CN113802144A - Preparation method and application of single-hole covalent organic framework compound and metal composite hydrogen evolution catalyst - Google Patents
Preparation method and application of single-hole covalent organic framework compound and metal composite hydrogen evolution catalyst Download PDFInfo
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- CN113802144A CN113802144A CN202111142359.9A CN202111142359A CN113802144A CN 113802144 A CN113802144 A CN 113802144A CN 202111142359 A CN202111142359 A CN 202111142359A CN 113802144 A CN113802144 A CN 113802144A
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 148
- 239000013310 covalent-organic framework Substances 0.000 title claims abstract description 147
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 118
- 239000001257 hydrogen Substances 0.000 title claims abstract description 118
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 118
- 239000003054 catalyst Substances 0.000 title claims abstract description 100
- 239000002905 metal composite material Substances 0.000 title claims abstract description 80
- 238000002360 preparation method Methods 0.000 title claims abstract description 37
- 229910052751 metal Chemical class 0.000 claims abstract description 46
- 239000002184 metal Chemical class 0.000 claims abstract description 43
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- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
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- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 claims description 10
- 239000000376 reactant Substances 0.000 claims description 10
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- 238000001291 vacuum drying Methods 0.000 claims description 9
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 8
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- 238000007789 sealing Methods 0.000 claims description 8
- HFGASMNBMUOCGQ-UHFFFAOYSA-N 6-(5-cyanopyridin-2-yl)pyridine-3-carbonitrile Chemical compound N1=CC(C#N)=CC=C1C1=CC=C(C#N)C=N1 HFGASMNBMUOCGQ-UHFFFAOYSA-N 0.000 claims description 6
- 238000007872 degassing Methods 0.000 claims description 6
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- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 229910000403 monosodium phosphate Inorganic materials 0.000 claims description 5
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- 238000005086 pumping Methods 0.000 claims description 5
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 5
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- 230000035484 reaction time Effects 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 abstract description 2
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical class [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 abstract 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
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- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
-
- 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
-
- 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 belongs to the field of catalyst preparation, and discloses a preparation method of a single-hole covalent organic framework compound and metal composite hydrogen evolution catalyst, which comprises the steps of firstly preparing the single-hole covalent organic framework compound, then dissolving the single-hole covalent organic framework compound, sodium dodecyl sulfate and metal salt in ultrapure water, and the like to obtain the catalyst; another preparation method of the single-hole covalent organic framework compound and metal composite hydrogen evolution catalyst comprises the steps of firstly preparing the single-hole covalent organic framework compound, then dissolving the single-hole covalent organic framework compound and metal salt in ultrapure water, and the like to obtain the catalyst. The preparation method is simple and low in cost. The preparation method is suitable for preparing the single-hole covalent organic framework compound and metal composite hydrogen evolution catalyst, and the prepared single-hole covalent organic framework compound and metal composite hydrogen evolution catalyst are suitable for preparing hydrogen in industrial electrocatalytic hydrogen evolution reaction.
Description
Technical Field
The invention belongs to the field of catalyst preparation, relates to a preparation method of a hydrogen evolution catalyst, and particularly relates to a preparation method and application of a single-hole covalent organic framework compound and metal composite hydrogen evolution catalyst.
Background
The rapid development of new energy industry, electrocatalytic energy conversion and storage technology plays an important role in replacing fossil energy, reducing carbon emission and obtaining high value-added chemicals. The electrocatalyst is a special catalyst for catalyzing the decomposition of water into the reaction of hydrogen and oxygen in the electrolyzer, the hydrogen generated by the reaction can be stored and can be converted into electric energy again at any time, the only byproduct in the whole process is electrolyzed water, and the water can be recycled, so that the water can be used as the most green energy system. The excellent electrocatalytic material is a key factor for realizing the technology, and the metal platinum is the catalyst with the best catalytic effect in the hydrogen production process, because the metal platinum has the best H+Adsorption and desorption capacity, but because the platinum metal is deficient in resources in nature and expensive, the platinum metal as a catalyst is not well developed in industrial production. Therefore, designing and developing new electrocatalysts and improving the electrocatalytic performance thereof are urgent matters of electrocatalytic energy conversion at present.
Disclosure of Invention
The invention aims to provide a preparation method of a single-hole covalent organic framework compound and metal composite hydrogen evolution catalyst, so as to prepare the catalyst which can replace noble metal platinum and is applied to the electrocatalytic hydrogen evolution in industrial production, thereby reducing the cost of the electrocatalytic hydrogen evolution reaction.
In order to achieve the purpose, the technical method comprises the following steps:
a preparation method of a single-hole covalent organic framework compound and metal composite hydrogen evolution catalyst comprises the following steps:
(a1) preparation of a Mono-porous covalent organic framework Compound
Adding anhydrous zinc chloride and 2,2 '-bipyridine-5, 5' -dicarbonitrile into a container, pumping air out of the container, and sealing the container in a degassing state; the sealed container is subjected to gradient temperature rise at room temperature and then reacts, and after the temperature is cooled to room temperature, the container is opened to obtain a reactant A; grinding the reactant A into powder, and removing zinc chloride to obtain black powder B; washing the black powder B, and drying to obtain a single-hole covalent organic framework compound;
(a2) preparation of single-hole covalent organic framework compound and metal composite hydrogen evolution catalyst
A single-hole covalent organic framework compound, sodium dodecyl sulfate and NiCl2·6H2O、CoCl2·6H2O、CuCl2·2H2Dissolving O, palladium acetate and chloroplatinic acid in ultrapure water to form a uniform solution C, then dripping a sodium hydroxide aqueous solution to form a uniform solution D, and then adding sodium dihydrogen phosphate to form a uniform solution E; and transferring the uniform solution E into a polytetrafluoroethylene-lined stainless steel autoclave, reacting to obtain a single-hole covalent organic framework compound and metal cluster composite material, removing useless ions, and drying in vacuum to obtain the single-hole covalent organic framework compound and metal composite hydrogen evolution catalyst.
As a limitation: in the step (a1), the container is pumped by a vacuum pump and kept for 5-10 min; the temperature of the sealed container is raised in a tubular furnace, and the temperature is raised from room temperature to 400 ℃ and 600 ℃ in a gradient manner and is kept for 30-40 h; the zinc chloride is removed by washing with deionized water for at least three times, stirring with dilute acid at room temperature for 10-20h to further remove zinc chloride, and filtering; the leaching mode is that the deionized water is used for leaching at least three times, and then the organic solvent is used for leaching at least three times; the drying mode is that the black powder B is put into a vacuum oven and dried for 20-30h at the temperature of 100-150 ℃.
As a further limitation: the diluted acid in the step (a1) is 0.1mol/L hydrochloric acid or sulfuric acid; the organic solvent is at least one of acetone, tetrahydrofuran and dichloromethane.
As another limitation: the stirring time required for forming the uniform solution C in the step (a2) is 2-5 h; the stirring time for forming the uniform solution D is 30-60 min; the stirring time for forming the uniform solution E is 30min-60 min; the reaction temperature of the uniform solution E in a polytetrafluoroethylene lining stainless steel autoclave is 80-120 ℃, and the reaction time is 12-48 h; the mode of removing useless ions is that the obtained single-hole covalent organic framework compound and the metal cluster composite material are respectively cleaned for at least 5 times by ultrapure water and alcohol; the vacuum drying mode is vacuum drying at 30-80 deg.C for 24 hr.
As a further limitation: step (a2) of single-well covalent organic framework Compound, NiCl2·6H2O、CoCl2·6H2O、CuCl2·2H2The molar ratio of O, palladium acetate and chloroplatinic acid is 10-12:1:1:1:1, the concentration of sodium dodecyl sulfate is 15-20mmol/L, the concentration of sodium hydroxide aqueous solution is 1-2 mmol/L, and the concentration of sodium dihydrogen phosphate solution is 0.1-0.5 mmol/L; the alcohol used for removing useless ions is one of methanol, ethanol and isopropanol.
A preparation method of a single-hole covalent organic framework compound and metal composite hydrogen evolution catalyst comprises the following steps:
(b1) preparation of a Mono-porous covalent organic framework Compound
Adding anhydrous zinc chloride and 2,2 '-bipyridine-5, 5' -dicarbonitrile into a container, pumping air out of the container, and sealing the container in a degassing state; the sealed container is subjected to gradient temperature rise at room temperature and then reacts, and after the temperature is cooled to room temperature, the container is opened to obtain a reactant A; grinding the reactant A into powder, and removing zinc chloride to obtain black powder B; washing the black powder B, and drying to obtain a single-hole covalent organic framework compound;
(b2) preparation of single-hole covalent organic framework compound and metal composite hydrogen evolution catalyst
A single-hole covalent organic framework compound, NiCl2·6H2O、CoCl2·6H2O、CuCl2·2H2Dissolving O, palladium acetate and chloroplatinic acid in ultrapure water, reacting to obtain the single-hole covalent organic framework compound and metal monoatomic composite material, removing useless ions, and drying in vacuum to obtain the single-hole covalent organic framework compound and metal composite hydrogen evolution catalyst.
As a limitation: in the step (b1), the container is pumped by a vacuum pump and kept for 5-10 min; the temperature of the sealed container is raised in a tubular furnace, and the temperature is raised from room temperature to 400 ℃ and 600 ℃ in a gradient manner and is kept for 30-40 h; the zinc chloride is removed by washing with deionized water for at least three times, stirring with dilute acid at room temperature for 10-20h to further remove zinc chloride, and filtering; the leaching mode is that the deionized water is used for leaching at least three times, and then the organic solvent is used for leaching at least three times; the drying mode is that the black powder B is put into a vacuum oven and dried for 20-30h at the temperature of 100-150 ℃.
As a further limitation: the diluted acid in the step (b1) is 0.1mol/L hydrochloric acid or sulfuric acid; the organic solvent is one or two of acetone, tetrahydrofuran and dichloromethane.
As another limitation: step (b2) of single-well covalent organic framework Compound, NiCl2·6H2O、CoCl2·6H2O、CuCl2·2H2The molar ratio of O, palladium acetate and chloroplatinic acid is 1:1-1.5:1-1.5:1-1.5:1-1.5: 1-1.5; dissolving in ultrapure water at 40-80 deg.C, and stirring for 2-5 hr; removing useless ions by respectively cleaning the obtained single-hole covalent organic framework compound and the metal single-atom composite material for at least 5 times by using ultrapure water and alcohol, wherein the alcohol is one of methanol, ethanol and isopropanol; the vacuum drying mode is 30-8Vacuum drying at 0 deg.C for 24 h.
The invention also provides an application of the single-hole covalent organic framework compound and the metal composite hydrogen evolution catalyst prepared by the preparation method of the single-hole covalent organic framework compound and the metal composite hydrogen evolution catalyst, and the single-hole covalent organic framework compound and the metal composite hydrogen evolution catalyst are used for preparing hydrogen in industrial electrocatalytic hydrogen evolution reaction.
Due to the adoption of the scheme, compared with the prior art, the invention has the beneficial effects that:
(1) according to the preparation method of the single-hole covalent organic framework compound and metal composite hydrogen evolution catalyst, the coordination sites are designed on the surface of the single-hole covalent organic framework compound, the coordination groups are used as 'claws' for capturing and anchoring the mononuclear metal precursor, and then stable monoatomic atoms are formed by utilizing the strong interaction between the metal monoatomic atoms and the coordination sites, so that the migration and agglomeration of the metal monoatomic atoms are prevented, and the single-hole covalent organic framework compound and metal monoatomic composite catalyst is formed; the prepared single-hole covalent organic framework compound and metal single-atom composite hydrogen evolution catalyst has low content of platinum metal in single atoms, greatly reduces the content of noble metal compared with 20 percent of commercial platinum carbon, and reduces the cost of hydrogen evolution;
(2) according to the single-hole covalent organic framework compound and metal cluster composite hydrogen evolution catalyst provided by the invention, the modification of the metal cluster increases the active sites of hydrogen evolution reaction, a good synergistic effect is formed with the single-hole covalent organic framework compound, a good hydrogen evolution effect is achieved, the platinum metal content in the metal cluster is low, the content of noble metal is greatly reduced compared with 20% of commercial platinum carbon, and the hydrogen evolution cost is reduced.
The preparation method is suitable for preparing the single-hole covalent organic framework compound and metal composite hydrogen evolution catalyst, and the prepared single-hole covalent organic framework compound and metal composite hydrogen evolution catalyst are suitable for preparing hydrogen in industrial electrocatalytic hydrogen evolution reaction.
Drawings
The invention is described in further detail below with reference to the figures and the embodiments.
FIG. 1 is a schematic structural diagram of a single-pore covalent organic framework compound and metal composite hydrogen evolution catalyst in example 1 of the present invention;
FIG. 2 is a chart of the infrared spectrum of a single-hole covalent organic framework compound of example 1 of the present invention;
FIG. 3 is a nitrogen adsorption/desorption isotherm of a single-pore covalent organic framework compound of example 1 of the present invention;
FIG. 4 is a plot of the pore size distribution of a single-pore covalent organic framework compound of example 1 of the present invention;
FIG. 5 is a nitrogen adsorption/desorption isotherm of a single-pore covalent organic framework compound and a metal composite hydrogen evolution catalyst according to example 1 of the present invention;
FIG. 6 is a plot of the pore size distribution of a single-pore covalent organic framework compound and metal composite hydrogen evolution catalyst of example 1 of the present invention;
FIG. 7 is an XPS plot of a single-pore covalent organic framework compound and metal complex hydrogen evolution catalyst of example 1 of the present invention;
FIG. 8 is a linear scan plot of the electrochemical hydrogen evolution performance of the single-pore covalent organic framework compound and metal composite hydrogen evolution catalyst of example 1 of the present invention;
FIG. 9 is a Tafel plot of the electrochemical hydrogen evolution performance of the single-pore covalent organic framework compound and metal composite hydrogen evolution catalyst of example 1 of the present invention;
FIG. 10 is a schematic structural diagram of a single-pore covalent organic framework compound and metal composite hydrogen evolution catalyst according to example 7 of the present invention;
FIG. 11 is a nitrogen adsorption/desorption isotherm of a single-pore covalent organic framework compound and a metal composite hydrogen evolution catalyst of example 7 of the present invention;
FIG. 12 is a plot of the pore size distribution of a single-pore covalent organic framework compound and metal composite hydrogen evolution catalyst of example 7 of the present invention;
FIG. 13 is an XPS plot of a single-pore covalent organic framework compound and metal complex hydrogen evolution catalyst of example 7 of the present invention;
FIG. 14 is a linear scan plot of the electrochemical hydrogen evolution performance of the single-pore covalent organic framework compound and metal composite hydrogen evolution catalyst of example 7 of the present invention;
fig. 15 is a tafel plot of the electrochemical hydrogen evolution performance of the single-pore covalent organic framework compound and metal composite hydrogen evolution catalyst of example 7 of the present invention.
Detailed Description
The present invention is further described with reference to the following examples, but it should be understood by those skilled in the art that the present invention is not limited to the following examples, and any modifications and equivalent changes based on the specific examples of the present invention are within the scope of the claims of the present invention.
Examples 1-6 preparation of a Single-pore covalent organic framework Compound and Metal composite Hydrogen evolution catalyst
Examples 1 to 6 are a method for preparing a single-pore covalent organic framework compound and metal composite hydrogen evolution catalyst, respectively, and the process parameters for preparing the single-pore covalent organic framework compound and metal composite hydrogen evolution catalyst are shown in table 1 and are carried out according to the following steps:
(a1) preparation of a Mono-porous covalent organic framework Compound
Anhydrous zinc chloride and 2,2 '-bipyridine-5, 5' -dicarbonitrile in a ratio of 1:10 mol ratio, and pumping air from the ampoule bottle by a vacuum pump for 5-10 min; then sealing the ampoule bottle in a degassing state by using an ampoule bottle sealing machine; placing the sealed ampoule bottle in a tube furnace, heating to 400-; grinding the reactant A into powder, washing the powder for at least three times by using deionized water to remove zinc chloride, stirring the powder for 10 to 20 hours at room temperature by using 0.1mol/L diluted acid to further remove the zinc chloride, and filtering the solution to obtain black powder B; leaching the black powder B with deionized water for at least three times, leaching with one or a combination of two of organic solvents for at least three times, placing into a vacuum oven, and drying at the temperature of 100-;
(a2) preparation of single-hole covalent organic framework compound and metal composite hydrogen evolution catalyst
A single-hole covalent organic framework compound and dodecyl sulfurSodium salt, NiCl2·6H2O、CoCl2·6H2O、CuCl2·2H2Dissolving O, palladium acetate and chloroplatinic acid in ultrapure water, stirring for 2-5h to form a uniform solution C, slowly dripping a sodium hydroxide aqueous solution, stirring for 30-60 min to form a uniform solution D, then adding sodium dihydrogen phosphate, and stirring for 30-60 min to form a uniform solution E; and transferring the uniform solution E into a polytetrafluoroethylene-lined stainless steel autoclave, heating to 80-120 ℃, reacting for 12-48h to obtain a single-hole covalent organic framework compound and metal cluster composite material, respectively cleaning the obtained single-hole covalent organic framework compound and metal cluster composite material with ultrapure water and alcohol for at least 5 times to remove useless ions, and then carrying out vacuum drying for 24h at 30-80 ℃ to obtain the single-hole covalent organic framework compound and metal composite hydrogen evolution catalyst.
In examples 1 to 6, the diluted acid is hydrochloric acid or sulfuric acid, the organic solvent is at least one of acetone, tetrahydrofuran, and dichloromethane, and the alcohol used for removing the useless ions is one of methanol, ethanol, and isopropanol.
Table 1 examples 1-6 preparation of single pore covalent organic framework compounds with metal composite hydrogen evolution catalysts
Examples 7-12 preparation of Single-pore covalent organic framework Compound and Metal composite Hydrogen evolution catalyst
Examples 7 to 12 are a method for preparing a single-pore covalent organic framework compound and metal composite hydrogen evolution catalyst, respectively, and the process parameters for preparing the single-pore covalent organic framework compound and metal composite hydrogen evolution catalyst are shown in table 2 and are carried out according to the following steps:
(b1) preparation of a Mono-porous covalent organic framework Compound
Adding anhydrous zinc chloride and 2,2 '-bipyridine-5, 5' -dicarbonitrile into an ampoule bottle according to a molar ratio of 1:10, and performing vacuum pump suction on the ampoule bottle for 5-10 min; then sealing the ampoule bottle in a degassing state by using an ampoule bottle sealing machine; placing the sealed ampoule bottle in a tube furnace, heating to 400-; grinding the reactant A into powder, washing the powder for at least three times by using deionized water to remove zinc chloride, stirring the powder for 10 to 20 hours at room temperature by using 0.1mol/L diluted acid to further remove the zinc chloride, and filtering the solution to obtain black powder B; leaching the black powder B with deionized water for at least three times, leaching with an organic solvent for at least three times, placing into a vacuum oven, and drying at the temperature of 100-;
(b2) preparation of single-hole covalent organic framework compound and metal composite hydrogen evolution catalyst
A single-hole covalent organic framework compound, NiCl2·6H2O、CoCl2·6H2O、CuCl2·2H2Dissolving O, palladium acetate and chloroplatinic acid in ultrapure water, stirring for 2-5h at 40-80 ℃ to obtain a single-hole covalent organic framework compound and metal monoatomic composite material, respectively cleaning the obtained single-hole covalent organic framework compound and metal monoatomic composite material with ultrapure water and alcohol for at least 5 times to remove useless ions, and then carrying out vacuum drying for 24h at 30-80 ℃ to obtain the single-hole covalent organic framework compound and metal composite hydrogen evolution catalyst.
In examples 7 to 12, the diluted acid is hydrochloric acid or sulfuric acid, the organic solvent is at least one of acetone, tetrahydrofuran and dichloromethane, and the method for removing the useless ions is that the alcohol is one of methanol, ethanol and isopropanol.
Table 2 examples 7-12 preparation of single-pore covalent organic framework compounds with metal composite hydrogen evolution catalysts
Example 13 use of a Single-pore covalent organic framework Compound with Metal composite Hydrogen evolution catalyst
The embodiment provides an application of a single-hole covalent organic framework compound and a metal composite hydrogen evolution catalyst prepared by using the preparation method of the single-hole covalent organic framework compound and the metal composite hydrogen evolution catalyst in the embodiments 1 to 6, and an application of the single-hole covalent organic framework compound and the metal composite hydrogen evolution catalyst prepared by using the preparation method of the single-hole covalent organic framework compound and the metal composite hydrogen evolution catalyst in the embodiments 7 to 12, which are used for preparing hydrogen by using the catalyst in an industrial electrocatalytic hydrogen evolution reaction. The structures of the single-pore covalent organic framework compounds prepared in examples 2-12 were similar to those of the single-pore covalent organic framework compound prepared in example 1. The structures of the single-hole covalent organic framework compound and the metal composite hydrogen evolution catalyst prepared in the embodiments 2 to 6 are similar to those of the single-hole covalent organic framework compound and the metal composite hydrogen evolution catalyst prepared in the embodiment 1. The structures of the single-hole covalent organic framework compound and the metal composite hydrogen evolution catalyst prepared in the embodiments 8 to 12 are similar to those of the single-hole covalent organic framework compound and the metal composite hydrogen evolution catalyst prepared in the embodiment 7.
A single-pore covalent organic framework compound, i.e., BPY-CTF; the composite material is characterized in that a single-hole covalent organic framework compound is compounded with metal copper to form BPY-CTF @ Cu-MC, the composite material is compounded with metal cobalt to form BPY-CTF @ Co-MC, the composite material is compounded with metal nickel to form BPY-CTF @ Ni-MC, the composite material is compounded with metal platinum to form BPY-CTF @ Pt-MC, and the composite material is compounded with metal palladium to form BPY-CTF @ Pd-MC; the single-hole covalent organic framework compound is BPY-CTF @ Cu after being compounded with metal copper ions2+The single-hole covalent organic framework compound is BPY-CTF @ Co after being compounded with metal cobalt ions2+The single-hole covalent organic framework compound is BPY-CTF @ Ni after being compounded with metal nickel ions2+Single-hole covalent organic frameThe complex of the frame compound and the metal platinum ion is BPY-CTF @ Pt2The single-hole covalent organic framework compound is compounded with metal palladium ions to form BPY-CTF @ Pd2+。
The structure of the single-hole covalent organic framework compound and metal composite hydrogen evolution catalyst prepared in example 1 is shown in fig. 1, wherein Culster represents a metal cluster; the infrared spectrum of the single-hole covalent organic framework compound prepared in example 1 is shown in fig. 2, the nitrogen adsorption/desorption isotherm is shown in fig. 3, and the pore size distribution curve is shown in fig. 4; the nitrogen adsorption/desorption isotherms of the single-pore covalent organic framework compound and the metal composite hydrogen evolution catalyst are shown in fig. 5, the pore size distribution curve is shown in fig. 6, and it can be known from fig. 3, fig. 4, fig. 5 and fig. 6 that when the metal cluster is introduced into the single-pore covalent organic framework compound, the BET specific surface areas of the obtained single-pore covalent organic framework compound and the metal composite hydrogen evolution catalyst are both reduced, which indicates that the metal cluster is successfully anchored on the single-pore covalent organic framework compound, and simultaneously the types of the adsorption/desorption isotherms of the single-pore covalent organic framework compound and the metal composite hydrogen evolution catalyst are not changed, and the pore size distribution diagram is not changed, which indicates that the introduction of the metal cluster does not affect the pore structure of the single-pore covalent organic framework compound; the XPS diagram of the single-hole covalent organic framework compound and the metal composite hydrogen evolution catalyst is shown in FIG. 7, and it can be seen that C, N, O metal elements which correspond to the metal elements exist; electrochemical tests were carried out at the electrochemical workstation of Zennium Pro using a three-electrode system consisting of a working electrode (platinum carbon electrode), a reference electrode (Ag/AgCl electrode) and a counter electrode (platinum sheet), the standard hydrogen potential being converted using the following formula: e (rhe) ═ e (ag)/AgCl) +0.197V +0.0591 × pH, pH in this system was 0, scan rate of linear scan test (LSV) was 5mV/s, overpotential and tafel slope were calculated from data of LSV, frequency range of alternating current impedance was 300mHz-100KHz, amplitude was 5mV, material stability was tested by cyclic voltammetry, potential range was 0.1-0.4V, scan rate was 50mV/s, 3000 cycles were cycled to obtain linear scan curve of electrochemical hydrogen evolution performance of the single-pore covalent organic framework compound and the metal composite hydrogen evolution catalyst as shown in fig. 8, tafel curve of electrochemical hydrogen evolution performance as shown in fig. 9, it was known that the single-pore covalent organic framework compound exhibited overpotential of 345mV by pi-conjugated structure and high nitrogen content, and the overpotential gradually decreased as the metal cluster was modified, overpotential is shown in table 3, and shows that modification of the metal cluster increases active sites of hydrogen evolution reaction, and forms good synergistic effect with the single-hole covalent organic framework compound.
TABLE 3 EXAMPLE 1 overpotential of a single-pore covalent organic framework compound and a metal complex hydrogen evolution catalyst
The structure of the single-hole covalent organic framework compound and the metal composite hydrogen evolution catalyst prepared in example 7 is shown in fig. 10, wherein M represents a metal single atom; the nitrogen adsorption/desorption isotherm of the single-pore covalent organic framework compound and the metal composite hydrogen evolution catalyst prepared in example 7 is shown in fig. 11, the pore size distribution curve is shown in fig. 12, and it can be known from fig. 3, 4, 11 and 12 that when metal ions are introduced into the single-pore covalent organic framework compound, BET specific surface areas of the obtained single-pore covalent organic framework compound and the metal composite hydrogen evolution catalyst are both reduced, which indicates that the metal ions are successfully anchored on the single-pore covalent organic framework compound, and simultaneously the types of adsorption/desorption isotherms of the single-pore covalent organic framework compound and the metal composite hydrogen evolution catalyst are not changed, and the pore size distribution diagram is not changed, which indicates that the introduction of the metal ions does not affect the pore structure of the single-pore covalent organic framework compound; the XPS diagram of the single-hole covalent organic framework compound and the metal composite hydrogen evolution catalyst is shown in FIG. 13, and it can be seen that C, N, O corresponding metal elements exist and the metal is non-zero-valent, so that the single-hole covalent organic framework compound and the metal composite hydrogen evolution catalyst are proved to be single-atom catalysts; electrochemical tests were carried out at the electrochemical workstation of Zennium Pro using a three-electrode system consisting of a working electrode (platinum carbon electrode), a reference electrode (Ag/AgCl electrode) and a counter electrode (platinum sheet), the standard hydrogen potential being converted using the following formula: e (rhe) ═ e (ag)/AgCl) +0.197V +0.0591 × pH, pH 0 in this system, scan rate of linear sweep test (LSV) was 5mV/s, overpotential and tafel slope were calculated from data of LSV, frequency range of ac impedance was 300mHz-100KHz, amplitude was 5mV, material stability was tested by cyclic voltammetry, potential range was 0.1-0.4V, scan rate was 50mV/s, 3000 cycles were cycled to obtain linear sweep curve of electrochemical hydrogen evolution performance of the single-pore covalent organic framework compound and the metal composite hydrogen evolution catalyst as shown in fig. 14, tafel curve of electrochemical hydrogen evolution performance as shown in fig. 15, it was found that, after modification of the single-pore covalent organic framework compound by a metal single atom, overpotential was significantly decreased as shown in table 4, overpotential of 20% commercial platinum carbon catalyst was 50mV, the atom size has obvious influence on the catalytic performance, and the single-hole covalent organic framework compound and the metal single-atom composite hydrogen evolution catalyst can expose more catalytic edges and realize the maximum atom utilization rate.
Table 4 example 7 overpotential of single-pore covalent organic framework compound and metal complex hydrogen evolution catalyst
Claims (10)
1. A preparation method of a single-hole covalent organic framework compound and metal composite hydrogen evolution catalyst is characterized by comprising the following steps:
(a1) preparation of a Mono-porous covalent organic framework Compound
Adding anhydrous zinc chloride and 2,2 '-bipyridine-5, 5' -dicarbonitrile into a container, pumping air out of the container, and sealing the container in a degassing state; the sealed container is subjected to gradient temperature rise at room temperature and then reacts, and after the temperature is cooled to room temperature, the container is opened to obtain a reactant A; grinding the reactant A into powder, and removing zinc chloride to obtain black powder B; washing the black powder B, and drying to obtain a single-hole covalent organic framework compound;
(a2) preparation of single-hole covalent organic framework compound and metal composite hydrogen evolution catalyst
A single-hole covalent organic framework compound, sodium dodecyl sulfate and NiCl2·6H2O、CoCl2·6H2O、CuCl2·2H2Dissolving O, palladium acetate and chloroplatinic acid in ultrapure water to form a uniform solution C, then dripping a sodium hydroxide aqueous solution to form a uniform solution D, and then adding sodium dihydrogen phosphate to form a uniform solution E; and transferring the uniform solution E into a polytetrafluoroethylene-lined stainless steel autoclave, reacting to obtain a single-hole covalent organic framework compound and metal cluster composite material, removing useless ions, and drying in vacuum to obtain the single-hole covalent organic framework compound and metal composite hydrogen evolution catalyst.
2. The method for preparing the single-hole covalent organic framework compound and metal composite hydrogen evolution catalyst according to claim 1, wherein in the step (a1), the container is pumped by a vacuum pump and kept for 5-10 min; the temperature of the sealed container is raised in a tubular furnace, the temperature is raised from room temperature to 400 + 600 ℃, and the temperature is kept for 30-40 h; the zinc chloride is removed by washing with deionized water for at least three times, stirring with dilute acid at room temperature for 10-20h to further remove zinc chloride, and filtering; the leaching mode is that the deionized water is used for leaching at least three times, and then the organic solvent is used for leaching at least three times; the drying mode is that the black powder B is put into a vacuum oven and dried for 20-30h at the temperature of 100-150 ℃.
3. The method for preparing a single-pore covalent organic framework compound and metal composite hydrogen evolution catalyst according to claim 2, wherein the diluted acid in the step (a1) is 0.1mol/L hydrochloric acid or sulfuric acid; the organic solvent is at least one of acetone, tetrahydrofuran and dichloromethane.
4. The method for preparing a single-pore covalent organic framework compound and metal composite hydrogen evolution catalyst according to any one of claims 1 to 3, wherein the stirring time required for forming the uniform solution C in the step (a2) is 2 to 5 hours; the stirring time for forming the uniform solution D is 30-60 min; the stirring time for forming the uniform solution E is 30min-60 min; the reaction temperature of the uniform solution E in a polytetrafluoroethylene-lined stainless steel autoclave is 80-120 ℃, and the reaction time is 12-48 h; the mode of removing useless ions is that the obtained single-hole covalent organic framework compound and the metal cluster composite material are respectively cleaned for at least 5 times by ultrapure water and alcohol; the vacuum drying mode is vacuum drying at 30-80 deg.C for 24 hr.
5. The method for preparing a single-pore covalent organic framework compound and metal composite hydrogen evolution catalyst according to claim 4, wherein the single-pore covalent organic framework compound and NiCl are obtained in the step (a2)2·6H2O、CoCl2·6H2O、CuCl2·2H2The molar ratio of O, palladium acetate and chloroplatinic acid is 10-12:1:1:1:1, the concentration of sodium dodecyl sulfate is 15-20mmol/L, the concentration of sodium hydroxide aqueous solution is 1-2 mmol/L, and the concentration of sodium dihydrogen phosphate solution is 0.1-0.5 mmol/L; the alcohol used for removing useless ions is one of methanol, ethanol and isopropanol.
6. A preparation method of a single-hole covalent organic framework compound and metal composite hydrogen evolution catalyst is characterized by comprising the following steps:
(b1) preparation of a Mono-porous covalent organic framework Compound
Adding anhydrous zinc chloride and 2,2 '-bipyridine-5, 5' -dicarbonitrile into a container, pumping air out of the container, and sealing the container in a degassing state; the sealed container is subjected to gradient temperature rise at room temperature and then reacts, and after the temperature is cooled to room temperature, the container is opened to obtain a reactant A; grinding the reactant A into powder, and removing zinc chloride to obtain black powder B; washing the black powder B, and drying to obtain a single-hole covalent organic framework compound;
(b2) preparation of single-hole covalent organic framework compound and metal composite hydrogen evolution catalyst
A single-hole covalent organic framework compound, NiCl2·6H2O、CoCl2·6H2O、CuCl2·2H2Dissolving O, palladium acetate and chloroplatinic acid in ultrapure water, and reactingAnd (3) obtaining the single-hole covalent organic framework compound and metal monoatomic composite material, removing useless ions, and drying in vacuum to obtain the single-hole covalent organic framework compound and metal composite hydrogen evolution catalyst.
7. The method for preparing the single-hole covalent organic framework compound and metal composite hydrogen evolution catalyst according to claim 6, wherein in the step (b1), the container is pumped by a vacuum pump and kept for 5-10 min; the temperature of the sealed container is raised in a tubular furnace, the temperature is raised from room temperature to 400 + 600 ℃, and the temperature is kept for 30-40 h; the zinc chloride is removed by washing with deionized water for at least three times, stirring with dilute acid at room temperature for 10-20h to further remove zinc chloride, and filtering; the leaching mode is that the deionized water is used for leaching at least three times, and then the organic solvent is used for leaching at least three times; the drying mode is that the black powder B is put into a vacuum oven and dried for 20-30h at the temperature of 100-150 ℃.
8. The method for preparing a single pore covalent organic framework compound and metal composite hydrogen evolution catalyst according to claim 7, wherein the diluted acid in the step (b1) is 0.1mol/L hydrochloric acid or sulfuric acid; the organic solvent is one or two of acetone, tetrahydrofuran and dichloromethane.
9. The method for preparing a single-pore covalent organic framework compound and metal composite hydrogen evolution catalyst according to any one of claims 6 to 8, wherein in the step (b2), the single-pore covalent organic framework compound and NiCl are adopted2·6H2O、CoCl2·6H2O、CuCl2·2H2The molar ratio of O, palladium acetate and chloroplatinic acid is 1:1-1.5:1-1.5:1-1.5:1-1.5: 1-1.5; dissolving in ultrapure water at 40-80 deg.C, and stirring for 2-5 hr; removing useless ions by respectively cleaning the obtained single-hole covalent organic framework compound and the metal single-atom composite material for at least 5 times by using ultrapure water and alcohol, wherein the alcohol is one of methanol, ethanol and isopropanol; the vacuum drying mode is vacuum drying at 30-80 deg.C for 24 hr.
10. Use of a single-pore covalent organic framework compound and metal composite hydrogen evolution catalyst prepared by the method of preparing a single-pore covalent organic framework compound and metal composite hydrogen evolution catalyst according to any one of claims 1 to 9, characterized in that the single-pore covalent organic framework compound and metal composite hydrogen evolution catalyst are used in industrial electrocatalytic hydrogen evolution reactions for the preparation of hydrogen.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014107726A1 (en) * | 2013-01-07 | 2014-07-10 | Northeastern University | Non-noble metal catalysts for oxygen depolarized cathodes and their uses |
| US20170130349A1 (en) * | 2015-11-10 | 2017-05-11 | Indian Educational and Research Institute | Covalent organic frameworks as porous supports for non-noble metal based water splitting electrocatalysts |
| CN110075902A (en) * | 2019-05-22 | 2019-08-02 | 浙江工业大学 | A kind of deficiency covalent triazine frame material derived material catalyst and its preparation method and application |
| CN110116025A (en) * | 2019-05-30 | 2019-08-13 | 河北科技大学 | Covalent triazine class framework compound and MoS2The preparation method of compound liberation of hydrogen catalyst and the application of liberation of hydrogen catalyst |
| CN110479379A (en) * | 2019-08-28 | 2019-11-22 | 浙江工业大学 | A kind of covalent organic frame material catalyst and its preparation method and application based on load Ru nano particle |
| CN111635523A (en) * | 2020-06-03 | 2020-09-08 | 河北科技大学 | Two-dimensional covalent organic framework material with trimeric quinazoline as junction, preparation method and application thereof |
-
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014107726A1 (en) * | 2013-01-07 | 2014-07-10 | Northeastern University | Non-noble metal catalysts for oxygen depolarized cathodes and their uses |
| US20170130349A1 (en) * | 2015-11-10 | 2017-05-11 | Indian Educational and Research Institute | Covalent organic frameworks as porous supports for non-noble metal based water splitting electrocatalysts |
| CN110075902A (en) * | 2019-05-22 | 2019-08-02 | 浙江工业大学 | A kind of deficiency covalent triazine frame material derived material catalyst and its preparation method and application |
| CN110116025A (en) * | 2019-05-30 | 2019-08-13 | 河北科技大学 | Covalent triazine class framework compound and MoS2The preparation method of compound liberation of hydrogen catalyst and the application of liberation of hydrogen catalyst |
| CN110479379A (en) * | 2019-08-28 | 2019-11-22 | 浙江工业大学 | A kind of covalent organic frame material catalyst and its preparation method and application based on load Ru nano particle |
| CN111635523A (en) * | 2020-06-03 | 2020-09-08 | 河北科技大学 | Two-dimensional covalent organic framework material with trimeric quinazoline as junction, preparation method and application thereof |
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