CN114892184A - Preparation method of MOFs derivative electrocatalyst - Google Patents
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- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 48
- 239000010411 electrocatalyst Substances 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 33
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims abstract description 32
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000000758 substrate Substances 0.000 claims abstract description 24
- 239000011259 mixed solution Substances 0.000 claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- 239000012046 mixed solvent Substances 0.000 claims abstract description 15
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims abstract description 14
- 239000003054 catalyst Substances 0.000 claims abstract description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000012018 catalyst precursor Substances 0.000 claims abstract description 10
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 8
- 239000010439 graphite Substances 0.000 claims abstract description 8
- 235000005074 zinc chloride Nutrition 0.000 claims abstract description 7
- 239000011592 zinc chloride Substances 0.000 claims abstract description 7
- 238000005406 washing Methods 0.000 claims abstract description 6
- 238000004729 solvothermal method Methods 0.000 claims abstract description 5
- 239000007864 aqueous solution Substances 0.000 claims abstract description 3
- 238000001035 drying Methods 0.000 claims abstract description 3
- LAIZPRYFQUWUBN-UHFFFAOYSA-L nickel chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Ni+2] LAIZPRYFQUWUBN-UHFFFAOYSA-L 0.000 claims abstract description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 15
- 229910052759 nickel Inorganic materials 0.000 claims description 13
- 239000000126 substance Substances 0.000 claims description 13
- 230000008569 process Effects 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 239000004744 fabric Substances 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 15
- 239000001301 oxygen Substances 0.000 abstract description 15
- 229910052760 oxygen Inorganic materials 0.000 abstract description 15
- 230000000694 effects Effects 0.000 abstract description 9
- 239000002243 precursor Substances 0.000 abstract description 8
- 238000001308 synthesis method Methods 0.000 abstract description 2
- 239000008367 deionised water Substances 0.000 description 10
- 229910021641 deionized water Inorganic materials 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 8
- 238000011010 flushing procedure Methods 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000002135 nanosheet Substances 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 239000006260 foam Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 3
- 239000013099 nickel-based metal-organic framework Substances 0.000 description 3
- 229920000557 Nafion® Polymers 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000001075 voltammogram Methods 0.000 description 2
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 1
- NONOLKTXYXUTHP-UHFFFAOYSA-L O[Ni](O)=O Chemical compound O[Ni](O)=O NONOLKTXYXUTHP-UHFFFAOYSA-L 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910001453 nickel ion Inorganic materials 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000003346 selenoethers Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- -1 transition metal sulfides Chemical class 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
Images
Classifications
-
- 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
- C25B11/073—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
- C25B11/085—Organic compound
-
- 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 preparation method of an MOFs derivative electrocatalyst comprises the following steps: dissolving nickel chloride hexahydrate, zinc chloride and terephthalic acid in a mixed solvent of N, N-dimethylformamide, water and ethanol to obtain a mixed solution, and transferring the mixed solution into a lining of a high-pressure reaction kettle; putting the conductive substrate into the mixed solution for solvothermal reaction, and washing the conductive substrate with water after the reaction is finished to obtain a precursor of the MOFs catalyst growing on the conductive substrate; an electrochemical workstation is utilized, in a 1M KOH aqueous solution, a conductive substrate with a self-grown MOFs catalyst precursor is used as a working electrode, an Hg/HgO electrode is used as a reference electrode, a graphite rod is used as a counter electrode, a three-electrode system is constructed, CV scanning is carried out within the voltage range of 0.2-1.0V vs Hg/HgO, and then washing and drying are carried out to obtain the MOFs derivative catalyst. The synthesis method is simple, the cost is low, and the prepared catalyst has excellent oxygen evolution reaction activity and electrochemical stability.
Description
Technical Field
The invention relates to a preparation method of an MOFs derivative electrocatalyst.
Background
Hydrogen is considered the most ideal energy carrier for the twenty-first century. The hydrogen production by electrolyzing water has the characteristics of simple equipment, reliable operation and capability of producing high-purity hydrogen. The disadvantage is that a large amount of electric energy is consumed while obtaining hydrogen, which results in high cost. The oxygen evolution reaction is the bottleneck of the whole hydrogen production by water electrolysis. How to develop an efficient oxygen evolution catalyst to reduce overpotential and reduce energy consumption becomes a research hotspot.
The existing catalysts for electrolytic water oxygen evolution reaction include sulfides, selenides, nitrides, phosphides, metal organic framework materials and the like. However, most of the reported transition metal sulfides (ACS Nano,2020,14, 4141-.
The metal organic framework Materials (MOFs) have the characteristics of large specific surface area, adjustable pore diameter, easy modification and the like, and are favored by scientific researchers. However, most MOFs are powdered and have poor conductivity, requiring nafion reagent to be loaded on a conductive substrate, which is a cumbersome process and not conducive to the improvement of oxygen evolution activity. The MOFs with single metal nodes have poor oxygen evolution activity, such as Ni-MOF constructed by nickel ions and terephthalic acid, and the oxygen evolution activity is limited. The oxygen evolution activity of Ni-MOFs can be improved by methods such as element doping and ultrasonic stripping preparation of ultrathin MOFs nanosheets (nat. energy,2016,1,16184), however, the MOFs types applicable to the methods are limited or the preparation process is long, so that a simple method needs to be explored for modifying the Ni-MOFs to improve the oxygen evolution activity.
Disclosure of Invention
The invention aims to solve the technical problem of providing a preparation method of an MOFs derivative electrocatalyst, which comprises the steps of firstly preparing an MOFs precursor material on a conductive substrate by a solvothermal method, and then scanning by using a cyclic voltammetry method by using the conductive substrate loaded with the MOFs precursor material as an electrode to prepare the MOFs derivative electrocatalyst.
In order to solve the technical problems, the invention provides a preparation method of an MOFs derivative electrocatalyst, which comprises the following steps:
(1) dissolving nickel chloride hexahydrate, zinc chloride and terephthalic acid in a mixed solvent of DMF (dimethyl formamide), water and ethanol, fully stirring and dissolving to obtain a mixed solution, and transferring the mixed solution into the lining of a high-pressure reaction kettle;
(2) putting the cleaned conductive substrate into the mixed solution, carrying out solvothermal reaction, and after the reaction is finished, washing the conductive substrate with water to obtain a MOFs catalyst precursor growing on the conductive substrate;
(3) and (2) constructing a three-electrode system by using an electrochemical workstation and a prepared conductive substrate with a self-grown MOFs catalyst precursor as a working electrode, a Hg/HgO electrode as a reference electrode and a graphite rod as a counter electrode in a 1M KOH aqueous solution, performing CV scanning within a voltage range of 0.2-1.0V vs Hg/HgO, and then performing water washing and drying to obtain the MOFs derivative catalyst.
Preferably, the ratio of the amounts of nickel chloride and zinc chloride in the mixed solution obtained in the step (1) is 1-10: 1.
preferably, the concentration of nickel chloride in the mixed liquid obtained in the step (1) is 10 to 800 mmol/L.
Preferably, the concentration of zinc chloride in the mixed solution obtained in the step (1) is in the range of 10 to 80 mmol/L.
Preferably, the concentration of the terephthalic acid in the mixed liquid obtained in the step (1) is in the range of 10 to 800 mmol/L.
Preferably, the volume ratio of DMF, water and ethanol in the mixed solvent in step (1) is 14: 1: 1.
preferably, the conductive substrate in step (1) is one of any conductive substrates such as nickel foam, carbon cloth, carbon paper, titanium sheet, copper foam, iron foam, and cobalt foam after cleaning.
Preferably, the solvent thermal reaction in the step (2) is carried out for 12-24 hours at the temperature of 100-150 ℃.
Preferably, the CV scan rate in said step (3) is 100mV s -1 。
Preferably, the number of CV scans in step (3) is not less than 200.
The invention has the advantages that: (1) the raw materials of the MOFs precursor are cheap, and the synthesis method is simple;
(2) the prepared MOFs precursor and the derivative are on the conductive substrate, so that the use of Nafion and other adhesives is avoided, the operation steps are simplified, and the cost is obviously reduced;
(3) the MOFs derivative electrocatalyst has excellent oxygen evolution activity and electrochemical stability. The prepared MOFs derivative electrocatalyst has excellent oxygen evolution reaction activity, and reaches 10 mA-cm, 100 mA-cm and 300 mA-cm in 1mol/L KOH electrolyte -2 The required overpotentials were 224, 336 and 425mV, respectively. The catalyst is used at a rate of 20mA cm -2 The current density is tested by constant current for 12 hours, and the overpotential of the catalyst is basically kept unchanged, which shows that the catalyst has excellent electrochemical stability.
Drawings
FIG. 1 is a scanning electron micrograph of the product obtained in example 1.
FIG. 2 is a transmission electron micrograph of the product obtained in example 1.
FIG. 3 is a scanning electron micrograph of the product obtained in comparative example 1.
FIG. 4 is a linear sweep voltammogram of the products obtained in examples 1,2, 3, 4 and comparative example 1.
FIG. 5 is a graph of potential/time of the constant current test for oxygen evolution of the product obtained in example 1.
Detailed Description
Example 1
Step 1, preparing a mixed solvent of DMF, ethanol and deionized water, wherein the adding amount of the DMF, the ethanol and the deionized water in the mixed solvent is respectively 10.5mL, 0.75mL and 0.75 mL. Weighing a certain amount of NiCl 2 ·6H 2 O，ZnCl 2 And terephthalic acid are dissolved in the mixed solution to make NiCl 2 The amount concentration of the substance(s) is 40mmol/L, ZnCl 2 The amount concentration of the substance(s) of (3) is 40mmol/L and the amount concentration of the substance(s) of terephthalic acid is 40 mmol/L.
And 2, transferring the mixed solution into a reaction kettle, adding the cleaned foamed nickel, controlling the temperature to be 120 ℃, and reacting for 12 hours. After the reaction is finished, carefully flushing the foamed nickel by water;
FIG. 1 is a SEM image of example 1. As can be seen from fig. 1, the MOFs derivatives prepared exhibited a microsporoidal shape, these flower spheres being constituted by nanosheets. The unique three-dimensional hierarchical structure obviously increases the electrochemical active area of the catalyst, increases the number of active sites and is beneficial to gas overflow.
FIG. 2 is a TEM image of example 1. As can be seen from the figure, the porous structure is presented on the nano-sheet, which is probably because the skeleton structure of the MOFs precursor is destroyed in the electrochemical oxidation process, the ligand is decomposed, and a large amount of pore structures are generated, and the lamellar porous structure is helpful for increasing the number of active sites, so that the MOFs derivative exposes more active sites, and the oxygen evolution activity is enhanced.
Example 2
Step 1, preparing a mixed solvent of DMF, ethanol and deionized water, wherein the adding amount of the DMF, the ethanol and the deionized water in the mixed solvent is respectively 10.5mL, 0.75mL and 0.75 mL. Weighing a certain amount of NiCl 2 ·6H 2 O，ZnCl 2 And terephthalic acid are dissolved in the mixed solution to make NiCl 2 The amount concentration of the substance(s) is 40mmol/L, ZnCl 2 The amount concentration of the substance(s) of (4) and the amount concentration of the substance(s) of terephthalic acid of (40) were each 4mmol/L and 40 mmol/L.
And 2, transferring the mixed solution into a reaction kettle, adding the cleaned foamed nickel, controlling the temperature to be 120 ℃, and reacting for 12 hours. After the reaction is finished, carefully flushing the foamed nickel by water;
Example 3
Step 1, preparing a mixed solvent of DMF, ethanol and deionized water, wherein the adding amount of the DMF, the ethanol and the deionized water in the mixed solvent is respectively 10.5mL, 0.75mL and 0.75 mL. Weighing a certain amount of NiCl 2 ·6H 2 O，ZnCl 2 And terephthalic acid are dissolved in the mixed solution to make NiCl 2 The amount concentration of the substance(s) is 40mmol/L, ZnCl 2 The quantitative concentration of the substance(s) of (3) was 13.3mmol/L, and the quantitative concentration of the terephthalic acid was 40 mmol/L.
And 2, transferring the mixed solution into a reaction kettle, adding the cleaned foamed nickel, controlling the temperature to be 120 ℃, and reacting for 12 hours. After the reaction is finished, carefully flushing the foamed nickel by water;
Example 4
Step 1, preparing a mixed solvent of DMF, ethanol and deionized water, wherein the adding amount of the DMF, the ethanol and the deionized water in the mixed solvent is respectively 10.5mL, 0.75mL and 0.7 mL5 mL. Weighing a certain amount of NiCl 2 ·6H 2 O，ZnCl 2 And terephthalic acid are dissolved in the mixed solution to make NiCl 2 The amount concentration of the substance(s) is 40mmol/L, ZnCl 2 The quantitative concentration of the substance(s) of (3) was 26.6mmol/L, and the quantitative concentration of the terephthalic acid was 40 mmol/L.
And 2, transferring the mixed solution into a reaction kettle, adding the cleaned foamed nickel, controlling the temperature to be 120 ℃, and reacting for 12 hours. After the reaction is finished, carefully flushing the foamed nickel by water;
Comparative example 1
Step 1, preparing a mixed solvent of DMF, ethanol and deionized water, wherein the adding amount of the DMF, the ethanol and the deionized water in the mixed solvent is respectively 10.5mL, 0.75mL and 0.75 mL. Weighing a certain amount of NiCl 2 ·6H 2 Dissolving O and terephthalic acid in the mixed solution to obtain NiCl 2 The amount concentration of the substance(s) of (3) is 40mmol/L and the amount concentration of the substance(s) of terephthalic acid is 40 mmol/L.
And 2, transferring the mixed solution into a reaction kettle, adding the cleaned foamed nickel, controlling the temperature to be 120 ℃, and reacting for 12 hours. After the reaction is finished, carefully flushing the foamed nickel by water;
Fig. 3 is a scanning electron micrograph of comparative example 1. It can be seen from the figure that the nanosheets grow on the foamed nickel, and no flower-ball-shaped structure composed of the nanosheets is found. Indicating that the addition of zinc salts can change the morphology of the MOFs precursors. Changes in the morphology of the precursor will change the electrochemically active area and the number of active sites of the catalyst.
FIG. 4 is a linear sweep voltammogram for examples 1,2, 3, 4 and comparative example 1. As can be seen from FIG. 4, the electrolyte concentration was 10mA cm at 1mol/L KOH -2 The overpotentials required for examples 1,2, 3, 4 and comparative example 1 were 224, 248, 260, 285 and 279mV, respectively, at current densities of (d); at 100mA cm -2 The overpotentials required for examples 1,2, 3, 4 and comparative example 1 were 336, 369, 378 and 382mV, respectively, at current densities of (d); at 300mA · cm -2 The overpotentials required for examples 1,2, 3, 4 and comparative example 1 were 425, 450, 452, 459 and 468mV, respectively, at current densities of (d).
FIG. 5 shows the results of the oxygen evolution constant current test in the electrolyte of 1mol/L KOH using example 1 as the subject, when the concentration is 20 mA/cm -2 The current density of (2) was continuously tested for oxygen evolution for 12 hours, and the overpotential was found to be almost unchanged, which indicates that the echinoid iron-doped nickel hydroxide oxygen evolution catalyst obtained in example 1 has better catalytic stability.
Claims (10)
1. A preparation method of an MOFs derivative electrocatalyst is characterized by comprising the following steps:
(1) dissolving nickel chloride hexahydrate, zinc chloride and terephthalic acid in a mixed solvent of N, N-Dimethylformamide (DMF), water and ethanol, fully stirring and dissolving to obtain a mixed solution, and transferring the mixed solution into a lining of a high-pressure reaction kettle;
(2) putting the cleaned conductive substrate into the mixed solution, carrying out solvothermal reaction, and after the reaction is finished, washing the conductive substrate with water to obtain a MOFs catalyst precursor growing on the conductive substrate;
(3) and (2) constructing a three-electrode system by using an electrochemical workstation and a prepared conductive substrate with a self-grown MOFs catalyst precursor as a working electrode, a Hg/HgO electrode as a reference electrode and a graphite rod as a counter electrode in a 1M KOH aqueous solution, performing CV scanning within a voltage range of 0.2-1.0V vs Hg/HgO, and then performing water washing and drying to obtain the MOFs derivative catalyst.
2. The process for the preparation of the electrocatalysts of MOFs derivatives according to claim 1, wherein: the ratio of the amount of nickel chloride to the amount of zinc chloride in the mixed solution obtained in the step (1) is 1-10: 1.
3. the process for the preparation of the electrocatalysts of MOFs derivatives according to claim 1, wherein: the mass concentration range of the nickel chloride in the mixed liquid obtained in the step (1) is 10-800 mmol/L.
4. The process for the preparation of the electrocatalysts of MOFs derivatives according to claim 1, wherein: the mass concentration range of zinc chloride substances in the mixed liquid obtained in the step (1) is 10-80 mmol/L.
5. The process for the preparation of the electrocatalysts of MOFs derivatives according to claim 1, wherein: the concentration range of the terephthalic acid in the mixed liquid obtained in the step (1) is 10-800 mmol/L.
6. The process for the preparation of the electrocatalysts of MOFs derivatives according to claim 1, wherein: the volume ratio of DMF, water and ethanol in the mixed solvent in the step (1) is 14: 1: 1.
7. the process for the preparation of the electrocatalysts of MOFs derivatives according to claim 1, wherein: the conductive substrate in the step (1) is any one of cleaned foamed nickel, carbon cloth, carbon paper, titanium sheet, foamed copper, foamed iron, foamed cobalt and the like.
8. The process for the preparation of the electrocatalysts of MOFs derivatives according to claim 1, wherein: the solvothermal reaction in the step (2) is carried out for 12-24 hours at the temperature of 100-150 ℃.
9. According toA process for the preparation of an MOFs derivative electrocatalyst according to claim 1, characterized in that: the CV scan rate in said step (3) is 100mV s -1 。
10. The process for the preparation of the electrocatalysts of MOFs derivatives according to claim 1, wherein: the number of CV scanning circles in the step (3) is not less than 200 circles.
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| CN112981429A (en) * | 2021-02-24 | 2021-06-18 | 江南大学 | Metal organic framework and hydroxide heterojunction electrocatalyst and in-situ preparation method and application thereof |
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| CN110773233A (en) * | 2019-08-28 | 2020-02-11 | 浙江工业大学 | Preparation method of electrocatalytic full-hydrolytic nanosheet array material |
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| Title |
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| PONMUTHUSELVI THANGASAMY ET AL.: ""A NiCo-MOF nanosheet array based electrocatalyst for the oxygen evolution reaction"", 《NANOSCALE ADVANCES》 * |
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