CN110639596A - MOFs-based heteroatom-doped porous carbon electrocatalyst and preparation method thereof - Google Patents
MOFs-based heteroatom-doped porous carbon electrocatalyst and preparation method thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 111
- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 86
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 54
- 239000010411 electrocatalyst Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 100
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 63
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 54
- 125000005842 heteroatom Chemical group 0.000 claims abstract description 42
- 239000013110 organic ligand Substances 0.000 claims abstract description 36
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000001354 calcination Methods 0.000 claims abstract description 11
- 239000002994 raw material Substances 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 83
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 61
- 239000012153 distilled water Substances 0.000 claims description 43
- 239000000463 material Substances 0.000 claims description 43
- 229910052759 nickel Inorganic materials 0.000 claims description 42
- 238000010438 heat treatment Methods 0.000 claims description 41
- 238000001035 drying Methods 0.000 claims description 32
- 239000007787 solid Substances 0.000 claims description 31
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 27
- 238000003756 stirring Methods 0.000 claims description 24
- GAMSSMZJKUMFEY-UHFFFAOYSA-N 4-[(4-carboxyphenyl)disulfanyl]benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1SSC1=CC=C(C(O)=O)C=C1 GAMSSMZJKUMFEY-UHFFFAOYSA-N 0.000 claims description 23
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 18
- 238000001816 cooling Methods 0.000 claims description 16
- 239000000047 product Substances 0.000 claims description 16
- 238000010992 reflux Methods 0.000 claims description 16
- 238000005406 washing Methods 0.000 claims description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 11
- 230000004913 activation Effects 0.000 claims description 10
- 239000002131 composite material Substances 0.000 claims description 10
- 238000004809 thin layer chromatography Methods 0.000 claims description 10
- 238000000498 ball milling Methods 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 8
- 238000000926 separation method Methods 0.000 claims description 8
- 239000012265 solid product Substances 0.000 claims description 8
- 239000003814 drug Substances 0.000 claims description 3
- 229940079593 drug Drugs 0.000 claims description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical group C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 abstract description 27
- 238000000034 method Methods 0.000 abstract description 19
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 12
- 229910052760 oxygen Inorganic materials 0.000 abstract description 12
- 239000001301 oxygen Substances 0.000 abstract description 12
- 238000005868 electrolysis reaction Methods 0.000 abstract description 11
- 239000003575 carbonaceous material Substances 0.000 abstract description 10
- WWNBZGLDODTKEM-UHFFFAOYSA-N sulfanylidenenickel Chemical compound [Ni]=S WWNBZGLDODTKEM-UHFFFAOYSA-N 0.000 abstract description 10
- 239000003792 electrolyte Substances 0.000 abstract description 8
- 238000003763 carbonization Methods 0.000 abstract description 7
- 239000011148 porous material Substances 0.000 abstract description 6
- 230000005540 biological transmission Effects 0.000 abstract description 5
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 230000009977 dual effect Effects 0.000 abstract description 3
- 230000005012 migration Effects 0.000 abstract description 3
- 238000013508 migration Methods 0.000 abstract description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 14
- 229910052739 hydrogen Inorganic materials 0.000 description 14
- 239000001257 hydrogen Substances 0.000 description 14
- 238000004519 manufacturing process Methods 0.000 description 8
- -1 nickel sulfide compound Chemical class 0.000 description 7
- 229910000510 noble metal Inorganic materials 0.000 description 5
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(IV) oxide Inorganic materials O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B01J35/33—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/086—Decomposition of an organometallic compound, a metal complex or a metal salt of a carboxylic acid
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- 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
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The invention relates to the technical field of water electrolysis catalysts, and discloses an MOFs-based heteroatom doped porous carbon electrocatalyst and a preparation method thereof, wherein the MOFs-based heteroatom doped porous carbon electrocatalyst comprises the following formula raw materials: nickel nitrate, 4-azopyridine, 4' -dithiodibenzoic acid and graphene. According to the MOFs-based heteroatom doped porous carbon electrocatalyst and the preparation method thereof, the Ni-based dual organic ligand MOFs complex has a regular porous structure and an adjustable pore diameter, the sulfur nickel compound-N/S doped porous carbon material is prepared by a calcination carbonization method, has a large number of catalytic active sites, has excellent conductivity and a lower oxygen evolution overpotential, and is uniformly dispersed on the huge specific surface and pores of graphene, so that the phenomenon that the catalyst is agglomerated in an electrolyte to reduce the active sites of the catalyst is avoided, a huge conductive network is formed between the interface of the catalyst and the graphene, and the migration and transmission processes of electrons are promoted.
Description
Technical Field
The invention relates to the technical field of water electrolysis catalysts, in particular to an MOFs-based heteroatom doped porous carbon electrocatalyst and a preparation method thereof.
Background
With the increasing exhaustion of fossil energy and the increasing severity of environmental pollution, energy and environmental problems have become the most important problems in sustainable development of human society, the gradual shift from fossil fuels to clean energy without pollution in sustainable development is a necessary trend in development, hydrogen is an ideal clean energy with abundant resources, and is widely applied to hydrogen-powered automobiles, hydrogen energy power generation, phosphate fuel cells, molten carbonate fuels and other aspects, and hydrogen production by electrolysis of water is an important means for realizing industrialization and cheap hydrogen preparation.
At present, the hydrogen production by water electrolysis is technically incomplete and cannot be realized in commercial scale water electrolysis, the hydrogen production by water electrolysis is realized by introducing direct current into an electrolytic cell filled with electrolyte, water molecules respectively generate electrochemical oxidation-reduction reactions on a positive electrode and a negative electrode to decompose water into hydrogen and oxygen, and the hydrogen and oxygen are separated into hydrogen evolution reaction and oxygen evolution reaction, wherein the oxygen evolution reaction process is difficult to realize the oxygen evolution process rapidly due to the restriction of dynamic factors, so that the hydrogen production process by water electrolysis is inhibited, and at present, a noble metal catalyst such as IrO (iron oxide) is mainly added to the hydrogen production process by adding the noble metal catalyst at present2And RuO2The oxygen evolution reaction is promoted, but the noble metal content is rare, the acquisition is difficult, the price is high, the cost of hydrogen production by water electrolysis is greatly increased, the cost of non-noble metal catalysts such as sulfide and transition metal oxide is low, the oxygen evolution overpotential is low, the potential application prospect is realized in the hydrogen production technology by water electrolysis, but the non-noble metal catalysts are easy to agglomerate, the active sites of the catalysts are reduced, the conductivity is poor, and the practicability of the catalysts is greatly reduced.
The metal organic framework MDFs material can be used for preparing a heteroatom doped porous carbon material to load a catalyst by a thermal decomposition carbonization method, and the MOFs derived catalyst has potential application value in the aspects of electrochemical energy conversion and electrocatalytic hydrogen production, and the existing MOFs derived carbon catalyst mainly adopts a direct carbonization method using MOFs as a precursor; a MOFs-heteroatom source mixture carbonization method; the carbonization method of the MOF compound, but the electrocatalytic performance of the catalyst is not high, the stability in an electrolyte is poor, and the catalyst is easy to agglomerate to form a large-particle compound, so that the specific surface area and the active sites of the electrocatalyst are reduced.
Disclosure of Invention
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides an MOFs-based heteroatom doped porous carbon electrocatalyst and a preparation method thereof, which solve the problem of low catalytic performance of the existing electrocatalyst and solve the problems of poor stability of the catalyst in an electrolyte and easy agglomeration to form a large-particle compound.
(II) technical scheme
In order to achieve the purpose, the invention provides the following technical scheme: an electro-catalyst of heteroatom doped porous carbon based on MOFs and a preparation method thereof, comprises the following formula raw materials in parts by weight: 30-38 parts of nickel nitrate, 16-20 parts of 4, 4-azopyridine, 12-20 parts of 4,4' -dithiodibenzoic acid and 22-42 parts of graphene, and the preparation method comprises the following experimental medicines: distilled water, N-dimethylformamide, absolute ethyl alcohol and dilute hydrochloric acid.
Preferably, the nickel nitrate is Ni (NO)3)2·6H2O。
Preferably, the 4, 4-azopyridine and the 4,4' -dithiodibenzoic acid are both chemically pure.
Preferably, the graphene is single-layer graphene powder, the sheet diameter is 0.5-5um, and the thickness is 0.8-1.2 nm.
Preferably, the preparation method of the MOFs-based heteroatom-doped porous carbon electrocatalyst comprises the following steps of:
(1) a reflux device is carried in the reaction bottle, and high-purity N is introduced2Removing air, then adding proper amount of distilled water and 30-38 parts of nickel nitrate Ni (NO) in turn3)2·6H2O, stirring until the solid is dissolved, then sequentially adding N, N-dimethylformamide, 16-20 parts of 4, 4-azopyridine and 12-20 parts of 4,4' -dithiodibenzoic acid, placing the reaction bottle in an oil bath pot, heating to 155-165 ℃ under the condition of N2Stirring at a constant speed under an atmosphere, heating for reflux reaction, observing the reaction process through a TLC (thin layer chromatography) method, cooling the solution to room temperature and filtering to remove N, N-dimethylformamide when 4,4' -dithiodibenzoic acid is completely reacted and a large amount of light yellow solid is produced, washing the obtained light yellow solid with a proper amount of distilled water and absolute ethyl alcohol in sequence, and fully drying to obtain the nickel-based diorganoligand MOFs.
(2) Adding a proper amount of distilled water into a reaction bottle, then adding 22-42 parts of graphene and the nickel-based diorganoligand MOFs prepared in the step (1), uniformly stirring, transferring the solution into a hydrothermal synthesis reaction kettle, placing the hydrothermal synthesis reaction kettle in a reaction kettle heating box, heating to 120-130 ℃, carrying out an activation reaction for 4-8h, removing the distilled water from the solution through a high-speed centrifuge after the reaction is finished, and fully drying the solid product to obtain the nickel-based diorganoligand MOFs loaded graphene composite.
(3) Introducing high-purity N into an atmosphere resistance furnace2And (3) adding the nickel-based double organic ligands MOFs load graphene composite prepared in the step (2), heating the temperature of the atmosphere resistance furnace to 820-850 ℃ at a heating rate of 5-10 ℃/min, keeping the temperature for calcining for 4-6h, cooling the calcined product to room temperature, washing the calcined product with proper amount of dilute hydrochloric acid and distilled water in sequence, and fully drying to obtain the heteroatom N/S doped porous carbon load graphene material.
(4) And (3) adding the heteroatom N/S doped porous carbon loaded graphene material prepared in the step (3) into a high-energy planetary ball mill, adding a small amount of absolute ethyl alcohol, wherein the revolution speed of the ball mill is 40-60rpm, the rotation speed is 580-620rpm, performing ball milling until the material passes through a 800-mesh screen, passing the material through a high-speed centrifuge, performing centrifugal separation to remove the absolute ethyl alcohol, and fully drying the solid to prepare the MOFs-based heteroatom doped porous carbon electrocatalyst.
(III) advantageous technical effects
Compared with the prior art, the invention has the following beneficial technical effects:
the MOFs-based heteroatom-doped porous carbon electrocatalyst and a preparation method thereof are characterized in that 4, 4-azopyridine and 4,4' -dithiodibenzoic acid are used as organic ligands to synthesize a Ni-based dual-organic ligand MOFs complex, the Ni-based dual-organic ligand MOFs complex has the advantages of regular porous structure, adjustable pore size and good crystallinity, highly dispersed heteroatoms can be doped to adjust the local electronic structure of the catalyst, a nickel sulfide compound-N/S doped porous carbon material is prepared by a calcination carbonization method, the transmission rate of electrons between the catalyst and an electrolyte in an electrolysis process can be promoted, a large number of catalytic active sites are formed, the nickel sulfide compound has excellent conductivity and lower oxygen evolution overpotential, the nickel sulfide compound-N/S doped porous carbon material has good electrocatalytic oxygen evolution performance, and the nickel sulfide compound-N/S doped porous carbon material is uniformly dispersed to the huge specific surface and pores of graphene by a hydrothermal synthesis activation method, the phenomenon that the catalyst is agglomerated in an electrolyte to reduce the active sites of the catalyst is avoided, and a huge conductive network is formed between the interface of the sulfur-nickel compound-N/S doped porous carbon material and the graphene, so that the migration and transmission processes of electrons are promoted, and the electrocatalytic performance of the catalyst is improved.
Detailed Description
In order to achieve the purpose, the invention provides the following technical scheme: an electro-catalyst of heteroatom doped porous carbon based on MOFs and a preparation method thereof, comprises the following formula raw materials in parts by weight: 30-38 parts of nickel nitrate, 16-20 parts of 4, 4-azopyridine, 12-20 parts of 4,4' -dithiodibenzoic acid and 22-42 parts of graphene, and the preparation method comprises the following experimental medicines: distilled water, N-dimethylformamide, absolute ethyl alcohol, dilute hydrochloric acid, and Ni (NO) as nickel nitrate3)2·6H2The O, 4, 4-azopyridine and the 4,4' -dithiodibenzoic acid are chemically pure, the graphene is single-layer graphene powder, the sheet diameter is 0.5-5um, and the thickness is 0.8-1.2 nm.
A preparation method of an electrocatalyst based on heteroatom-doped porous carbon of MOFs comprises the following steps:
(1) a reflux device is carried in the reaction bottle, and high-purity N is introduced2Removing air, then adding proper amount of distilled water and 30-38 parts of nickel nitrate Ni (NO) in turn3)2·6H2O, stirring until the solid is dissolved, then sequentially adding N, N-dimethylformamide, 16-20 parts of 4, 4-azopyridine and 12-20 parts of 4,4' -dithiodibenzoic acid, placing the reaction bottle in an oil bath pot, heating to 155-165 ℃ under the condition of N2Stirring at a constant speed under an atmosphere, heating for reflux reaction, observing the reaction process through a TLC (thin layer chromatography) method, cooling the solution to room temperature and filtering to remove N, N-dimethylformamide when 4,4' -dithiodibenzoic acid is completely reacted and a large amount of light yellow solid is produced, washing the obtained light yellow solid with a proper amount of distilled water and absolute ethyl alcohol in sequence, and fully drying to obtain the nickel-based diorganoligand MOFs.
(2) Adding a proper amount of distilled water into a reaction bottle, then adding 22-42 parts of graphene and the nickel-based diorganoligand MOFs prepared in the step (1), uniformly stirring, transferring the solution into a hydrothermal synthesis reaction kettle, placing the hydrothermal synthesis reaction kettle in a reaction kettle heating box, heating to 120-130 ℃, carrying out an activation reaction for 4-8h, removing the distilled water from the solution through a high-speed centrifuge after the reaction is finished, and fully drying the solid product to obtain the nickel-based diorganoligand MOFs loaded graphene composite.
(3) Introducing high-purity N into an atmosphere resistance furnace2And (3) adding the nickel-based double organic ligands MOFs load graphene composite prepared in the step (2), heating the temperature of the atmosphere resistance furnace to 820-850 ℃ at a heating rate of 5-10 ℃/min, keeping the temperature for calcining for 4-6h, cooling the calcined product to room temperature, washing the calcined product with proper amount of dilute hydrochloric acid and distilled water in sequence, and fully drying to obtain the heteroatom N/S doped porous carbon load graphene material.
(4) And (3) adding the heteroatom N/S doped porous carbon loaded graphene material prepared in the step (3) into a high-energy planetary ball mill, adding a small amount of absolute ethyl alcohol, wherein the revolution speed of the ball mill is 40-60rpm, the rotation speed is 580-620rpm, performing ball milling until the material passes through a 800-mesh screen, passing the material through a high-speed centrifuge, performing centrifugal separation to remove the absolute ethyl alcohol, and fully drying the solid to prepare the MOFs-based heteroatom doped porous carbon electrocatalyst.
Example 1:
(1) preparing nickel-based double organic ligands MOFs: a reflux device is carried in the reaction bottle, and high-purity N is introduced2Air is removed, then appropriate amount of distilled water and 30 parts of nickel nitrate Ni (NO) are added in sequence3)2·6H2O, stirring until the solid is dissolved, then adding N, N-dimethylformamide, 16 parts of 4, 4-azopyridine and 12 parts of 4,4' -dithiodibenzoic acid in sequence, placing the reaction bottle in an oil bath pot, heating to 155 ℃, and dissolving the N, N-dimethylformamide in the oil bath pot under the action of N2Stirring at constant speed under atmosphere, heating, refluxing, observing the reaction process by TLC thin-layer chromatography, cooling the solution to room temperature and filtering to remove N, N-dimethylformamide when 4,4' -dithiodibenzoic acid is completely reacted and a large amount of pale yellow solid is produced, and sequentially adding appropriate amount of distilled water and appropriate amount of N, N-dimethylformamide to obtain the pale yellow solidWashing with absolute ethyl alcohol, and fully drying to obtain the nickel-based dual-organic ligand MOFs complex 1.
(2) Preparing a nickel-based double organic ligand MOFs loaded graphene compound: adding a proper amount of distilled water into a reaction bottle, adding 42 parts of graphene and the nickel-based double organic ligand MOFs complex 1 prepared in the step (1), uniformly stirring, transferring the solution into a hydrothermal synthesis reaction kettle, placing the hydrothermal synthesis reaction kettle in a reaction kettle heating box, heating to 120 ℃, carrying out activation reaction for 4 hours, removing the distilled water from the solution through a high-speed centrifuge after the reaction is finished, and fully drying a solid product to obtain the nickel-based double organic ligand MOFs loaded graphene complex 1.
(3) Preparing a heteroatom N/S doped porous carbon loaded graphene material: introducing high-purity N into an atmosphere resistance furnace2And (3) adding the nickel-based double organic ligands MOFs loaded graphene composite 1 prepared in the step (2), raising the temperature of an atmosphere resistance furnace to 820 ℃ at a rate of 5 ℃/min, keeping the temperature for calcining for 4h, cooling the calcined product to room temperature, washing the calcined product with proper amount of dilute hydrochloric acid and distilled water in sequence, and fully drying to obtain the heteroatom N/S doped porous carbon loaded graphene material 1.
(4) Preparing an electrocatalyst based on heteroatom-doped porous carbon of the MOFs: and (3) adding the heteroatom N/S doped porous carbon loaded graphene material 1 prepared in the step (3) into a high-energy planetary ball mill, adding a small amount of absolute ethyl alcohol, wherein the revolution speed of the ball mill is 40rpm, the rotation speed of the ball mill is 580rpm, performing ball milling until the material passes through a 800-mesh screen, passing the material through a high-speed centrifuge, performing centrifugal separation to remove the absolute ethyl alcohol, fully drying the solid, and preparing the heteroatom doped porous carbon based electrocatalyst material 1 based on MOFs.
Example 2:
(1) preparing nickel-based double organic ligands MOFs: a reflux device is carried in the reaction bottle, and high-purity N is introduced2Air was removed and then an appropriate amount of distilled water and 31 parts of nickel nitrate Ni (NO) were added in sequence3)2·6H2O, stirring until the solid is dissolved, then sequentially adding N, N-dimethylformamide, 17 parts of 4, 4-azopyridine and 14 parts of 4,4' -dithiodibenzoic acid, placing the reaction bottle in an oil bath pot,heating to 155 ℃ under N2Stirring at a constant speed under an atmosphere, heating for reflux reaction, observing the reaction process through a TLC (thin layer chromatography) method, cooling the solution to room temperature and filtering to remove N, N-dimethylformamide when 4,4' -dithiodibenzoic acid is completely reacted and a large amount of light yellow solid is produced, washing the obtained light yellow solid with a proper amount of distilled water and absolute ethyl alcohol in sequence, and fully drying to obtain the nickel-based diorganoligand MOFs complex 2.
(2) Preparing a nickel-based double organic ligand MOFs loaded graphene compound: adding a proper amount of distilled water into a reaction bottle, adding 38 parts of graphene and the nickel-based double organic ligand MOFs complex 2 prepared in the step (1), uniformly stirring, transferring the solution into a hydrothermal synthesis reaction kettle, placing the hydrothermal synthesis reaction kettle in a reaction kettle heating box, heating to 125 ℃, carrying out activation reaction for 5 hours, removing the distilled water from the solution through a high-speed centrifuge after the reaction is finished, and fully drying a solid product to obtain the nickel-based double organic ligand MOFs loaded graphene complex 2.
(3) Preparing a heteroatom N/S doped porous carbon loaded graphene material: introducing high-purity N into an atmosphere resistance furnace2And (3) adding the nickel-based double organic ligands MOFs prepared in the step (2) to load the graphene composite 2, raising the temperature of an atmosphere resistance furnace to 830 ℃ at a rate of 5 ℃/min, keeping the temperature for calcining for 4h, cooling the calcined product to room temperature, washing the calcined product with proper amount of dilute hydrochloric acid and distilled water in sequence, and fully drying to obtain the heteroatom N/S doped porous carbon loaded graphene material 2.
(4) Preparing an electrocatalyst based on heteroatom-doped porous carbon of the MOFs: and (3) adding the heteroatom N/S doped porous carbon loaded graphene material 2 prepared in the step (3) into a high-energy planetary ball mill, adding a small amount of absolute ethyl alcohol, wherein the revolution speed of the ball mill is 45rpm, the rotation speed of the ball mill is 590rpm, performing ball milling until the material passes through a 800-mesh screen, passing the material through a high-speed centrifuge, performing centrifugal separation to remove the absolute ethyl alcohol, fully drying the solid, and preparing the heteroatom doped porous carbon based electrocatalyst material 2 based on MOFs.
Example 3:
(1) preparing nickel-based double organic ligands MOFs: to the direction ofA reflux device is carried in the reaction bottle, and high-purity N is introduced2Air is removed and then an appropriate amount of distilled water and 34 parts of nickel nitrate Ni (NO) are added in sequence3)2·6H2O, stirring until the solid is dissolved, then adding N, N-dimethylformamide, 18 parts of 4, 4-azopyridine and 16 parts of 4,4' -dithiodibenzoic acid in sequence, placing the reaction bottle in an oil bath pot, heating to 160 ℃, and dissolving the N-dimethylformamide in the N-dimethylformamide solution2Stirring at a constant speed under an atmosphere, heating for reflux reaction, observing the reaction process through a TLC (thin layer chromatography) method, cooling the solution to room temperature and filtering to remove N, N-dimethylformamide when 4,4' -dithiodibenzoic acid is completely reacted and a large amount of light yellow solid is produced, washing the obtained light yellow solid with a proper amount of distilled water and absolute ethyl alcohol in sequence, and fully drying to obtain the nickel-based diorganoligand MOFs complex 3.
(2) Preparing a nickel-based double organic ligand MOFs loaded graphene compound: adding a proper amount of distilled water into a reaction bottle, adding 32 parts of graphene and the nickel-based double organic ligand MOFs complex 3 prepared in the step (1), uniformly stirring, transferring the solution into a hydrothermal synthesis reaction kettle, placing the hydrothermal synthesis reaction kettle in a reaction kettle heating box, heating to 125 ℃, carrying out an activation reaction for 6 hours, removing the distilled water from the solution through a high-speed centrifuge after the reaction is finished, and fully drying a solid product to obtain the nickel-based double organic ligand MOFs loaded graphene complex 3.
(3) Preparing a heteroatom N/S doped porous carbon loaded graphene material: introducing high-purity N into an atmosphere resistance furnace2And (3) adding the nickel-based double organic ligands MOFs loaded graphene composite 3 prepared in the step (2), raising the temperature of an atmosphere resistance furnace to 830 ℃ at a rate of 8 ℃/min, keeping the temperature for calcining for 5h, cooling the calcined product to room temperature, washing the calcined product with proper amount of dilute hydrochloric acid and distilled water in sequence, and fully drying to obtain the heteroatom N/S doped porous carbon loaded graphene material 3.
(4) Preparing an electrocatalyst based on heteroatom-doped porous carbon of the MOFs: and (3) adding the heteroatom N/S doped porous carbon loaded graphene material 3 prepared in the step (3) into a high-energy planetary ball mill, adding a small amount of absolute ethyl alcohol, wherein the revolution speed of the ball mill is 50rpm, the rotation speed of the ball mill is 600rpm, performing ball milling until the material passes through a 800-mesh screen, passing the material through a high-speed centrifuge, performing centrifugal separation to remove the absolute ethyl alcohol, fully drying the solid, and preparing the heteroatom doped porous carbon based electrocatalyst material 3 based on MOFs.
Example 4:
(1) preparing nickel-based double organic ligands MOFs: a reflux device is carried in the reaction bottle, and high-purity N is introduced2Air is removed, then appropriate amounts of distilled water and 36 parts of nickel nitrate Ni (NO) are added in succession3)2·6H2O, stirring until the solid is dissolved, then adding N, N-dimethylformamide, 18 parts of 4, 4-azopyridine and 17 parts of 4,4' -dithiodibenzoic acid in sequence, placing the reaction bottle in an oil bath pot, heating to 160 ℃, and dissolving the N-dimethylformamide in the N-dimethylformamide solution2Stirring at a constant speed under an atmosphere, heating for reflux reaction, observing the reaction process through a TLC (thin layer chromatography) method, cooling the solution to room temperature and filtering to remove N, N-dimethylformamide when 4,4' -dithiodibenzoic acid is completely reacted and a large amount of light yellow solid is produced, washing the obtained light yellow solid with a proper amount of distilled water and absolute ethyl alcohol in sequence, and fully drying to obtain the nickel-based diorganoligand MOFs complex 4.
(2) Preparing a nickel-based double organic ligand MOFs loaded graphene compound: adding a proper amount of distilled water into a reaction bottle, adding 29 parts of graphene and the nickel-based double organic ligand MOFs complex 4 prepared in the step (1), uniformly stirring, transferring the solution into a hydrothermal synthesis reaction kettle, placing the hydrothermal synthesis reaction kettle in a reaction kettle heating box, heating to 125 ℃, carrying out an activation reaction for 6 hours, removing the distilled water from the solution through a high-speed centrifuge after the reaction is finished, and fully drying a solid product to obtain the nickel-based double organic ligand MOFs loaded graphene complex 4.
(3) Preparing a heteroatom N/S doped porous carbon loaded graphene material: introducing high-purity N into an atmosphere resistance furnace2Adding the nickel-based double-organic ligand MOFs prepared in the step (2) to load the graphene compound 4, heating the mixture in an atmosphere resistance furnace at a heating rate of 8 ℃/min to 840 ℃, keeping the temperature for calcining for 5 hours, cooling the calcined product to room temperature, washing the calcined product with proper amount of dilute hydrochloric acid and distilled water in sequence, and fully drying to obtain the heteroatom N/S doped porous carbon load stoneA graphene material 4.
(4) Preparing an electrocatalyst based on heteroatom-doped porous carbon of the MOFs: and (3) adding the heteroatom N/S doped porous carbon loaded graphene material 4 prepared in the step (3) into a high-energy planetary ball mill, adding a small amount of absolute ethyl alcohol, wherein the revolution speed of the ball mill is 60rpm, the rotation speed of the ball mill is 620rpm, performing ball milling until the material passes through a 800-mesh screen, passing the material through a high-speed centrifuge, performing centrifugal separation to remove the absolute ethyl alcohol, fully drying the solid, and preparing the heteroatom doped porous carbon based on MOFs (metal organic frameworks) electrocatalyst material 4.
Example 5:
(1) preparing nickel-based double organic ligands MOFs: a reflux device is carried in the reaction bottle, and high-purity N is introduced2Air was removed and then appropriate amounts of distilled water and 38 parts of nickel nitrate Ni (NO) were added in sequence3)2·6H2O, stirring until the solid is dissolved, then adding N, N-dimethylformamide, 20 parts of 4, 4-azopyridine and 20 parts of 4,4' -dithiodibenzoic acid in sequence, placing the reaction bottle in an oil bath pot, heating to 165 ℃, and dissolving in N2Stirring at a constant speed under an atmosphere, heating for reflux reaction, observing the reaction process through a TLC (thin layer chromatography) method, cooling the solution to room temperature and filtering to remove N, N-dimethylformamide when 4,4' -dithiodibenzoic acid is completely reacted and a large amount of light yellow solid is produced, washing the obtained light yellow solid with a proper amount of distilled water and absolute ethyl alcohol in sequence, and fully drying to obtain the nickel-based diorganoligand MOFs complex 5.
(2) Preparing a nickel-based double organic ligand MOFs loaded graphene compound: adding a proper amount of distilled water into a reaction bottle, adding 22 parts of graphene and the nickel-based double-organic-ligand MOFs complex 5 prepared in the step (1), uniformly stirring, transferring the solution into a hydrothermal synthesis reaction kettle, placing the hydrothermal synthesis reaction kettle in a reaction kettle heating box, heating to 130 ℃, carrying out activation reaction for 8 hours, removing the distilled water from the solution through a high-speed centrifuge after the reaction is finished, and fully drying a solid product to obtain the nickel-based double-organic-ligand MOFs loaded graphene complex 5.
(3) Preparing a heteroatom N/S doped porous carbon loaded graphene material: introducing high-purity N into an atmosphere resistance furnace2And (3) adding the nickel-based double organic ligands MOFs loaded graphene composite 5 prepared in the step (2), heating the temperature of an atmosphere resistance furnace to 850 ℃ at a rate of 10 ℃/min, keeping the temperature for calcining for 6h, cooling the calcined product to room temperature, washing the calcined product with proper amount of dilute hydrochloric acid and distilled water in sequence, and fully drying to obtain the heteroatom N/S doped porous carbon loaded graphene material 5.
(4) Preparing an electrocatalyst based on heteroatom-doped porous carbon of the MOFs: and (3) adding the heteroatom N/S doped porous carbon loaded graphene material 5 prepared in the step (3) into a high-energy planetary ball mill, adding a small amount of absolute ethyl alcohol, wherein the revolution speed of the ball mill is 60rpm, the rotation speed of the ball mill is 620rpm, performing ball milling until the material passes through a 800-mesh screen, passing the material through a high-speed centrifuge, performing centrifugal separation to remove the absolute ethyl alcohol, fully drying the solid, and preparing the heteroatom doped porous carbon based on MOFs (metal organic frameworks) electrocatalyst material 5.
To sum up, the MOFs-based heteroatom doped porous carbon electrocatalyst and the preparation method thereof are characterized in that 4, 4-azopyridine and 4,4' -dithiodibenzoic acid are used as organic ligands to synthesize the Ni-based dual organic ligand MOFs complex, the Ni-based dual organic ligand MOFs complex has the advantages of regular porous structure, adjustable pore size and good crystallinity, highly dispersed heteroatoms can be doped to adjust the local electronic structure of the catalyst, the calcination carbonization method is used for preparing the sulfur nickel compound-N/S doped porous carbon material, the transmission rate of electrons between the catalyst and the electrolyte in the electrolysis process and the formation of a large number of catalytic active sites can be promoted, the sulfur nickel compound has excellent conductivity and low oxygen evolution overpotential, the sulfur nickel compound-N/S doped porous carbon material has good electrocatalytic oxygen evolution performance, and the sulfur nickel compound-N/S doped porous carbon material is uniformly dispersed on the huge specific surface and pores of graphene by the hydrothermal synthesis activation method In the method, the phenomenon that the catalyst is agglomerated in an electrolyte to reduce the active sites of the catalyst is avoided, and a huge conductive network is formed between the interface of the sulfur-nickel compound-N/S doped porous carbon material and the graphene, so that the migration and transmission processes of electrons are promoted, and the electrocatalysis performance of the catalyst is improved.
Claims (5)
1. An electro-catalyst based on heteroatom doped porous carbon of MOFs and a preparation method thereof, comprises the following formula raw materials in parts by weight, and is characterized in that: 30-38 parts of nickel nitrate, 16-20 parts of 4, 4-azopyridine, 12-20 parts of 4,4' -dithiodibenzoic acid and 22-42 parts of graphene, and the preparation method comprises the following experimental medicines: distilled water, N-dimethylformamide, absolute ethyl alcohol and dilute hydrochloric acid.
2. The electrocatalyst of claim 1, and its preparation method, based on heteroatom-doped porous carbon of MOFs, wherein: the nickel nitrate is Ni (NO)3)2·6H2O。
3. The electrocatalyst of claim 1, and its preparation method, based on heteroatom-doped porous carbon of MOFs, wherein: the 4, 4-azopyridine and the 4,4' -dithiodibenzoic acid are both chemically pure.
4. The electrocatalyst of claim 1, and its preparation method, based on heteroatom-doped porous carbon of MOFs, wherein: the graphene is single-layer graphene powder, the sheet diameter is 0.5-5um, and the thickness is 0.8-1.2 nm.
5. The electrocatalyst of claim 2, and its preparation method, based on heteroatom-doped porous carbon of MOFs, wherein: the preparation method of the MOFs-based heteroatom doped porous carbon electrocatalyst comprises the following steps of:
(1) a reflux device is carried in the reaction bottle, and high-purity N is introduced2Removing air, then adding proper amount of distilled water and 30-38 parts of nickel nitrate Ni (NO) in turn3)2·6H2O, stirring until the solid is dissolved, then sequentially adding N, N-dimethylformamide, 16-20 parts of 4, 4-azopyridine and 12-20 parts of 4,4' -dithiodibenzoic acid, placing the reaction bottle in an oil bath pot, heating to 155-165 ℃ under the condition of N2Stirring at constant speed under atmosphere, heating, refluxing, observing reaction process by TLC thin layer chromatography, and reacting when 4And when the 4' -dithiodibenzoic acid is completely reacted and a large amount of light yellow solid is produced, cooling the solution to room temperature, filtering to remove N, N-dimethylformamide, washing the obtained light yellow solid by using a proper amount of distilled water and absolute ethyl alcohol in sequence, and fully drying to obtain the nickel-based diorganoligand MOFs.
(2) Adding a proper amount of distilled water into a reaction bottle, then adding 22-42 parts of graphene and the nickel-based diorganoligand MOFs prepared in the step (1), uniformly stirring, transferring the solution into a hydrothermal synthesis reaction kettle, placing the hydrothermal synthesis reaction kettle in a reaction kettle heating box, heating to 120-130 ℃, carrying out an activation reaction for 4-8h, removing the distilled water from the solution through a high-speed centrifuge after the reaction is finished, and fully drying the solid product to obtain the nickel-based diorganoligand MOFs loaded graphene composite.
(3) Introducing high-purity N into an atmosphere resistance furnace2And (3) adding the nickel-based double organic ligands MOFs load graphene composite prepared in the step (2), heating the temperature of the atmosphere resistance furnace to 820-850 ℃ at a heating rate of 5-10 ℃/min, keeping the temperature for calcining for 4-6h, cooling the calcined product to room temperature, washing the calcined product with proper amount of dilute hydrochloric acid and distilled water in sequence, and fully drying to obtain the heteroatom N/S doped porous carbon load graphene material.
(4) And (3) adding the heteroatom N/S doped porous carbon loaded graphene material prepared in the step (3) into a high-energy planetary ball mill, adding a small amount of absolute ethyl alcohol, wherein the revolution speed of the ball mill is 40-60rpm, the rotation speed is 580-620rpm, performing ball milling until the material passes through a 800-mesh screen, passing the material through a high-speed centrifuge, performing centrifugal separation to remove the absolute ethyl alcohol, and fully drying the solid to prepare the MOFs-based heteroatom doped porous carbon electrocatalyst.
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| CN112191273A (en) * | 2020-10-12 | 2021-01-08 | 中国科学技术大学 | High-entropy coordination polymer catalyst for oxygen production by electrolyzing water and preparation method and application thereof |
| CN114685809A (en) * | 2022-04-25 | 2022-07-01 | 黄金 | Nickel-based metal complex, electrocatalyst and preparation method of nickel-based metal complex |
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| CN111468164A (en) * | 2020-05-22 | 2020-07-31 | 青岛品泰新材料技术有限责任公司 | Preparation method and application of nitrogen-doped nano ZnS/graphene photocatalytic material |
| CN112191273A (en) * | 2020-10-12 | 2021-01-08 | 中国科学技术大学 | High-entropy coordination polymer catalyst for oxygen production by electrolyzing water and preparation method and application thereof |
| CN114685809A (en) * | 2022-04-25 | 2022-07-01 | 黄金 | Nickel-based metal complex, electrocatalyst and preparation method of nickel-based metal complex |
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