CN115522215A - Preparation and application of MIL-88@ CoMg electrolyzed water hydrogen evolution catalyst with foamed nickel as substrate - Google Patents
Preparation and application of MIL-88@ CoMg electrolyzed water hydrogen evolution catalyst with foamed nickel as substrate Download PDFInfo
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 60
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 60
- 239000001257 hydrogen Substances 0.000 title claims abstract description 60
- 239000003054 catalyst Substances 0.000 title claims abstract description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 30
- 229910001868 water Inorganic materials 0.000 title claims abstract description 25
- 239000000758 substrate Substances 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims description 22
- 239000000463 material Substances 0.000 claims abstract description 41
- 230000003197 catalytic effect Effects 0.000 claims abstract description 21
- 239000006260 foam Substances 0.000 claims abstract description 19
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910001425 magnesium ion Inorganic materials 0.000 claims abstract description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052742 iron Inorganic materials 0.000 claims abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 52
- 239000000203 mixture Substances 0.000 claims description 23
- 239000002105 nanoparticle Substances 0.000 claims description 22
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 18
- 239000012621 metal-organic framework Substances 0.000 claims description 15
- 238000005303 weighing Methods 0.000 claims description 15
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 235000019441 ethanol Nutrition 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 14
- 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 13
- SZQUEWJRBJDHSM-UHFFFAOYSA-N iron(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SZQUEWJRBJDHSM-UHFFFAOYSA-N 0.000 claims description 13
- 239000010941 cobalt Substances 0.000 claims description 12
- 229910017052 cobalt Inorganic materials 0.000 claims description 12
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 12
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(2+);cobalt(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 9
- 239000001530 fumaric acid Substances 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- 239000002086 nanomaterial Substances 0.000 claims description 8
- 239000012153 distilled water Substances 0.000 claims description 7
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 7
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 7
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 7
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 7
- 229910020599 Co 3 O 4 Inorganic materials 0.000 claims description 6
- STGNLGBPLOVYMA-MAZDBSFSSA-N (E)-but-2-enedioic acid Chemical compound OC(=O)\C=C\C(O)=O.OC(=O)\C=C\C(O)=O STGNLGBPLOVYMA-MAZDBSFSSA-N 0.000 claims description 5
- 239000012922 MOF pore Substances 0.000 claims description 5
- 238000005119 centrifugation Methods 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 238000010304 firing Methods 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 5
- 239000011248 coating agent Substances 0.000 claims description 4
- 238000000576 coating method Methods 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims description 2
- 238000003837 high-temperature calcination Methods 0.000 claims 1
- 238000006555 catalytic reaction Methods 0.000 abstract description 7
- 229910001429 cobalt ion Inorganic materials 0.000 abstract description 5
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 abstract description 5
- 238000005868 electrolysis reaction Methods 0.000 abstract description 4
- 238000000034 method Methods 0.000 abstract description 4
- 230000008569 process Effects 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 230000002195 synergetic effect Effects 0.000 abstract description 3
- 229910052723 transition metal Inorganic materials 0.000 abstract description 3
- 150000003624 transition metals Chemical class 0.000 abstract description 3
- 238000001179 sorption measurement Methods 0.000 abstract description 2
- LSSAUVYLDMOABJ-UHFFFAOYSA-N [Mg].[Co] Chemical compound [Mg].[Co] LSSAUVYLDMOABJ-UHFFFAOYSA-N 0.000 abstract 1
- 229910052751 metal Inorganic materials 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 21
- 238000012360 testing method Methods 0.000 description 15
- 238000002484 cyclic voltammetry Methods 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 3
- 238000004502 linear sweep voltammetry Methods 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 230000002441 reversible effect Effects 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000002803 fossil fuel Substances 0.000 description 2
- QZRHHEURPZONJU-UHFFFAOYSA-N iron(2+) dinitrate nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QZRHHEURPZONJU-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical group [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 238000004832 voltammetry Methods 0.000 description 2
- 229910020634 Co Mg Inorganic materials 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- YZCKVEUIGOORGS-NJFSPNSNSA-N Tritium Chemical compound [3H] YZCKVEUIGOORGS-NJFSPNSNSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229940011182 cobalt acetate Drugs 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical group [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 1
- 229940044175 cobalt sulfate Drugs 0.000 description 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical group [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical group [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013256 coordination polymer Substances 0.000 description 1
- 229920001795 coordination polymer Polymers 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical group [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 239000010411 electrocatalyst Substances 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- UGKDIUIOSMUOAW-UHFFFAOYSA-N iron nickel Chemical compound [Fe].[Ni] UGKDIUIOSMUOAW-UHFFFAOYSA-N 0.000 description 1
- 229910000358 iron sulfate Inorganic materials 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 239000011344 liquid material Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 239000002073 nanorod Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 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
- 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
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B23/00—Obtaining nickel or cobalt
- C22B23/02—Obtaining nickel or cobalt by dry processes
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
- C22B26/20—Obtaining alkaline earth metals or magnesium
- C22B26/22—Obtaining magnesium
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- C22B5/00—General methods of reducing to metals
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Abstract
The invention discloses a MIL-88@ CoMg catalytic material for hydrogen production by water electrolysis with foamed nickel as a substrate, which selects three metal elements of iron and cobalt magnesium as main elements of a catalyst, combines the high activity of catalytic hydrogen evolution of transition metal with an MOF porous structure, increases the relative ratio surface area of a hydrogen evolution material by utilizing the high porosity of the MOF material, and improves the conductivity of the material, thereby greatly increasing the hydrogen evolution efficiency of the electrolyzed water. Meanwhile, the synergistic effect of cobalt ions and magnesium ions can accelerate the adsorption of active sites of the catalyst and the foam nickel substrate material, so that the binding capacity of the material and the substrate is greatly increased in the catalysis process, and the catalysis stability is improved.
Description
Technical Field
The invention belongs to the technical field of hydrogen energy, and particularly relates to a preparation method and application of an MIL-88@ CoMg electrolytic water hydrogen evolution catalyst with foamed nickel as a substrate.
Background
The heavy use of traditional fossil fuels poses the dual problems of energy crisis and environmental deterioration, thus creating an urgent need for clean and sustainable alternative energy sources. The technical difficulty of renewable energy preparation is one of the key technologies for restricting the development of renewable energy. In a new energy system, hydrogen energy is an ideal secondary energy, compared with other energy sources, the hydrogen heat value is high, a combustion product is water, and the hydrogen energy is the most environment-friendly energy and can be stored in a high-pressure tank in a gas-liquid phase mode and a hydrogen storage material in a solid-phase mode. Another unique feature of hydrogen is the simplicity of the chemical bond. When the energy is released rapidly, the bonds formed by breaking are relatively few, the reaction rate constant is high, the electrode process kinetics is fast, and the energy can be released electrochemically. Therefore, hydrogen is considered to be the most promising energy carrier to replace traditional fossil fuels. The hydrogen is used as a clean and pollution-free renewable energy source, the energy problem and the environmental problem can be effectively solved, the hydrogen production reaction by electrolysis is considered as the reverse reaction of hydrogen combustion, and the combination of the hydrogen and the hydrogen is used for forming an energy circulation system with zero carbon emission. The existing materials for catalyzing the water electrolysis have the problems that the stability of the known materials is poor, and the catalytic effect of the catalyst is poor when the catalyst faces different pH values, temperatures and current intensities, so that the popularization of the water electrolysis hydrogen production technology is greatly hindered.
Metal-organic framework Materials (MOFs) are coordination polymers which develop rapidly in the last two decades, have three-dimensional pore structures and have the advantages of high porosity, low density, large specific surface area, regular pore channels, adjustable pore diameter, diversity and tailorability of topological structures and the like. Wherein MIL-88 is a metal organic framework compound with an MOF structure and taking an iron element as a main element, and is widely applied to the fields of catalytic sensing and the like. The invention combines the porous structure of the MOF material and the high catalytic activity of the Fe-Co-Mg material to prepare the MIL-88@ CoMg hydrogen evolution catalyst which can stabilize the electrolyzed water and takes the foamed nickel as the substrate.
Disclosure of Invention
The invention relates to a preparation method of a MIL-88@ CoMg electrolyzed water hydrogen evolution catalyst taking foamed nickel as a substrate, which has the characteristics of high hydrogen evolution catalytic activity and good stability of an iron-nickel catalyst, and also combines the structural advantages of multiple channels, high porosity and large specific surface area of an MOF material. The invention is realized by the following technical scheme:
s1, preparing a porous MOF framework: weighing 10-15 parts of ferric nitrate nonahydrate and 3 parts of fumaric acid, dissolving the ferric nitrate nonahydrate and the fumaric acid fumarate into 50 parts of distilled water, uniformly stirring the mixture by using a magnetic stirrer at the temperature of 30-70 ℃, stirring the mixture for 10-15min, then putting the mixture into a muffle furnace, heating the mixture for 4-7h at the temperature of 120-150 ℃, cooling the mixture, taking out the mixture, and centrifuging the mixture to generate MIL-88 nano particles;
s2, introducing a cobalt element into an MOF framework: dissolving 1 part of centrifuged MIL-88 particles and 1-4 parts of cobalt nitrate hexahydrate in 50 parts of ethanol, and treating for 1h at the constant temperature of 100 ℃ in an oil bath to obtain MIL-88@ Co;
s3: placing the MIL-88@ Co nano-particles obtained by preparation in a centrifugal machine for centrifugation under the condition of 4000r/min and 5min, then drying the nano-particles by using absolute ethyl alcohol, and carrying out N treatment on the obtained nano-particles in a tubular furnace 2 Firing under the atmosphere, wherein the heating rate is 2 ℃/min, the temperature is kept at 130 ℃ for 1h, the temperature is kept at 350 ℃ for 2.5h, the cobalt element form is converted into cobaltosic oxide, and MIL-88@ Co is obtained 3 O 4 ；
S4, weighing 0.4-1 part of magnesium sulfate and MIL-88@ Co 3 O 4 0.5 part of Co, reduced by a tube furnace under hydrogen conditions 3 O 4 And introducing magnesium ions to form MIL-88@ CoMg under the reaction conditions: 400 ℃ for 2h;
s5: washing with 3M hydrochloric acid and absolute ethanol to 0.8 × 1.0cm 2 Weighing 0.007-0.01 parts of MIL-88@ CoMg nano material, 0.015 parts of carbon powder, 0.05 parts of 0.1 mg/muL PTFE and 5 parts of ethanol, putting the materials into an ultrasonic cleaning machine for 30min, drying the materials, and then uniformly coating the dried materials on the surface of the processed foamed nickel to obtain the MIL-88@ CoMg hydrogen evolution catalytic material taking the foamed nickel as the substrate.
One part of solid material used in the technical scheme is 1g, and one part of liquid material is 1mL.
Preferably: 10g of ferric nitrate nonahydrate, 3g of fumaric acid and 50mL of distilled water are weighed in the S1;
preferably: 1g of cobalt nitrate hexahydrate and 50mL of ethanol are weighed in the S2;
preferably: the magnesium sulfate weighed in the S4 is 0.4g;
preferably: 0.007g of MIL-88@ CoMg nano material, 0.015g of carbon powder, 0.05mL of 0.1 mg/muL PTFE and 5mL of ethanol which are weighed in the S5.
The invention has the advantages that:
1. the preparation process of the electrolyzed water hydrogen evolution catalyst prepared by the invention is relatively simple, three transition metals of iron, cobalt and magnesium are selected as main elements of the catalyst, the high activity of the transition metals for catalyzing hydrogen evolution is combined with the MOF porous structure, the high porosity of the MOF material is utilized, the relative ratio surface area of the hydrogen evolution material is increased, the conductivity of the material is improved, and thus the hydrogen evolution efficiency of electrolyzed water is greatly increased.
2. Meanwhile, the synergistic effect of cobalt ions and magnesium ions can accelerate the adsorption of active sites of the catalyst and the foam nickel substrate material, so that the binding capacity of the material and the substrate is greatly increased in the catalysis process, and the catalysis stability is improved.
3. The catalyst prepared by the invention has good stability and can be repeatedly used for many times.
Drawings
FIG. 1 is a scan (100 μm) of the microstructure of example 1 of the present invention.
FIG. 2 is a scan (2 μm) of the microstructure of example 2 of the present invention.
FIG. 3 is a plot of linear voltammetry scans for examples 1-3 of the present invention.
FIG. 4 is a Tafel slope plot for examples 1-3 of the present invention.
FIG. 5 is a voltage-time graph of example 1 of the present invention.
FIG. 6 is a plot of cyclic voltammetry scans for example 3 of the present invention.
Fig. 7 is an electric double layer capacitance curve of example 3 of the present invention.
Detailed Description
The following embodiments of the present invention are 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. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention. It is to be noted that the features in the following embodiments and examples may be combined with each other without conflict.
Example 1
S1, preparing a porous MOF framework: weighing 10g of ferric nitrate nonahydrate and 3g of fumaric acid, dissolving the ferric nitrate nonahydrate and the fumaric acid fumarate into 50mL of distilled water, uniformly stirring the mixture by using a magnetic stirrer at the temperature of 30 ℃, stirring the mixture for 10min, and then putting the mixture into a muffle furnace for high-temperature treatment, wherein the heating conditions are as follows: heating at 150 ℃ for 4h, cooling, taking out, centrifuging and generating MIL-88 nano particles;
s2, introducing a cobalt element into an MOF framework: 1g of centrifuged MIL-88 particles and 1g of cobalt nitrate hexahydrate are dissolved in 50mL of ethanol and treated for 1h at the constant temperature of 100 ℃ in an oil bath to obtain MIL-88@ Co;
s3: placing the MIL-88@ Co nano-particles obtained by preparation in a centrifugal machine for centrifugation under the condition of 4000r/min and 5min, then drying the nano-particles by using absolute ethyl alcohol, and carrying out N treatment on the obtained nano-particles in a tubular furnace 2 Firing under the atmosphere, wherein the heating rate is 2 ℃/min, the temperature is kept at 130 ℃ for 1h, the temperature is kept at 350 ℃ for 2.5h, the cobalt element form is converted into cobaltosic oxide, and MIL-88@ Co is obtained 3 O 4 ；
S4, weighing 0.4g of magnesium sulfate and MIL-88@ Co 3 O 4 0.5g, co reduction Using a tube furnace under Hydrogen conditions 3 O 4 And introducing magnesium ions to form MIL-88@ CoMg under the reaction conditions: 400 ℃ for 2h;
s5: washing with 3M hydrochloric acid and absolute ethanol to 0.8 × 1.0cm 2 The foam nickel substrate material is prepared by weighing 0.007g of MIL-88@ CoMg nano material, 0.015g of carbon powder and 0.0.05mL of 1 mg/mu L PTFE and 5mL of ethanol are put into an ultrasonic cleaning machine for 30min, and are dried and then evenly coated on the surface of the processed foam nickel, thus obtaining the MIL-88@ CoMg hydrogen evolution catalytic material taking the foam nickel as the substrate.
Comparative example 1, the same parameters as in example 1 were used except that fumaric acid was changed to maleic acid of the same mass in the step S1.
Comparative example 2, the same parameters as in example 1 were used except that iron nitrate nonahydrate was changed to equal mass of iron sulfate in the S1 step.
Comparative example 3, the same parameters as in example 1 were used except that iron nitrate nonahydrate was changed to equal mass of ferrous nitrate in the S1 step.
Example 2
S1, preparing a porous MOF framework: weighing 12g of ferric nitrate nonahydrate and 3g of fumaric acid, dissolving the ferric nitrate nonahydrate and the fumaric acid fumarate into 50mL of distilled water, uniformly stirring the mixture by using a magnetic stirrer at the temperature of 40 ℃, stirring the mixture for 12min, and then putting the mixture into a muffle furnace for high-temperature treatment, wherein the heating conditions are as follows: heating at 130 ℃ for 5h, cooling, taking out, centrifuging, and generating MIL-88 nano particles;
s2, introducing a cobalt element into an MOF framework: 1g of centrifuged MIL-88 particles and 2g of cobalt nitrate hexahydrate are dissolved in 50mL of ethanol and treated for 1h at the constant temperature of 100 ℃ in an oil bath to obtain MIL-88@ Co;
s3: placing the MIL-88@ Co nano-particles obtained by preparation in a centrifugal machine for centrifugation under the condition of 4000r/min and 5min, then drying the nano-particles by using absolute ethyl alcohol, and carrying out N treatment on the obtained nano-particles in a tubular furnace 2 Firing under the atmosphere, wherein the heating rate is 2 ℃/min, the temperature is kept at 130 ℃ for 1h, the temperature is kept at 350 ℃ for 2.5h, the cobalt element form is converted into cobaltosic oxide, and MIL-88@ Co is obtained 3 O 4 ；
S4, weighing 0.6g of magnesium sulfate and MIL-88@ Co 3 O 4 0.5g, co reduction Using a tube furnace under Hydrogen conditions 3 O 4 And introducing magnesium ions to form MIL-88@ CoMg under the reaction conditions: 400 ℃ for 2h;
s5: washing 0.8 x 1.0cm with 3M hydrochloric acid and absolute ethanol 2 Foamed nickel baseAnd (3) weighing 0.009g of MIL-88@ CoMg nano material, 0.015g of carbon powder, 0.05mL of 0.1 mg/muL PTFE and 5mL of ethanol, putting the materials into an ultrasonic cleaning machine for 30min, drying, and then uniformly coating the materials on the surface of the treated foam nickel to obtain the MIL-88@ CoMg hydrogen evolution catalytic material taking the foam nickel as the substrate.
Comparative example 4, the same parameters as in example 2 were used except that cobalt nitrate hexahydrate was replaced with cobalt chloride of equal mass in the step S2.
Comparative example 5 the same parameters as in example 2 were used except that cobalt nitrate hexahydrate was replaced with cobalt acetate of equal mass in the S2 step.
Comparative example 6 the same parameters as in example 2 were used except that cobalt nitrate hexahydrate was replaced with cobalt sulfate of equal mass in the S2 step.
Example 3
S1, preparing a porous MOF framework: weighing 15g of ferric nitrate nonahydrate and 3g of fumaric acid, dissolving the ferric nitrate nonahydrate and the fumaric acid fumarate into 50mL of distilled water, uniformly stirring the mixture by using a magnetic stirrer at 70 ℃, stirring the mixture for 15min, and then putting the mixture into a muffle furnace for high-temperature treatment, wherein the heating conditions are as follows: heating at 120 ℃ for 7h, cooling, taking out, centrifuging, and generating MIL-88 nano particles;
s2, introducing a cobalt element into an MOF framework: dissolving 1g of centrifuged MIL-88 particles and 4g of cobalt nitrate hexahydrate in 50mL of ethanol, and treating for 1h at the constant temperature of 100 ℃ in an oil bath to obtain MIL-88@ Co;
s3: placing the MIL-88@ Co nano-particles obtained by preparation in a centrifugal machine for centrifugation under the condition of 4000r/min and 5min, then drying the nano-particles by using absolute ethyl alcohol, and carrying out N treatment on the obtained nano-particles in a tubular furnace 2 Firing under atmosphere with heating rate of 2 deg.C/min, maintaining at 130 deg.C for 1h, maintaining at 350 deg.C for 2.5h, converting cobalt element form into cobaltosic oxide to obtain MIL-88@ Co 3 O 4 ；
S4, weighing 0.4-1g of magnesium sulfate and MIL-88@ Co 3 O 4 0.5g, reduction of Co in a tube furnace under Hydrogen 3 O 4 And introducing magnesium ions to form MIL-88@ CoMg under the reaction conditions: 400 ℃ for 2h;
s5: using 3M saltWashing with acid and absolute ethanol at 0.8 x 1.0cm 2 Weighing 0.01g of MIL-88@ CoMg nano material, 0.015g of carbon powder, 0.05mL of 0.1 mg/muL PTFE and 5mL of ethanol, putting the materials into an ultrasonic cleaning machine for 30min, drying the materials, and then uniformly coating the dried materials on the surface of the processed foam nickel to obtain the MIL-88@ CoMg hydrogen evolution catalytic material taking the foam nickel as the substrate.
Comparative example 7, the same parameters as in example 3 were used except that cobalt nitrate hexahydrate was replaced with silver nitrate of equal mass in the S2 step.
Comparative example 8, the same parameters as in example 3 were used except that cobalt nitrate hexahydrate was replaced with copper nitrate of equal mass in the step S2.
Comparative example 9, the same parameters as in example 3 were used except that cobalt nitrate hexahydrate was changed to ferrous nitrate of equal mass in the S2 step.
The electrodes of the electrolytic water hydrogen evolution catalyst prepared in examples 1 to 3 and comparative examples 1 to 9 were held by electrode holders so that the exposed portions were 0.8X 0.8cm 2 The square of (a) as the working electrode in the three-electrode system test. Taking a prepared 1M KOH solution as a test electrolyte, continuously introducing 10min of nitrogen into the solution to remove air dissolved in the electrolyte, completely immersing a prepared hydrogen evolution catalytic electrode into the solution, starting an electrolytic water hydrogen evolution catalytic reaction in the electrolyte after connecting a main electrode in a three-electrode system with an Hg/HgO electrode and a counter electrode with a platinum electrode to a Shanghai Chenghua electrochemical workstation CHI660E, and testing a Linear Sweep Voltammetry (LSV) performance curve of the catalyst, wherein the purpose of testing the LSV curve is to determine the catalytic activity of the catalyst, and the testing sweep rate is 5mV s -1 The hydrogen evolution reaction voltage is tested to be-2V-0V (vs. RHE), and the obtained potential is converted into the potential of the reversible hydrogen electrode according to the formula: e RHE ＝E Hg/HgO +0.098+0.059 × pH, converting the obtained current into current density per unit electrode area, and obtaining the current density of 500mAcm -2 Then, corresponding overpotential drawing tables are arranged, the test results are shown in table 1 and fig. 3, the current density numerical value in the LSV curve is subjected to data processing to obtain a Tafel slope curve, and the results are shown in table 2 and fig. 4; voltage-timeThe curve mainly tests the catalytic stability of the electrocatalyst, the electrolyte solution for the durability test also uses 1M KOH solution, and the test result is shown in fig. 5; cyclic voltammetry CVs are respectively 20, 40, 60, 80, 100, 120, 140, 160, 180 and 200mV s at room temperature -1 The cycle stability of the catalyst of example 3 was tested at each of the scan rates, the test results are shown in fig. 6, and the electric double layer capacitance curve of example 3 was obtained by data calculation, and the results are shown in fig. 7.
TABLE 1 test samples at a current density of 500mA cm -2 Corresponding overpotential
TABLE 2 Tafel slope of test samples
| Test sample | Tafel slope (mVdec) -1 ) |
| Example 1 | 43 |
| Example 2 | 86 |
| Example 3 | 69 |
| Comparative example 1 | 78 |
| Comparative example 2 | 73 |
| Comparative example 3 | 89 |
| Comparative example 4 | 87 |
| Comparative example 5 | 83 |
| Comparative example 6 | 91 |
| Comparative example 7 | 102 |
| Comparative example 8 | 106 |
| Comparative example 9 | 100 |
According to the microstructure scanning diagrams of the embodiment 1 and the embodiment 2 shown in the figure 1 and the figure 2, the microstructure of the MIL-88@ CoMg nano particle presents a nanorod structure, the ordered regular microstructure can increase the actual catalytic reaction area in the process of catalyzing and electrolyzing water, and cobalt ions and magnesium ions are added for performance regulation through structure regulation of a pore channel framework introduced with MOF, so that the efficiency of catalyzing and hydrogen evolution is improved.
From the linear voltammetry scan data of the test samples of Table 1 and FIG. 3, it can be seen that at the same 500mA cm -2 The overpotential required for the sample of example 1 was the lowest, only-0.550V at current density, atComparing the hydrogen evolution catalytic performance of the examples with different material proportions, it can be seen that the material proportion of example 1 is most scientific, and the best hydrogen evolution catalytic effect can be achieved, and in the contrary comparative example, no matter the raw material of the MIL-88 nano particles prepared from fumaric acid and ferric nitrate nonahydrate is changed or the addition of any one of cobalt ions and magnesium ions is changed, the improvement of the catalytic performance cannot be obtained, which indicates that the MOF structure framework of MIL-88 and the synergistic effect of the cobalt ions and the magnesium ions play an important role in the catalysis of the hydrogen evolution reaction; as can be seen from the observation of the Tafel slopes of the test samples in Table 2 and FIG. 4, the Tafel slope of example 1 was the smallest and 43mV dec -1 This shows that the material subjected to the least hydraulic resistance in examples 1-3 and comparative examples 1-9 is example 1, i.e., the catalytic material of example 1 is the most conductive and can catalytically electrolyze water to generate more hydrogen energy under the same applied voltage.
The voltage-time graph of example 1 of fig. 5 was tested for 100 hours of hydrogen evolution reaction, and it can be seen that example 1 can maintain a substantially constant voltage during the catalytic hydrogen evolution reaction, indicating that the stability of the reaction process is very good; the cyclic voltammetry sweep curve of example 3 of FIG. 6 demonstrates a range from 20mV s -1 The scanning rate of (2) is increased to 200mV s -1 The curve closure of cyclic voltammetry was good in the course of the scan rate (b), which indicates that the catalytic hydrogen evolution reaction process of example 3 was reversible, and the prepared hydrogen evolution catalytic material could be repeatedly used for a long time, and fig. 7 shows that the electric double layer capacitance of example 3 was 20.38mF cm -2 The material has better electrochemical specific surface area.
The above-mentioned embodiments only express the specific embodiments of the present invention, and the description thereof is specific and detailed, but not construed as limiting the scope of the present invention. It should be understood that any other changes, modifications, substitutions, combinations and simplifications which do not depart from the spirit and principles of the invention should be construed as equivalents thereof, which should be construed by those skilled in the art and are within the scope of the invention.
Claims (9)
1. The preparation and application of the MIL-88@ CoMg electrolyzed water hydrogen evolution catalyst with foamed nickel as a substrate are disclosed, and the hydrogen evolution catalyst containing iron, cobalt and magnesium is characterized in that: the preparation method comprises the following steps:
s1, preparing a porous MOF framework: weighing 10-15 parts of ferric nitrate nonahydrate and 3 parts of fumaric acid, dissolving the ferric nitrate nonahydrate and the fumaric acid fumarate into 50 parts of distilled water, uniformly stirring the mixture by using a magnetic stirrer at the temperature of 30-70 ℃, stirring the mixture for 10-15min, then putting the mixture into a muffle furnace, heating the mixture for 4-7h at the temperature of 120-150 ℃, cooling the mixture, taking out the mixture, and centrifuging the mixture to generate MIL-88 nano particles;
s2, introducing a cobalt element into an MOF framework: dissolving 1 part of centrifuged MIL-88 particles and 1-4 parts of cobalt nitrate hexahydrate in 50 parts of ethanol, and treating for 1h at the constant temperature of 100 ℃ in an oil bath to obtain MIL-88@ Co;
s3: placing the MIL-88@ Co nano particle obtained by preparation in a centrifuge for centrifugation under the conditions of 4000r/min and 5min, then drying the nano particle by absolute ethyl alcohol, and carrying out N treatment on the obtained nano particle in a tubular furnace 2 Firing under the atmosphere, wherein the heating rate is 2 ℃/min, the temperature is kept at 130 ℃ for 1h, the temperature is kept at 350 ℃ for 2.5h, the cobalt element form is converted into cobaltosic oxide, and MIL-88@ Co is obtained 3 O 4 ；
S4, weighing 0.4-1 part of magnesium sulfate and MIL-88@ Co 3 O 4 0.5 part of Co, reduced by a tube furnace under hydrogen conditions 3 O 4 And introducing magnesium ions to form MIL-88@ CoMg under the reaction conditions: 400 ℃ for 2h;
s5: washing with 3M hydrochloric acid and absolute ethanol to 0.8 × 1.0cm 2 The foam nickel substrate material is prepared by weighing 0.007-0.01 part of MIL-88@ CoMg nano material, 0.015 part of carbon powder, 0.05 part of 0.1 mg/microliter PTFE and 5 parts of ethanol, putting the materials into an ultrasonic cleaning machine for 30min, drying the materials, and then uniformly coating the materials on the surface of the processed foam nickel to obtain the MIL-88@ CoMg hydrogen evolution catalytic material taking the foam nickel as the substrate.
2. The preparation and application of MIL-88@ CoMg electrolytic water hydrogen evolution catalyst based on nickel foam as claimed in claim 1, wherein the catalyst comprises: 10g of ferric nitrate nonahydrate, 3g of fumaric acid and 50mL of distilled water are weighed in the S1.
3. The preparation and application of the catalyst for hydrogen evolution from MIL-88@ CoMg electrolyzed water based on nickel foam as claimed in claim 1 or 2, wherein the catalyst comprises the following components in percentage by weight: the temperature of the muffle furnace in the S1 is set to be 150 ℃, and the heating time is 4h.
4. The preparation and application of MIL-88@ CoMg electrolytic water hydrogen evolution catalyst based on nickel foam as claimed in claim 1, wherein the catalyst comprises: 1g of cobalt nitrate hexahydrate and 50mL of ethanol weighed in the S2.
5. The preparation and application of MIL-88@ CoMg electrolytic water hydrogen evolution catalyst based on nickel foam as claimed in claim 1, wherein the catalyst comprises: and in the S4, 0.4g of magnesium sulfate is weighed.
6. The preparation and application of the catalyst for hydrogen evolution from MIL-88@ CoMg electrolyzed water based on nickel foam as claimed in claim 1, wherein the catalyst comprises the following components in percentage by weight: 0.007g of MIL-88@ CoMg nano material, 0.015g of carbon powder, 0.05mL of 0.1 mg/muL PTFE and 5mL of ethanol which are weighed in the S5.
7. The preparation and application of the catalyst for hydrogen evolution from MIL-88@ CoMg electrolyzed water based on nickel foam as claimed in claim 6, wherein the catalyst comprises the following components in percentage by weight: and 0.01 part of MIL-88@ CoMg nano material weighed in the S5.
8. The preparation and application of MIL-88@ CoMg electrolytic water hydrogen evolution catalyst based on nickel foam as claimed in claim 1 or 5, wherein the catalyst comprises: and the high-temperature calcination of S4 is carried out at 400 ℃ for 2h.
9. The catalyst prepared by the preparation method mentioned in the preparation and application of MIL-88@ CoMg electrolyzed water hydrogen evolution catalyst using foamed nickel as the substrate in any one of claims 1 to 8.
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