metal catalyst, so that the metal nickel has an application prospect in industrial production.
However, non-noble metal catalysts have encountered several problems in practical applications: (1) the high-activity transition metal catalyst 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) there is a lack of a simple, inexpensive synthesis method to prepare highly efficient and stable catalysts.
Disclosure of Invention
The invention aims to provide a catalyst which has an original multi-layer different nickel crystal form coating structure, is good in structural stability, does not use noble metal and is low in 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 large-scale production.
The invention also aims to provide the application of the catalyst in hydrogen production by water electrolysis, which has the characteristics of high catalytic activity and good stability.
The invention adopts the following technical scheme that,
a catalyst comprises a copper material as a substrate, wherein cubic phase structure metallic nickel is coated on the surface of the copper material, and hexagonal phase structure metallic nickel is coated on the surface of the cubic phase structure metallic 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 metal nickel is 50-130 nm.
Preferably, the thickness of the metal nickel with the hexagonal phase structure is 2-15 nm.
More preferably, the thickness of the metal nickel with the hexagonal phase structure 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 of preparing a catalyst as described in any of the above embodiments, comprising the steps of,
s1, ultrasonically degreasing and deoiling the copper material in acetone or absolute ethyl alcohol, washing with ultrapure water, ultrasonically removing surface oxides in hydrochloric acid, and then cleaning 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 a 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, reacting for 12-24 hours at 150-180 ℃, cooling, taking out the copper material, cleaning, and drying in vacuum to obtain the catalyst.
Preferably, the nickel source in step S3 is at least one selected from the group consisting of nickel chloride, nickel acetylacetonate, nickel sulfate and nickel nitrate.
Preferably, the sodium formate solution and the nickel solution are added into the reaction kettle in step S4, and the copper material is immersed in the solution.
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 filling proportion 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, before sealing, the reaction kettle is placed in an ultrasonic generator to be subjected to ultrasonic oscillation for 5-15 minutes.
Use of a catalyst according to any one of the preceding embodiments for the electrocatalytic decomposition of water to produce hydrogen.
The invention has the beneficial effects that:
(1) the preparation method provided by the invention adopts one-step hydrothermal reaction to directly synthesize the final product, and has the advantages of mild synthesis conditions, simple method, easiness in operation, cheap and easily-obtained raw materials, simple product post-treatment, environmental friendliness, suitability for large-scale production and good actual application prospect.
(2) The catalyst has more catalytic active sites, the surface exposed surface is metal nickel with a hexagonal phase structure, and the metal nickel and the cubic phase metal nickel in the inner layer form a crystalline phase heterojunction, so that the catalyst shows better electrocatalytic activity and stability.
(3) The catalyst can be directly used as an electrode material for electrocatalysis reaction, and the nickel metal and the copper material substrate form a tightly combined heterojunction without an additional binder, so that the structural stability of the electrocatalysis electrode is greatly improved.
Drawings
FIG. 1 is a schematic diagram of the structure of the catalyst of the present invention,
wherein, 1-copper material, 2-cubic phase structure metallic nickel, and 3-hexagonal phase structure metallic 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 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 an SEM image of the surface morphology of catalyst 5 of example 5.
Fig. 7 is an SEM image of the surface morphology of catalyst 6 of example 6.
Fig. 8 is an SEM image of the surface morphology of catalyst 7 of example 7.
FIG. 9 is a graph of the polarization curve (LSV) of catalyst 1 in a 1M KOH electrolyte,
wherein, 1-catalyst 1, 2-foam nickel, 3-foam copper.
FIG. 10 is a graph of the polarization curve (LSV) of catalyst 2 in a 6M KOH electrolyte at 80 ℃.
Detailed Description
The following description of the embodiments of the present invention is provided by way of specific examples, and other advantages and effects of the present invention will be readily apparent to those skilled in the art from the disclosure herein.
It should be understood that the structures, ratios, sizes, and the like shown in the drawings and described in the specification are only used for matching with the contents disclosed in the specification, so as to be understood and read by those skilled in the art, and are not used to limit the conditions under which the present invention can be implemented, so that the present invention has no technical essence, and any structural modifications, ratio changes or size adjustments should fall within the scope of the present invention without affecting the function and the achievable purpose of the present invention. In addition, the terms "above", "inside", "outside", "bottom", "one", "in" and the like used in the present specification are for convenience of description and are not intended to limit the scope of the present invention, and changes or modifications in the relative relationship thereof are to be made without substantial changes in the technical content and the scope of the present invention.
Example 1
Cutting the foamy copper into small blocks of 1 × 2 × 2cm, ultrasonically degreasing and deoiling in acetone for 10min, washing with ultrapure water for 3 times, ultrasonically removing surface oxides in 1mol/L hydrochloric acid for 10min, and then cleaning with ultrapure water for 3 times to obtain pretreated foamy copper;
weighing 0.33g of sodium formate, and adding the sodium formate into 1.5ml of ultrapure water to obtain a sodium formate solution; 0.05g of NiCl was weighed2·6H2Adding O into 13ml of DMF, and ultrasonically dissolving to obtain a nickel chloride solution;
mixing a sodium formate solution and a nickel chloride solution, uniformly oscillating with ultrasound, adding the mixture into a 25ml reaction kettle, adding pretreated foamy copper, sealing, placing the mixture into a temperature programming oven, heating at the rate of 3 ℃/min, reacting at 160 ℃ for 18 hours, cooling to room temperature, taking out the foamy copper, alternately cleaning with water and ethanol for 3 times, and drying in vacuum at 60 ℃ for 12 hours to obtain the catalyst 1.
As can be seen from the attached figure 2, the three-dimensional skeleton surface of the catalyst 1 is rough, has a structure similar to a honeycomb structure, has a large specific surface area, can provide more catalytic sites, and is favorable for promoting the catalytic reaction. As can be seen from FIGS. 3 and 4, the thickness of the nickel metal having a hexagonal surface structure in the catalyst 1 is about 5nm, and the thickness of the nickel metal having a cubic internal structure is about 100 nm.
Example 2
Weighing 0.2g of sodium formate, and adding the sodium formate into 1.5ml of ultrapure water to obtain a sodium formate solution; 0.2g of NiCl was weighed2·6H2Adding O into 13ml of DMF, and ultrasonically dissolving to obtain a nickel chloride solution;
mixing a sodium formate solution and a nickel chloride solution, uniformly oscillating with ultrasonic waves, adding the mixture into a 25ml reaction kettle, adding the pretreated foamy copper obtained in the example 1, sealing, placing the mixture into a temperature programming oven, reacting at 150 ℃ for 24 hours at a heating rate of 3 ℃/min, cooling to room temperature, taking out the foamy copper, alternately cleaning with water and ethanol for 3 times, and drying in vacuum at 60 ℃ for 12 hours to obtain a catalyst 2.
Example 3
Weighing 0.1g of sodium formate, and adding the sodium formate into 1.5ml of ultrapure water to obtain a sodium formate solution; weighing 0.4g of nickel acetylacetonate, adding the nickel acetylacetonate into 13ml of DMF, and carrying out ultrasonic dissolution to obtain a nickel acetylacetonate solution;
mixing a sodium formate solution and a nickel acetylacetonate solution, uniformly oscillating by ultrasonic waves, adding the mixture into a 25ml reaction kettle, adding the pretreated foamy copper in the embodiment 1, sealing, placing the mixture into a temperature programming oven, reacting for 20 hours at 160 ℃, cooling to room temperature, taking out the foamy copper, alternately cleaning with water and ethanol for 3 times, and drying in vacuum for 12 hours at 60 ℃ to obtain a catalyst 3. As shown in fig. 3, the catalyst 3 is coated with about 50nm of metallic nickel on the surface of the copper substrate, and the thickness of the surface-exposed hexagonal phase metallic nickel is about 5 nm.
Example 4
Weighing 0.15g of sodium formate, and adding the sodium formate into 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 carrying out ultrasonic dissolution to obtain a nickel nitrate solution;
mixing a sodium formate solution and a nickel nitrate solution, uniformly oscillating with ultrasonic waves, adding the mixture into a 25ml reaction kettle, adding the pretreated foamy copper in the embodiment 1, sealing, placing the mixture into a temperature programming oven, reacting at 160 ℃ for 20 hours at a heating rate of 3 ℃/min, cooling to room temperature, taking out the foamy copper, alternately cleaning with water and ethanol for 3 times, and drying in vacuum at 60 ℃ for 12 hours to obtain a catalyst 4.
Example 5
Ultrasonic degreasing and oil removal of copper powder in acetone for 10min, rinsing with ultrapure water for 3 times, putting the copper powder in 2mol/L hydrochloric acid for ultrasonic degreasing for 10min to remove surface oxides, and then rinsing with ultrapure water for 3 times to obtain pretreated copper powder;
weighing 0.06g of sodium formate, and adding the sodium formate into 1.5ml of ultrapure water to obtain a sodium formate solution; weighing 0.1g of nickel acetylacetonate, adding the nickel acetylacetonate into 13ml of DMF, and carrying out ultrasonic dissolution to obtain a nickel acetylacetonate solution;
mixing a sodium formate solution and a nickel acetylacetonate solution, uniformly oscillating by ultrasonic, adding the mixture into a 25ml reaction kettle, adding pretreated copper powder, sealing, placing the mixture into a temperature programming oven, heating at the rate of 4 ℃/min, reacting for 12 hours at 180 ℃, cooling to room temperature, taking out the copper powder, alternately cleaning with water and ethanol for 3 times, and drying in vacuum for 10 hours at 60 ℃ to obtain the catalyst 5.
Example 6
Cutting the copper mesh into small pieces of 0.5 multiplied by 3cm, ultrasonically degreasing and deoiling in acetone for 10min, washing with ultrapure water for 3 times, ultrasonically removing surface oxides in 1mol/L hydrochloric acid for 10min, and then cleaning with ultrapure water for 3 times to obtain a pretreated copper mesh;
weighing 0.25g of sodium formate, and adding the sodium formate into 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 carrying out ultrasonic dissolution to obtain a nickel nitrate solution;
mixing a sodium formate solution and a nickel nitrate solution, uniformly oscillating with ultrasonic waves, adding the mixture into a 25ml reaction kettle, adding a pretreated copper mesh, sealing, placing the mixture into a temperature programming oven, heating at the rate of 3 ℃/min, reacting at 170 ℃ for 15 hours, cooling to room temperature, taking out the copper mesh, alternately cleaning with water and ethanol for 3 times, and drying in vacuum at 50 ℃ for 20 hours to obtain the catalyst 6.
Example 7
Cutting the copper foil into small pieces of 0.5 multiplied by 3cm, ultrasonically degreasing and deoiling in acetone for 10min, washing with ultrapure water for 3 times, ultrasonically removing surface oxides in 1mol/L hydrochloric acid for 10min, and then cleaning with ultrapure water for 3 times to obtain a pretreated copper foil;
weighing 0.12g of sodium formate, and adding the sodium formate into 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 carrying out ultrasonic dissolution to obtain a nickel nitrate solution;
mixing a sodium formate solution and a nickel nitrate solution, uniformly oscillating with ultrasonic waves, adding the mixture into a 25ml reaction kettle, adding a pretreated copper foil, sealing, placing the mixture into a temperature programming oven, heating at the speed of 3 ℃/min, reacting for 15 hours at the temperature of 170 ℃, cooling to room temperature, taking out the copper foil, alternately cleaning with water and ethanol for 3 times, and drying in vacuum for 20 hours at the temperature of 50 ℃ to obtain the catalyst 7.
Electrocatalytic water decomposition hydrogen production test 1: a three-electrode test system was used in electrochemical workstation CHI660E, with the working electrode being the catalyst 1 electrode of example 1, the counter electrode being a graphite carbon plate, and the reference electrode being a mercury-mercury oxide electrode. The electrolyte for testing is 1mol/L potassium hydroxide aqueous solution at 25 ℃, high-purity nitrogen is introduced for saturation treatment in the test, and the test temperature is room temperature. When the linear sweep voltammogram is tested, the sweep rate is 1mV/s, the solution ohmic drop iR compensation correction is carried out, and the electrode potential is converted into the electrode potential of a Reversible Hydrogen Electrode (RHE).
FIG. 9 is a graph of the polarization curve (LSV) of the catalyst 1 obtained by the present invention in a 1M KOH electrolyte, and it can be seen that the electrode of the catalyst 1 shows a high hydrogen evolution activity in an alkaline medium, and the current density is-10 mA cm-2And-100 mA · cm-2The 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 foamed nickel and foamed copper.
Electrocatalytic water decomposition hydrogen production test 2: a three-electrode test system was used in electrochemical workstation CHI660E, with the working electrode being the catalyst 2 electrode of example 2, the counter electrode being a graphite carbon plate, and the reference electrode being a mercury-mercury oxide electrode. The electrolyte is tested to be 6mol/L potassium hydroxide aqueous solution at 80 ℃, high-purity nitrogen is introduced for saturation treatment in the test, and the test temperature is room temperature. When the linear sweep voltammogram is tested, the sweep rate is 1mV/s, the solution ohmic drop iR compensation correction is carried out, and the electrode potential is converted into the electrode potential of a Reversible Hydrogen Electrode (RHE).
FIG. 10 is a plot of the polarization curve (LSV) of the test in 6M KOH electrolyte at 80 deg.C, showing that the catalyst 2 electrode of the present invention can still exhibit high hydrogen evolution activity in strong and harsh alkaline media.
Claims (10)
1. The catalyst is characterized in that a substrate 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.
2. The catalyst according to claim 1, wherein the cubic metallic nickel has a thickness of 30 to 180 nm.
3. The catalyst according to claim 2, wherein the cubic metallic nickel has a thickness of 50 to 130 nm.
4. The catalyst according to claim 1, wherein the hexagonal phase structure metal nickel has a thickness of 2 to 15 nm.
5. The catalyst according to claim 4, wherein the hexagonal phase structure metal nickel has a thickness of 3 to 10 nm.
6. The catalyst of any of claims 1 to 5 wherein the copper material is selected from at least one of copper foam, copper powder, copper mesh and copper foil.
7. A method for preparing the catalyst according to any one of claims 1 to 6, comprising the steps of,
s1, ultrasonically degreasing and deoiling the copper material in acetone or absolute ethyl alcohol, washing with ultrapure water, ultrasonically removing surface oxides in hydrochloric acid, and then cleaning 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;
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, reacting for 12-24 hours at 150-180 ℃, cooling, taking out the copper material, cleaning, and drying in vacuum to obtain the catalyst.
8. The method according to claim 7, wherein the nickel source in step S3 is at least one selected from the group consisting of nickel chloride, nickel acetylacetonate, nickel sulfate, and nickel nitrate.
9. The preparation method of claim 7, wherein the reaction filling ratio is 45-75% after the copper material, the sodium formate solution and the nickel source solution are added into the reaction kettle in the step S4.
10. Use of a catalyst according to any one of claims 1 to 6 for the electrocatalytic decomposition of water to produce hydrogen.
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| CN115928127A (en) * | 2022-11-28 | 2023-04-07 | 厦门大学 | Self-supporting catalyst and preparation method and application thereof |
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