CN114808027A - N-MoS with efficient electro-catalytic hydrogen evolution performance 2 /COF-C 4 N composite catalyst and preparation method thereof - Google Patents
N-MoS with efficient electro-catalytic hydrogen evolution performance 2 /COF-C 4 N composite catalyst and preparation method thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 45
- 239000002131 composite material Substances 0.000 title claims abstract description 38
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- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 25
- 239000001257 hydrogen Substances 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910052982 molybdenum disulfide Inorganic materials 0.000 claims abstract description 27
- 239000006185 dispersion Substances 0.000 claims abstract description 25
- 239000000463 material Substances 0.000 claims abstract description 18
- 239000013310 covalent-organic framework Substances 0.000 claims abstract description 11
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- 238000003786 synthesis reaction Methods 0.000 claims abstract description 5
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 239000007788 liquid Substances 0.000 claims description 16
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 12
- 239000012265 solid product Substances 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 10
- 239000007795 chemical reaction product Substances 0.000 claims description 9
- -1 cyclohexane octahydrate Chemical compound 0.000 claims description 7
- 239000012153 distilled water Substances 0.000 claims description 7
- 238000009210 therapy by ultrasound Methods 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 6
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 5
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 239000013078 crystal Substances 0.000 claims description 5
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- PUXBEKLSMBVFNW-UHFFFAOYSA-N triphenylene-2,3,6,7,10,11-hexamine hexahydrochloride Chemical compound Cl.Cl.Cl.Cl.Cl.Cl.NC1=CC=2C3=CC(=C(C=C3C3=CC(=C(C=C3C2C=C1N)N)N)N)N PUXBEKLSMBVFNW-UHFFFAOYSA-N 0.000 claims description 5
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- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims 1
- PCNDJXKNXGMECE-UHFFFAOYSA-N Phenazine Natural products C1=CC=CC2=NC3=CC=CC=C3N=C21 PCNDJXKNXGMECE-UHFFFAOYSA-N 0.000 abstract 1
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
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- 238000001035 drying Methods 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 238000005868 electrolysis reaction Methods 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- 229910052750 molybdenum Inorganic materials 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
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- 230000003647 oxidation Effects 0.000 description 1
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
- C25B11/095—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 at least one of the compounds being organic
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
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Abstract
The invention relates to the technical field of electrocatalytic hydrogen evolution and the technical field of catalyst preparation. The invention discloses N-MoS with efficient electrocatalytic hydrogen evolution performance 2 /COF‑C 4 An N composite catalyst and a preparation method thereof. The material is firstly synthesized into a phenazine bond covalent organic framework material (COF-C) by a solvothermal method 4 N), followed by in situ synthesis on COF-C 4 N surface in-situ synthesis of nitrogen-doped molybdenum disulfide (N-MoS) 2 ) Thereby forming N-MoS 2 /COF‑C 4 An N heterostructure. The in-situ synthesis method not only dopes N into MoS 2 Skeleton, also N-MoS 2 More uniform dispersion into COF-C 4 N-MoS with more hydrogen-separating active sites exposed on N surface and improved charge separating and transmitting capacity 2 /COF‑C 4 The N composite catalyst has unique structure and can be used asIs an excellent electro-catalytic water-decomposing hydrogen-producing catalyst material.
Description
Technical Field
The invention relates to N-MoS with efficient electro-catalytic hydrogen evolution performance 2 /COF-C 4 An N composite catalyst and a preparation method thereof belong to the technical field of electrocatalytic hydrogen evolution and the technical field of catalyst preparation.
Technical Field
Since the industrial revolution, people increasingly rely on fossil fuels to rapidly advance industrialization and urbanization, and thus problems of environmental pollution and energy crisis begin to emerge. Therefore, there is an urgent need for the development of clean energy and sustainable energy. The production of hydrogen and oxygen by electrolysis of water is an effective strategy for the production of clean energy and renewable resources. How to improve the efficiency of hydrogen and oxygen production by water electrolysis and reduce the production cost is an important challenge for popularization and production of water electrolysis, and the core factor is the development of a high-efficiency catalyst. Although commercial Pt/C catalysts have the advantages of high catalytic activity and good stability, their large-scale application is limited due to their high cost and limited reserves. Therefore, the development of an efficient and cheap electrocatalyst is of great significance;
two-dimensional covalent organic framework materials (COFs) are an emerging graphene-like material, which are typically porous crystalline materials connected by covalent bonds, with a strong pi-pi stacked rigid backbone. In recent years, a great number of reports on the preparation of oxygen by electrocatalytic decomposition of water by covalent organic frameworks are excellent potential materials for electrocatalytic decomposition of water. Molybdenum disulfide (MoS) in transition metal dihalo-compounds (TMD) 2 ) The catalyst is basically composed of a two-dimensional S-Mo-S layer, is considered as a substitute of the traditional Pt group metal in hydrogen production by electrocatalytic decomposition of water, and has low cost but insufficient exposure of active sites, small specific surface area and the like, so that the hydrogen production efficiency is limited. Therefore, designing a molybdenum disulfide material with more active sites is an effective way for improving the electrocatalytic hydrogen production efficiency. And molybdenum disulfide and two-dimensional covalent organic framework material are compounded to form a heterostructure, so that the hydrogen production efficiency of molybdenum disulfide can be greatly improved.
Disclosure of Invention
The invention aims to provide nitrogen-doped molybdenum disulfide and COF-C synthesized in situ 4 N composite catalyst (N-MoS) 2 /COF-C 4 N) and method for the production thereof by means of N-doped MoS 2 (N-MoS 2 ) And COF-C 4 N-formed heterostructure for substantially enhanced MoS 2 Electrocatalytic hydrogen evolution performance.
In order to achieve the purpose, the invention adopts the technical scheme that: preparation of COF-C by hydrothermal method 4 N-MoS in situ synthesis on N surface 2 Further form N-MoS 2 And COF-C 4 And an N heterojunction. Comprises the following raw materials and components: triphenylene-2, 3,6,7,10, 11-hexamine hexahydrochloride, hexaketone cyclohexaneThe mass ratio of the alkyl octahydrate to the alkyl octahydrate is 25.5mg to 25.0 mg; 1, 4-dioxane, 1,3, 5-mesitylene and acetic acid, wherein the volume ratio is 1.5mL:1.5mL:0.5 mL; COF-C 4 N, thiourea and molybdenum trioxide, the mass ratio is: 10 mg: 19.7 mg: 19.0mg.
The N-MoS 2 /COF-C 4 The N composite catalyst is specifically prepared according to the following steps:
(1)COF-C 4 preparation of N:
sufficiently grinding triphenylene-2, 3,6,7,10, 11-hexamine hexahydrochloride and hexaketone cyclohexane octahydrate at room temperature, adding the mixture into an organic solvent mixed solution of 1, 4-dioxane and 1,3, 5-mesitylene, performing ultrasonic treatment at 25 ℃ for 30min, and adding 4mol/L acetic acid to obtain a dispersion liquid; introducing nitrogen into the dispersion liquid, vacuumizing, and then performing degassing by freezing and unfreezing, wherein the operation is repeated for three times; putting the degassed dispersion liquid into a drying oven at 150 ℃ for reaction for 72 hours, and taking out the test tube after the temperature of the drying oven is reduced to normal temperature to obtain a crude reaction product; filtering and washing the crude reaction product by tetrahydrofuran, and naturally airing to obtain a brownish black solid product; performing Soxhlet extraction on the solid product by using tetrahydrofuran, and stopping extracting until effluent liquid is colorless; vacuum drying the obtained solid product at 100 ℃ for 24h to obtain a two-dimensional covalent organic framework material (COF-C) with a crystal structure 4 N).
(2)N-MoS 2 /COF-C 4 Preparation of the N composite catalyst:
and (2) adding 59.1mg of thiourea and 57.2mg of molybdenum trioxide into 60mL of distilled water at room temperature, carrying out ultrasonic treatment for 30min to uniformly disperse the ligand, then adding 30mg of the pure product obtained in the step one into the dispersion, fully stirring for 1h to form uniform dispersion, putting the dispersion into a 200 ℃ oven to react for 24h, and taking out the reaction kettle after the temperature of the oven is reduced to normal temperature to obtain a crude reaction product. Filtering the crude product with a large amount of distilled water, and vacuum drying the obtained solid product at 100 ℃ for 12h to obtain the N-MoS 2 /COF-C 4 And (3) N composite catalyst.
The N-MoS is added 2 /COF-C 4 At N positionAfter treatment, coating the mixture on carbon cloth, taking the carbon cloth as a working electrode, and measuring the N-MoS 2 /COF-C 4 The linear voltammogram of the N composite catalyst is used for measuring the hydrogen evolution capability of the N composite catalyst in the electrocatalytic decomposition of water. It can be concluded that: the overpotential of the molybdenum disulfide at 10mA is only 106mV, which is improved by nearly 6 times compared with 629mV of the overpotential of the original molybdenum disulfide at 10 mA.
The benefits of the invention are:
(1) the manufacturing method is simple and efficient, has low cost and has practical application significance;
(2) the invention synthesizes N-MoS in situ 2 /COF-C 4 The obtained material has excellent performance of producing hydrogen by electrocatalytic decomposition of water;
(3) the invention uses covalent organic framework COF-C 4 N as synthetic N-MoS 2 A carrier of, COF-C 4 The porous structure and the ultra-high surface area of N reduce N-MoS 2 Achieve high dispersion, thereby exposing the N-MoS 2 More active sites and COF-C in electrocatalytic hydrogen evolution 4 The excellent conductivity and abundant porosity of N provide good conditions for charge separation and transport. Make N-MoS 2 /COF-C 4 Compared with single MoS, the electrocatalytic hydrogen evolution performance of the N composite catalyst 2 The material is greatly improved.
Drawings
FIG. 1 is a two-dimensional covalent organic framework material (COF-C) 4 N), molybdenum disulfide (MoS) 2 ) Nitrogen doped molybdenum disulfide (N-MoS) 2 ) And N-MoS 2 /COF-C 4 X-ray powder diffraction contrast diagram of N composite catalyst
FIG. 2 shows (a) COF-C 4 Scanning electron micrograph of N at 1 μm Scale (b) N-MoS 2 Scanning Electron microscopy at 1 μm Scale (c) N-MoS 2 /COF-C 4 Scanning electron microscope images of the N composite catalyst under a scale of 1 mu m; (d) (e) and (f) are each N-MoS 2 /COF-C 4 Element map of N, Mo and S elements in N composite catalyst
FIG. 3 is (a) COF-C 4 N(b)N-MoS 2 (c)N-MoS 2 /COF-C 4 N is compoundTransmission electron microscope contrast image of synthesized catalyst under 5nm scale
FIG. 4 shows N-MoS 2 /COF-C 4 X-ray photoelectron spectroscopy (XPS) total spectrum of N composite catalyst
FIG. 5 shows N-MoS 2 /COF-C 4 XPS spectrogram of each element of N composite catalyst
FIG. 6 is pure MoS 2 Pure COF-C 4 N and N-MoS 2 /COF-C 4 Linear voltammetric scan (LSV) of N composite catalyst
Detailed Description
The invention is further illustrated by the following examples, but is not limited to the following examples:
(1)COF-C 4 preparation of N
Sufficiently grinding triphenylene-2, 3,6,7,10, 11-hexamine hexahydrochloride and hexaketone cyclohexane octahydrate at room temperature, adding the mixture into an organic solvent mixed solution of 1, 4-dioxane and 1,3, 5-mesitylene, performing ultrasonic treatment at 25 ℃ for 30min, and adding 4mol/L acetic acid to obtain a dispersion liquid; introducing nitrogen into the dispersion liquid, vacuumizing, and then performing degassing by freezing and unfreezing, wherein the operation is repeated for three times; putting the degassed dispersion liquid into a drying oven at 150 ℃ for reaction for 72 hours, and taking out the test tube after the temperature of the drying oven is reduced to normal temperature to obtain a crude reaction product; filtering and washing the crude reaction product by tetrahydrofuran, and naturally airing to obtain a brownish black solid product; performing Soxhlet extraction on the solid product by using tetrahydrofuran, and stopping extracting until effluent liquid is colorless; vacuum drying the obtained solid product at 100 ℃ for 24h to obtain a two-dimensional covalent organic framework material (COF-C) with a crystal structure 4 N)；
(2)N-MoS 2 /COF-C 4 Preparation of N composite catalyst
Adding 59.1mg of thiourea and 57.2mg of molybdenum trioxide into 60mL of distilled water at room temperature, carrying out ultrasonic treatment for 30min to uniformly disperse a ligand, then adding 30mg of the pure product obtained in the step one into the dispersion, fully stirring for 1h to form uniform dispersion, putting the dispersion into a 200 ℃ oven, reacting for 24h, and taking out the reaction kettle after the temperature of the oven is reduced to normal temperature to obtain the productCrude reaction product. Filtering the crude product with a large amount of distilled water, and vacuum drying the obtained solid product at 100 ℃ for 12h to obtain the N-MoS 2 /COF-C 4 N composite catalyst;
the N-MoS is added 2 /COF-C 4 Adding the N composite catalyst and carbon black into a mortar according to the mass ratio of 1:1, fully grinding, then filling into a small centrifugal tube, adding distilled water, glacial acetic acid and naphthylene into the centrifugal tube to form a dispersion liquid, and carrying out ultrasonic treatment on the dispersion liquid for 1h to obtain a uniform dispersion liquid. Uniformly coating the dispersion liquid on a surface of 1cm 2 The carbon cloth is taken as a working electrode, Hg/Hg 2 SO 4 As a reference electrode, a Pt wire as a counter electrode, and a 0.5mol/l sulfuric acid solution as an electrolyte, by measuring the N-MoS 2 /COF-C 4 A linear voltammogram of the N composite catalyst was used to measure its ability to evolve hydrogen in electrocatalytic decomposition water, as shown in FIG. 6;
FIG. 1 is a two-dimensional covalent organic framework material (COF-C) 4 N), molybdenum disulfide (MoS) 2 ) Nitrogen doped molybdenum disulfide (N-MoS) 2 ) And N-MoS 2 /COF-C 4 X-ray powder diffraction contrast plot of N-composite catalyst. The nitrogen-doped molybdenum disulfide N-MoS can be seen in the figure 2 With pure MoS 2 In contrast, the characteristic peak disappeared, indicating that N was doped into MoS 2 In the skeleton, N-MoS corresponds to 14.4, 32.6 and 39.5 2 The 002, 100, and 103 crystal planes. Pure COF-C 4 Peaks with N at 7.2 ° and 27 ° at 2 θ corresponding to the 100 and 001 crystal planes, respectively, corresponding to regular pores and layered structures, respectively, after recombination, N-MoS 2 /COF-C 4 The N composite catalyst retains and shifts partial characteristic peak of 7.2 degrees, the peak of 27 degrees is obviously reduced, and the COF-C is shown 4 N as a substrate, in situ synthesized N-MoS 2 Well grown and dispersed in COF-C 4 N is the material of the substrate;
FIG. 2 shows (a) COF-C 4 Scanning electron micrograph of N at 1 μm Scale (b) N-MoS 2 Scanning Electron microscopy at 1 μm Scale (c) N-MoS 2 /COF-C 4 Scanning electron microscope images of the N composite catalyst under a scale of 1 mu m; (d) respectively, (e) and (f) are N-MoS 2 /COF-C 4 Elemental mapping of N, Mo and S elements in N composite catalysts (SEM and EDS). The comparison shows that the N-MoS is obvious 2 In COF-C 4 N is well dispersed, and N elements are uniformly distributed on the surface of the material;
FIG. 3(a) COF-C 4 N(b)N-MoS 2 (c)N-MoS 2 /COF-C 4 Transmission Electron Microscopy (TEM) contrast images of the N composite catalysts at 5nm scale. By contrast, it can be seen that the two-dimensional layered N-MoS 2 Uniformly dispersed in COF-C 4 N surface;
FIG. 4 shows N-MoS 2 /COF-C 4 An X-ray photoelectron spectroscopy (XPS) total spectrum of the N composite catalyst; XPS spectra confirmed the presence of C, N, Mo, S and O elements in the samples prepared. Wherein the presence of O may be due to oxidation of the sample or absorption of oxygen-containing species by the sample;
FIG. 5 shows N-MoS 2 /COF-C 4 XPS spectra of each element of the N composite catalyst. Wherein in the S2 p spectrum, two peaks at 161.46eV and 161.97eV correspond to S2 p 3/2 And S2 p 1/2 Two orbitals, which are divalent sulfide ions (S) of molybdenum disulfide 2- ) The typical characteristics of (A); whereas in the N1s spectrum, the peak at 395.41eV is attributable to the Mo — N bond, and the peak at 401.60eV demonstrates the presence of the C ═ N — C bond; in the spectrum of C1s, 284.57eV corresponds to a C-C bond; in the 3d spectrum of Mo, 229.16eV is also attributed to the Mo-N bond. From the above, it can be shown that N is successfully doped into MoS 2 On the backbone, and COF-C 4 N basically keeps the original structure, and we successfully prepare N-MoS 2 /COF-C 4 N composite catalyst;
FIG. 6 is pure MoS 2 Pure COF-C 4 N and N-MoS 2 /COF-C 4 Linear voltammetric scan (LSV) of N-composite catalyst. The N-MoS after the composition can be seen 2 /COF-C 4 The overpotential of the N composite catalyst at 10mA is only 106mV compared with the original MoS 2 Compared with 629mV, the overpotential is increased by 6 times;
in conclusion, we succeeded in preparing N-MoS by in situ synthesis 2 /COF-C 4 N composite catalyst, and the material is excellentThe electro-catalysis decomposition of water to produce hydrogen.
Claims (2)
1. N-MoS with efficient electro-catalytic hydrogen evolution performance 2 /COF-C 4 N composite catalyst characterized in that
(1) The feed consists of the following raw materials: triphenylene-2, 3,6,7,10, 11-hexamine hexahydrochloride and hexaketone cyclohexane octahydrate in a mass ratio of 25.5mg to 25.0 mg; 1, 4-dioxane, 1,3, 5-mesitylene and acetic acid, wherein the volume ratio of the 1.5mL to the 0.5 mL; c 4 N, thiourea and molybdenum trioxide, the mass ratio is: 10 mg: 19.7 mg: 19.0 mg;
(2) doping molybdenum disulfide (N-MoS) with nitrogen containing Mo-N bonds 2 ) Uniformly dispersed in two-dimensional COF-C 4 On N nano-chip, N is in MoS 2 Successful doping of surfaces and N-MoS 2 In COF-C 4 The surface hydrogen evolution active sites are increased by the uniform dispersion on the N nanosheets;
(3) the electrocatalytic hydrogen evolution performance is excellent, and N-MoS 2 /COF-C 4 The hydrogen evolution overpotential of the N composite catalyst at 10mA is only 106mV compared with that of pure MoS 2 The improvement is nearly 6 times.
2. N-MoS with high-efficiency electrocatalytic hydrogen evolution performance as defined in claim 1 2 /COF-C 4 The in-situ synthesis preparation method of the N composite catalyst is characterized by comprising the following steps:
(1)COF-C 4 preparation of N:
sufficiently grinding triphenylene-2, 3,6,7,10, 11-hexamine hexahydrochloride and hexaketone cyclohexane octahydrate at room temperature, adding the mixture into an organic solvent mixed solution of 1, 4-dioxane and 1,3, 5-mesitylene, performing ultrasonic treatment at 25 ℃ for 30min, and adding 4mol/L acetic acid to obtain a dispersion liquid; introducing nitrogen into the dispersion liquid, vacuumizing, and then performing degassing by freezing and unfreezing, wherein the operation is repeated for three times; placing the degassed dispersion liquid into an oven to react for 72 hours at the temperature of 150 ℃, and taking out the test tube after the temperature of the oven is reduced to normal temperature to obtain a crude reaction product; filtering and washing the crude reaction product by tetrahydrofuran, and naturally airing to obtain a brownish black solidA product; performing Soxhlet extraction on the solid product by using tetrahydrofuran, and stopping extracting until effluent liquid is colorless; vacuum drying the obtained solid product at 100 ℃ for 24h to obtain a two-dimensional covalent organic framework material (COF-C) with a crystal structure 4 N)；
(2)N-MoS 2 /COF-C 4 Preparation of the N composite catalyst:
and (2) adding 59.1mg of thiourea and 57.2mg of molybdenum trioxide into 60mL of distilled water at room temperature, carrying out ultrasonic treatment for 30min to uniformly disperse the ligand, then adding 30mg of the pure product obtained in the step one into the dispersion, fully stirring for 1h to form uniform dispersion, putting the dispersion into an oven to react for 24h at 200 ℃, and taking out the reaction kettle after the temperature of the oven is reduced to normal temperature to obtain a crude reaction product. Filtering the crude product with a large amount of distilled water, and vacuum drying the obtained solid product at 100 ℃ for 12h to obtain the N-MoS 2 /COF-C 4 And (3) N composite catalyst.
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