CN115573000B - A highly active self-supporting bifunctional water electrolysis catalyst and its preparation and application - Google Patents
A highly active self-supporting bifunctional water electrolysis catalyst and its preparation and application Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 52
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 230000001588 bifunctional effect Effects 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 238000005868 electrolysis reaction Methods 0.000 title abstract description 11
- 239000010949 copper Substances 0.000 claims abstract description 32
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052802 copper Inorganic materials 0.000 claims abstract description 18
- 239000006260 foam Substances 0.000 claims abstract description 15
- 230000000694 effects Effects 0.000 claims abstract description 12
- 239000002057 nanoflower Substances 0.000 claims abstract description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 60
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 36
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 34
- 238000006243 chemical reaction Methods 0.000 claims description 31
- 239000002243 precursor Substances 0.000 claims description 24
- 150000001868 cobalt Chemical class 0.000 claims description 22
- 150000002815 nickel Chemical class 0.000 claims description 22
- 239000011259 mixed solution Substances 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 16
- 239000000243 solution Substances 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 13
- 238000005406 washing Methods 0.000 claims description 13
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 10
- 239000012498 ultrapure water Substances 0.000 claims description 10
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- 238000004729 solvothermal method Methods 0.000 claims description 5
- 239000011258 core-shell material Substances 0.000 claims description 4
- 239000002070 nanowire Substances 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 claims description 3
- 238000007254 oxidation reaction Methods 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 230000002194 synthesizing effect Effects 0.000 claims description 3
- GFHNAMRJFCEERV-UHFFFAOYSA-L cobalt chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Co+2] GFHNAMRJFCEERV-UHFFFAOYSA-L 0.000 claims description 2
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 claims description 2
- ZGDWHDKHJKZZIQ-UHFFFAOYSA-N cobalt nickel Chemical compound [Co].[Ni].[Ni].[Ni] ZGDWHDKHJKZZIQ-UHFFFAOYSA-N 0.000 claims description 2
- ZBYYWKJVSFHYJL-UHFFFAOYSA-L cobalt(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Co+2].CC([O-])=O.CC([O-])=O ZBYYWKJVSFHYJL-UHFFFAOYSA-L 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 2
- 238000011065 in-situ storage Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 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 2
- RRIWRJBSCGCBID-UHFFFAOYSA-L nickel sulfate hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-]S([O-])(=O)=O RRIWRJBSCGCBID-UHFFFAOYSA-L 0.000 claims description 2
- 229940116202 nickel sulfate hexahydrate Drugs 0.000 claims description 2
- UQPSGBZICXWIAG-UHFFFAOYSA-L nickel(2+);dibromide;trihydrate Chemical compound O.O.O.Br[Ni]Br UQPSGBZICXWIAG-UHFFFAOYSA-L 0.000 claims description 2
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 238000000840 electrochemical analysis Methods 0.000 abstract 1
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 27
- 229910052739 hydrogen Inorganic materials 0.000 description 15
- 239000001257 hydrogen Substances 0.000 description 15
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 12
- 239000012621 metal-organic framework Substances 0.000 description 12
- 239000002131 composite material Substances 0.000 description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 6
- 238000004502 linear sweep voltammetry Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 239000010411 electrocatalyst Substances 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000002064 nanoplatelet Substances 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 230000010287 polarization Effects 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 238000004506 ultrasonic cleaning Methods 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000002803 fossil fuel Substances 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241000080590 Niso Species 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- -1 platinum group metals Chemical class 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000012085 test solution Substances 0.000 description 1
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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
-
- 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
- C25B11/02—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form
- C25B11/03—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form perforated or foraminous
- C25B11/031—Porous electrodes
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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
- C25B11/055—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
- C25B11/061—Metal or alloy
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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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- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Abstract
本发明属于电催化领域，具体涉及一种自支撑双功能电解水催化剂及其制备方法。催化剂为纳米花层结构的CoNiCu‑LDH负载在泡沫铜上(CF)形成三维的自支撑稳定结构；其中，催化剂的负载量大约为5‑20mg cm‑2。本发明采用的实际价格较低，电化学测试表明得到的催化剂电解水效果较好。
The present invention belongs to the field of electrocatalysis, and specifically relates to a self-supporting bifunctional water electrolysis catalyst and a preparation method thereof. The catalyst is a nano-flower layer structure of CoNiCu-LDH loaded on a foam copper (CF) to form a three-dimensional self-supporting stable structure; wherein the loading amount of the catalyst is about 5-20 mg cm -2 . The actual price adopted by the present invention is relatively low, and electrochemical tests show that the obtained catalyst has a good water electrolysis effect.
Description
Technical field:
The invention belongs to the field of electrocatalysis, and particularly relates to a self-supporting bifunctional electrolyzed water catalyst and a preparation method thereof.
The background technology is as follows:
Hydrogen is one of the most ideal alternative energy carriers for conventional fossil fuels, and has the outstanding advantages of (1) energy density (142 MJ/Kg) far higher than that of gasoline (44 MJ/Kg), (2) wide application, being used as fuel, and also being important industrial raw materials in many chemical processes, such as Fischer-Tropsch reaction, ammonia synthesis reaction and the like, (3) easy transportation, and (4) energy release by direct combustion or reaction in a hydrogen fuel cell, and the obtained byproduct is only water. Therefore, hydrogen is considered to be one of the most potential clean energy sources in the 21 st century. However, so far, the main modes of industrial hydrogen production are still steam methane conversion and coal gasification, and the purity of the hydrogen produced by the processes is low, and a large amount of fossil fuel is consumed, so that a large amount of pollutants and CO 2 are discharged. Thus, there is an urgent need to seek clean, sustainable hydrogen production strategies.
The water electrolysis is a high-efficiency clean industrial hydrogen production technology, and can prepare high-purity hydrogen. Electrochemical water splitting consists of two half reactions, hydrogen Evolution Reaction (HER) on the cathode and Oxygen Evolution Reaction (OER) on the anode. Although water electrolysis provides an efficient method for producing high purity hydrogen, the practical use of electrochemical water splitting to produce hydrogen is limited because it is a strong uphill reaction with a large overpotential. The use of OER and HER electrocatalysts is an effective way to reduce the water splitting overpotential, which reduces energy consumption and increases energy efficiency. The ideal HER and OER catalysts must meet two basic requirements-firstly, the electrocatalyst must be highly active, capable of producing a greater current density with a smaller overpotential, and secondly, it must exhibit long-term stability. Currently, platinum group metals and oxides of Ir and Ru are the benchmark electrocatalysts for HER and OER, respectively, but the scarcity and high cost of these noble metals severely hamper their large-scale practical use.
The invention comprises the following steps:
Aiming at the problems, the invention provides a self-supporting bifunctional water electrolysis catalyst and a preparation method thereof.
In order to achieve the above purpose, the invention adopts the technical scheme that:
A high-activity self-supporting bifunctional water electrolysis catalyst is characterized in that CoNiCu-LDH with a nano flower layer structure is supported on foam Copper (CF) to form a three-dimensional self-supporting stable structure, wherein the supporting capacity of the catalyst is about 5-20mg cm -2, preferably 5-10mg cm -2.
A preparation method of a high-activity self-supporting bifunctional electrolyzed water catalyst adopts a redox method to directly grow Cu (OH) 2 nano wires on the surface of foam copper in situ, then the Cu (OH) 2 nano wires are placed in a core-shell structure precursor formed in a mixed solution of metal salts containing Co 2+ and Ni 2+ and terephthalic acid through a solvothermal method, and then the core-shell structure precursor is immersed in a solvent containing nickel salt and cobalt salt to form cobalt-nickel layered double hydroxide (CoNiCu-LDH) on the foam copper through a solvothermal mode.
The method comprises the following steps:
1) At room temperature, placing foam copper into aqueous solution of NaOH and (NH 4)2S2O8 for chemical oxidation to obtain a precursor 1;
2) Adding nickel salt, cobalt salt and terephthalic acid into the mixed solution, stirring uniformly at normal temperature to obtain a mixed solution, placing the precursor 1 into the mixed solution, synthesizing the precursor 2 by a hydrothermal method, and washing and drying after the reaction;
3) Immersing the precursor 2 obtained in the step 2) in ethanol solution containing nickel salt and cobalt salt for hydrothermal synthesis, washing and drying after the reaction to obtain the bifunctional electrolyzed water catalyst.
The final concentration of NaOH in the aqueous solution of NaOH and (NH 4)2S2O8) in the step 1) is 1mol/L-5mol/L, and the concentration ratio of NaOH to (NH 4)2S2O8) is 5:1-20:1.
The nickel salt, the cobalt salt and the terephthalic acid are added into a mixed solution, and the total final concentration of the nickel salt, the cobalt salt and the terephthalic acid in the mixed solution is 1mmol/L-3mmol/L, wherein the mass ratio of the nickel salt, the cobalt salt and the terephthalic acid is 1:1:1.5-1:1:3.
The mixed solution is prepared by mixing methyl formamide, ethanol and ultrapure water in sequence according to the volume ratio of 12:1:1.
The nickel salt is one or more of nickel nitrate hexahydrate, nickel sulfate hexahydrate, nickel chloride hexahydrate and nickel bromide, and the cobalt salt is one or more of cobalt nitrate hexahydrate, cobalt chloride hexahydrate and cobalt acetate tetrahydrate.
In the step 2), the precursor 1 is placed in a mixed solution to be subjected to solvothermal synthesis reaction at 70-150 ℃ for 10-14h, and after the reaction, the precursor is washed by ethanol and dried at 60-100 ℃ to obtain the precursor 2.
The precursor 2 obtained in the step 3) is immersed in ethanol solution containing nickel salt and cobalt salt for hydrothermal synthesis for 2-4h at the temperature of 110-140 ℃, and is washed by ethanol after reaction and dried at the temperature of 60-100 ℃ to obtain the bifunctional electrolyzed water catalyst, wherein the total final concentration of the nickel salt and the cobalt salt in the ethanol is 1mmol-3mmol, and the mass ratio of the nickel salt to the cobalt salt is 1:1.
Use of an electrolyzed water catalyst for use in a reaction to electrolyze water.
The invention has the advantages that:
1. The catalyst is a double-function CoNiCu-LDH@CuO/CF self-supporting electrode, can effectively perform full water dissolution, changes the growth process of CoNiCu-LDH by using CoNiCu-MOF as a precursor through a rapid phase change process, and has excellent electrocatalyst performance due to the obtained nano flower structure with rich active site surfaces.
2. The preparation process of the invention is simple and controllable, the cost of raw materials is lower, the catalyst performance is better, and the invention has potential of industrial application.
3. The catalyst provided by the invention has good electrocatalytic oxygen evolution and hydrogen evolution performances in alkaline electrolyte, and has the characteristics of low overpotential and strong catalytic stability.
Description of the drawings:
FIG. 1 shows the results of electrochemical performance tests of the products obtained in example 1 and comparative examples 1-2, wherein FIG. 1a shows the LSV curve of OER test, FIG. 1b shows the EIS chart of OER test, FIG. 1c shows the LSV curve of HER test, and FIG. 1d shows the EIS chart of HER test.
FIG. 2 is a graph of the catalytic performance of the product of example 1 of the present invention, wherein FIG. 2a is a graph of the LSV of the full water electrolysis and FIG. 2b is a graph of the stability of the full water electrolysis.
FIG. 3 is an SEM image of a catalyst prepared according to example 1
FIG. 4 is a TEM image of the catalyst prepared in example 1
FIG. 5 is an XRD pattern of the catalyst prepared in example 1
FIG. 6 is an SEM image of the catalyst prepared in comparative example 2
The specific embodiment is as follows:
The present invention will be further described with reference to the accompanying drawings and detailed description, wherein it is to be understood that, under the precondition of no conflict, the following embodiments can be arbitrarily combined to form new embodiments.
Example 1:
A copper-based self-supporting electrolytic water catalyst, the preparation process comprises the following steps:
(1) Firstly, placing a piece of foam Copper (CF) in acetone, ethanol and deionized water in sequence for ultrasonic cleaning to remove surface impurities, immersing the cleaned CF in aqueous solution containing NaOH (2.0M) and (NH 4)2S2O8 (0.1M)) for about 10-30 min, taking out light blue Cu (OH) 2/CF from the solution, washing and drying for later use.
(2) Firstly, weighing 0.124g of terephthalic acid, placing the terephthalic acid in a beaker, sequentially adding ethanol, ultrapure water and an organic solvent dimethylformamide (wherein the volume ratio of the dimethylformamide to the ethanol to the ultrapure water is 12:1:1), stirring uniformly at normal temperature, then adding 0.267g of Ni (NO 3)2·6H2 O and 0.267g of Co (NO 3)2·6H2 O), continuously stirring at normal temperature for 6 hours, transferring the mixture into a polyfluortetraethylene lining of a hydrothermal kettle, placing Cu (OH) 2/CF obtained in the step (1) in the polyfluortetraethylene lining, sealing the polyfluortetraethylene lining, placing the Cu (OH) 2/CF in an oven, preserving heat for 12 hours at 140 ℃, then taking out the polyfluortetraethylene lining, sequentially washing with the dimethylformamide, ethanol and water, and drying to obtain dark brown CoNiCu-MOF@Cu 2 O/CF.
(3) 0.3G Ni (NO 3)2·6H2 O and 0.3g Co (NO 3)2·6H2 O are dissolved in 30mL ethanol solution and stirred uniformly), then the solution is transferred into a 50mL stainless steel reaction kettle, the prepared CoNiCu-MOF@Cu 2 O/CF is put into the reaction kettle, the reaction kettle is put into an oven after being sealed, the temperature is kept at 120 ℃ for 3 hours, then the reaction kettle is taken out, washed and dried to obtain the dual-function electrolyzed water catalyst CoNiCu-LDH@CuO/CF composite material, and the mass difference before and after the foam copper load is measured by a microbalance, so that the load amount is 5mg cm -2 (see figures 3-5)
Example 2:
A copper-based self-supporting electrolytic water catalyst, the preparation process comprises the following steps:
(1) Firstly, placing a piece of foam Copper (CF) in acetone, ethanol and deionized water in sequence for ultrasonic cleaning to remove surface impurities, immersing the cleaned CF in aqueous solution containing NaOH (2.0M) and (NH 4)2S2O8 (0.1M)) for about 10-30 min, taking out light blue Cu (OH) 2/CF from the solution, washing and drying for later use.
(2) Firstly, weighing 0.124g of terephthalic acid, placing the terephthalic acid in a beaker, sequentially adding ethanol, ultrapure water and an organic solvent dimethylformamide (wherein the volume ratio of the dimethylformamide to the ethanol to the ultrapure water is 12:1:1), stirring uniformly at normal temperature, then adding 0.321g of NiCl 2·6H2 O and 0.321g of CoCl 2·6H2 O, continuously stirring at normal temperature for 8 hours, transferring the mixture into a polyfluortetraethylene lining of a hydrothermal kettle, placing Cu (OH) 2/CF obtained in the step (1) in the polyfluortetraethylene lining, sealing the polyfluortetraethylene lining, placing the polyfluortetraethylene lining in an oven at 150 ℃ for 10 hours, then taking out the polyfluortetraethylene lining, sequentially washing with the dimethylformamide, the ethanol and water, and drying to obtain the dark brown CoNiCu-MOF@Cu 2 O/CF.
(3) 0.203G of Ni (NO 3)2·6H2 O and 0.203g of Co (NO 3)2·6H2 O are dissolved in 30mL of ethanol solution and stirred uniformly), then the solution is transferred into a 50mL stainless steel reaction kettle, the prepared CoNiCu-MOF@Cu 2 O/CF is put into the reaction kettle, the reaction kettle is put into an oven after being sealed, the temperature is kept at 110 ℃ for 4 hours, and then the double-function electrolyzed water catalyst CoNiCu-LDH@CuO/CF composite material is obtained after being taken out, washed and dried.
Example 3:
A copper-based self-supporting electrolytic water catalyst, the preparation process comprises the following steps:
(1) Firstly, placing a piece of foam Copper (CF) in acetone, ethanol and deionized water in sequence for ultrasonic cleaning to remove surface impurities, immersing the cleaned CF in aqueous solution containing NaOH (2.0M) and (NH 4)2S2O8 (0.1M)) for about 10-30 min, taking out light blue Cu (OH) 2/CF from the solution, washing and drying for later use.
(2) Firstly, weighing 0.124g of terephthalic acid, placing the terephthalic acid in a beaker, sequentially adding ethanol, ultrapure water and an organic solvent dimethylformamide (wherein the volume ratio of the dimethylformamide to the ethanol to the ultrapure water is 12:1:1), stirring uniformly at normal temperature, then adding 0.296g of NiSO 4·6H2 O and 0.28g of CH 3COO)2Co·4H2 O, continuously stirring at normal temperature for 6 hours, transferring the mixture into a polyfluortetraethylene lining of a hydrothermal kettle, placing Cu (OH) 2/CF obtained in the step (1) into the polyfluortetraethylene lining, sealing the polyfluortetraethylene lining, placing the polyfluortetraethylene lining into an oven, preserving heat for 14 hours at 120 ℃, then taking out the polyfluortetraethylene lining, sequentially washing with the dimethylformamide, the ethanol and water, and drying to obtain the dark brown CoNiCu-MOF@Cu 2 O/CF.
(3) 0.5G of Ni (NO 3)2·6H2 O and 0.5g of Co (NO 3)2·6H2 O are dissolved in 30mL of ethanol solution and stirred uniformly), then the solution is transferred into a 50mL stainless steel reaction kettle, the prepared CoNiCu-MOF@Cu 2 O/CF is put into the reaction kettle, the reaction kettle is put into an oven after being sealed, the temperature is kept at 140 ℃ for 2 hours, and then the double-function electrolyzed water catalyst CoNiCu-LDH@CuO/CF composite material is obtained after being taken out, washed and dried.
Comparative example 1:
Comparative example 1 differs from example 1 in that only step (1) was performed to obtain a Cu (OH) 2/CF composite.
Comparative example 2:
Comparative example 2 differs from example 1 in that step (3) was omitted and the remainder was the same as in example 1, yielding CoNiCu-MOF@Cu 2 O/CF composite (see FIG. 6).
The products obtained in examples 1, comparative examples 1 to 2 were used as catalysts for the respective electrolyzed water hydrogen evolution and oxygen evolution tests in a solution with an electrolyte of 1.0m koh, and the electrochemical measurements were carried out on an electrochemical workstation (CHI 750E) using a standard three-electrode system in which the Hg/HgO electrode was a reference electrode graphite electrode as a counter electrode and the products prepared in examples 1, comparative examples 1 to 2 according to the present invention were working electrodes (geometric area 1cm x 1 cm). Linear Sweep Voltammetry (LSV) was measured in an O 2 saturated electrolyte at a scan rate of 5mV s -1, and the equation E vs.RHE＝Evs.Hg/HgO +0.059×ph+0.098 calculates the potential versus the potential of the Reversible Hydrogen Electrode (RHE). Electrochemical stability was tested with a chronoamperometric curve at a current density of 200mA cm -2.
The results are shown in FIG. 1, wherein FIG. 1-a shows OER performance of example 1, comparative example 1 and comparative example 2, and FIG. 1-c shows HER performance of example 1, comparative example 1 and comparative example 2, and it is clear that the overpotential of CoNiCu-LDH@CuO/CF is the lowest, and that at a current density of 100mA cm -2, the oxygen evolution overpotential of the material is 286mV and the hydrogen evolution overpotential is 262mV. EIS (1-b, 1-c) results show that compared with CoNiCu-MOF@Cu 2 O/CF composite materials and Cu (OH) 2/CF composite materials, the internal resistance of the CoNiCu-LDH@CuO/CF composite materials is minimum in OER and HER tests, so that the polarization phenomenon of the catalyst in the catalytic process is reduced, and the overpotential of the catalyst in the catalytic process can be effectively reduced.
FIG. 2 is a plot of polarization of CoNiCu-LDH@CuO/CF self-supporting electrode as a bifunctional catalytic material in alkaline electrolyte with almost no decay for a full water splitting cycle up to 24h at a current density of 100mA cm -2.
FIG. 3 is an SEM image of CoNiCu-LDH@CuO/CF material showing the self-assembly of CoNiCu-LDH nanoplatelets into a nanoflower structure.
FIG. 4 is a TEM image of CoNiCu-LDH@CuO/CF material highlighting the nanoplatelet structure of CoNiCu-LDH.
FIG. 6 is an SEM image of CoNiCu-MOF@Cu 2 O/CF material showing that CoNiCu-MOF nanoplatelets self-assemble and randomly arrange on a Cu (OH) 2/CF substrate after MOF engineering is completed.
The OER performance of the catalysts prepared by further examples was then compared with that of the catalysts tested using an electrochemical workstation LSV, the test solutions were 1M KOH, see Table 1 in particular
TABLE 1
Reference is made to:
[1]L.Hu,T.Xiong,R.Liu,Y.Hu,Y.Mao,M.J.T.Balogun,Y.Tong,Co3O4@Cu-Based Conductive Metal-Organic Framework Core-Shell Nanowire Electrocatalysts Enable Efficient Low-Overall-Potential Water Splitting,Chem-Eur.J.25(26)(2019)6575-6583,https://doi.org/10.1002/chem.201900045.
[2]J.S.Shaikh,R.C.Pawar,R.S.Devan,Y.R.Ma,P.P.Salvi,S.S.Kolekar,P.S.Patil,Synthesis and characterization of Ru doped CuO thin films for supercapacitor based on Bronsted acidic ionic liquid,Electrochimi.Acta 56(5)(2011)2127-2134,https://doi.org/10.1016/j.electacta.2010.11.046.
[3]Z.Sun,L.Lin,C.Nan,H.Li,G.Sun,X.Yang,Amorphous Boron Oxide Coated NiCo Layered Double Hydroxide Nanoarrays for Highly Efficient Oxygen Evolution Reaction,Acs.Sustain.Chen.Eng.6(11)(2018)14257-14263,https://doi.org/10.1021/acssuschemeng.8b02893.
[4]L.Tabassum,H.Tasnim,S.Shubhashish,I.Perera,T.Bhosale,M.Li,S.March,M.K.Islam,S.L.Suib,Selenium-doped copper oxide nanoarrays:Robust electrocatalyst for the oxygen evolution reaction with ultralow overpotential,Appl.Mater.Today 27(2022)101485,https://doi.org/10.1016/j.apmt.2022.101485.
[5]H.Liang,F.Meng,M.Caban-Acevedo,L.Li,A.Forticaux,L.Xiu,Z.Wang,S.Jin,Hydrothermal continuous flow synthesis and exfoliation of NiCo layered double hydroxide nanosheets for enhanced oxygen evolution catalysis,Nano Lett.15(2)(2015)1421-1427,https://doi.org/10.1021/nl504872s.
[6]C.Yu,Z.Liu,X.Han,H.Huang,C.Zhao,J.Yang,J.Qiu,NiCo-layered double hydroxides vertically assembled on carbon fiber papers as binder-free high-active electrocatalysts for water oxidation,Carbon 110(2016)1-7,https://doi.org/10.1016/j.carbon.2016.08.020.
[7]F.Gu,Q.Zhang,X.H.Chen,T.Li,H.C.Fu,H.Q.Luo,N.B.Li,Electronic regulation and core-shell hybrids engineering of palm-leaf-like NiFe/Co(PO3)2bifunctional electrocatalyst for efficient overall water splitting,Int.J.Hydrogen Energy 47(66)(2022)28475-28485,https://doi.org/10.1016/j.ijhydene.2022.06.148. As can be seen from Table 1 above, coNiCu-LDH@CuO/CF electrodes possess excellent electrocatalytic properties.
In summary, the invention provides a self-supporting bifunctional water electrolysis catalyst, which is applied to OER and HER and full water electrolysis performance tests under alkaline conditions, shows smaller internal resistance, can effectively reduce polarization phenomenon in the electrocatalytic process, and enables the catalyst to show lower overpotential in the catalytic process. According to the preparation method, coNiCu-LDH is loaded on the foam copper through a hydrothermal method to form a stable three-dimensional self-supporting structure, so that the preparation process is simplified, and the long-term stability of the catalyst is improved.
The above embodiments are only preferred embodiments of the present invention, and the scope of the present invention is not limited thereto, but any insubstantial changes and substitutions made by those skilled in the art on the basis of the present invention are intended to be within the scope of the present invention as claimed.
Claims (9)
1. A high-activity self-supporting bifunctional electrolyzed water catalyst is characterized in that the catalyst is a self-supporting stable structure formed by carrying CoNiCu-LDH with a nano flower layer structure on foam copper CF, wherein the carrying capacity of the catalyst is 5-20mg cm -2;
The preparation method comprises the following steps:
1) At room temperature, placing foam copper into aqueous solution of NaOH and (NH 4)2S2O8 for chemical oxidation to obtain a precursor 1;
2) Adding nickel salt, cobalt salt and terephthalic acid into a mixed solution composed of methyl formamide, ethanol and ultrapure water, uniformly stirring at normal temperature to obtain a mixed solution, placing the precursor 1 into the mixed solution, synthesizing the precursor 2 by a hydrothermal method, and washing and drying after the reaction;
3) Immersing the precursor 2 obtained in the step 2) in ethanol solution containing nickel salt and cobalt salt for hydrothermal synthesis, washing and drying after the reaction to obtain the bifunctional electrolyzed water catalyst.
2. A method for preparing the high-activity self-supporting bifunctional electrolyzed water catalyst as defined in claim 1, which is characterized in that a redox method is adopted to directly grow Cu (OH) 2 nanowire in situ on the surface of foam copper, then the Cu (OH) 2 nanowire is placed in a core-shell structure precursor formed by a mixed solution of metal salt containing Co 2+ and Ni 2+ and terephthalic acid through a solvothermal method, and then the core-shell structure precursor is immersed in a solvent containing nickel salt and cobalt salt to form cobalt-nickel layered double hydroxide (CoNiCu-LDH) on the foam copper through a solvothermal method;
The preparation method comprises the following steps:
1) At room temperature, placing foam copper into aqueous solution of NaOH and (NH 4)2S2O8 for chemical oxidation to obtain a precursor 1;
2) Adding nickel salt, cobalt salt and terephthalic acid into a mixed solution composed of methyl formamide, ethanol and ultrapure water, uniformly stirring at normal temperature to obtain a mixed solution, placing the precursor 1 into the mixed solution, synthesizing the precursor 2 by a hydrothermal method, and washing and drying after the reaction;
3) Immersing the precursor 2 obtained in the step 2) in ethanol solution containing nickel salt and cobalt salt for hydrothermal synthesis, washing and drying after the reaction to obtain the bifunctional electrolyzed water catalyst.
3. The method for preparing the high-activity self-supporting bifunctional electrolyzed water catalyst according to claim 2, wherein the final concentration of NaOH in the aqueous solution of NaOH and (NH 4)2S2O8) in step 1) is 1mol/L to 5mol/L, and the concentration ratio of NaOH and (NH 4)2S2O8) is 5:1 to 20:1.
4. The method for preparing the high-activity self-supporting bifunctional electrolyzed water catalyst according to claim 2, wherein the nickel salt, the cobalt salt and the terephthalic acid are added into a mixed solution, and the total final concentration of the nickel salt, the cobalt salt and the terephthalic acid in the mixed solution is 1mmol/L-3mmol/L, wherein the mass ratio of the nickel salt, the cobalt salt and the terephthalic acid is 1:1:1.5-1:1:3.
5. The method for preparing a high-activity self-supporting bifunctional electrolytic water catalyst as recited in claim 4, wherein the mixed solution is prepared by mixing methyl formamide, ethanol and ultrapure water in a volume ratio of 12:1:1.
6. The preparation method of the high-activity self-supporting bifunctional electrolyzed water catalyst according to claim 2, wherein the nickel salt is one or more of nickel nitrate hexahydrate, nickel sulfate hexahydrate, nickel chloride hexahydrate and nickel bromide, and the cobalt salt is one or more of cobalt nitrate hexahydrate, cobalt chloride hexahydrate and cobalt acetate tetrahydrate.
7. The method for preparing the high-activity self-supporting bifunctional electrolyzed water catalyst according to claim 2, wherein in the step 2), the precursor 1 is placed in a mixed solution to perform solvothermal synthesis reaction at 70-150 ℃ for 10-14h, and after the reaction, the precursor 2 is obtained by washing with ethanol and drying at 60-100 ℃.
8. The method for preparing the high-activity self-supporting bifunctional electrolyzed water catalyst according to claim 2, wherein in the step 3), the precursor 2 obtained in the step 2) is immersed in an ethanol solution containing nickel salt and cobalt salt for hydrothermal synthesis for 2-4 hours at 110-140 ℃, and after the reaction, the catalyst is washed by ethanol and dried at 60-100 ℃, so that the bifunctional electrolyzed water catalyst is obtained, wherein the total final concentration of the nickel salt and the cobalt salt in the ethanol is 1mmol-3mmol, and the mass ratio of the nickel salt to the cobalt salt is 1:1.
9. Use of the electrolyzed water catalyst of claim 1, wherein the catalyst is used in an electrolyzed water reaction.
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