CN111203250A - One-dimensional bimetal carbide and preparation method thereof - Google Patents
One-dimensional bimetal carbide and preparation method thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 20
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- 238000001354 calcination Methods 0.000 claims abstract description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000001257 hydrogen Substances 0.000 claims abstract description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 9
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- 239000002070 nanowire Substances 0.000 claims description 25
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- 238000003756 stirring Methods 0.000 claims description 17
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- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 12
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- 230000002194 synthesizing effect Effects 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 10
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- 238000000034 method Methods 0.000 claims description 9
- 239000000843 powder Substances 0.000 claims description 9
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- 238000006243 chemical reaction Methods 0.000 claims description 7
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- ZULISPCCQYDDNG-UHFFFAOYSA-N zinc methanol dinitrate Chemical compound CO.[N+](=O)([O-])[O-].[Zn+2].[N+](=O)([O-])[O-] ZULISPCCQYDDNG-UHFFFAOYSA-N 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
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- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 6
- 238000009210 therapy by ultrasound Methods 0.000 claims description 6
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- 229910052786 argon Inorganic materials 0.000 claims description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 3
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 3
- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 claims description 3
- MFLKDEMTKSVIBK-UHFFFAOYSA-N zinc;2-methylimidazol-3-ide Chemical compound [Zn+2].CC1=NC=C[N-]1.CC1=NC=C[N-]1 MFLKDEMTKSVIBK-UHFFFAOYSA-N 0.000 claims description 3
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- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
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- 239000010411 electrocatalyst Substances 0.000 description 2
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- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 1
- -1 2-methylimidazolyl alcohol Chemical compound 0.000 description 1
- 239000012919 MOF-derived carbon material Substances 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
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- 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
- B01J27/20—Carbon compounds
- B01J27/22—Carbides
-
- B01J35/33—
-
- 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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- 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
- C25B11/093—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 noble metal or noble metal oxide and at least one non-noble metal oxide
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- 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 discloses a one-dimensional bimetallic carbide and a preparation method thereof, belonging to the technical field of new materials. The invention provides a one-dimensional bimetallic carbide and a preparation method thereof, wherein Ag nanowires is used as a template to controllably synthesize a one-dimensional ZIF-8@ ZIF-67nano composite structure, and the bimetallic carbide can be formed by subsequent calcination. The carbon-doped material with the hierarchical pore structure prepared by the invention can be used as a catalyst for hydrogen evolution by electrolytic water, has better catalytic activity, and has a current density of 10mA cm when the performance of the electrolytic water is tested in a KOH solution of 1.0M‑2The overpotential in time was only 48.6 mV. In addition, this nanowire-oriented templating approach also provides new opportunities for rational design and synthesis of composite MOF structures and their derived porous carbon or metal oxide materials.
Description
Technical Field
The invention relates to a one-dimensional bimetallic carbide and a preparation method thereof, belonging to the technical field of new materials.
Background
Metal Organic Frameworks (MOFs) are a class of crystalline porous structures with supramolecular structures, which are formed by the association of metal ions and organic ligands by coordination bonds. In recent years, MOF-derived carbon materials have attracted interest for their research in energy conversion and energy storage applications due to their ultra-high specific surface area and controlled pore structure. To date, there have been many studies reporting that various MOFs with other carbon sources can be directly pyrolyzed under an inert atmosphere and converted into amorphous microporous carbon without any activation. Unfortunately, research in this area has focused primarily on MOF crystallites or nanocrystals, and there is a lack of rational design for the shape and size of the synthetic materials. During carbonization, MOF crystals are transformed into bulk carbon powder due to high temperature, resulting in a decrease in effective specific surface area. Thus, while a small amount of MOF-derived microporous carbon has been introduced as an electrocatalyst in the electrochemical field, most catalysts are less electrochemically active. MOF crystals tend to exhibit unique morphologies that are difficult to alter based on the intrinsic driving force for crystallization. Therefore, the search for new strategies to control MOF crystal size has raised a great deal of attention.
Over the past few years, a wide variety of higher order MOF structures have been successfully developed. For example, Furukawa et al report a method for rapidly controlling nucleation sites, forming microscopic MOFs structures in two and three dimensions; maspoch et al used a spray drying method to construct hollow multicomponent MOF structures; zhang et al synthesized a one-dimensional MOF structure using a template method. The one-dimensional nanometer material has the characteristics of structural rigidity, anisotropy and the like, and the one-dimensional MOF structure combines the advantages of a one-dimensional nanometer structure and a porous structure, and has important application in the field of electrochemistry. However, the composition of the one-dimensional MOF structure is still relatively single at present, and is not fully developed. In recent years, the reported one-dimensional MOF has fewer structures and single appearance, such as Te @ ZIF-8 structure, ZnO @ ZIF-8 structure and the like, and a single-metal MOF structure is wrapped on the surface of a one-dimensional material by selecting the one-dimensional material as a template, but the material has poor electrochemical performance and is not widely applied in the field of catalysis.
Disclosure of Invention
In the electrochemical performance test process of the existing microcrystalline or nanocrystalline MOF material, the material is easy to agglomerate to reduce the performance of the material, and in order to overcome the defect, the invention provides a one-dimensional bimetallic carbide and a preparation method thereof.
The first purpose of the invention is to provide a preparation method of one-dimensional bimetallic carbide, which comprises the following synthetic route:
(1) synthesizing Ag nano wires Ag nanowires;
(2) coating ZIF-8 on the surface of Ag nanowires by taking the Ag nanowires as a template to synthesize Ag @ ZIF-8 nanowires;
(3) wrapping ZIF-67 on the surface of the Ag @ ZIF-8nanowires synthesized in the step (2) to synthesize Ag @ ZIF-8@ ZIF-67 nanowires;
(4) and (4) calcining the Ag @ ZIF-8@ ZIF-67nanowires synthesized in the step (3) to obtain the Ag @ Zn-Co-C material.
The schematic diagram of the synthesis steps of the Ag @ Zn-Co-C material is shown in FIG. 1.
In one embodiment of the present invention, the detailed synthesis steps of the preparation method are as follows:
(1) synthesis of Ag nanowires
Dissolving appropriate amount of polyvinylpyrrolidone (PVP) in ethylene glycol, vigorously stirring at about 90-110 deg.C to dissolve PVP completely to form clear and transparent solution, and cooling to room temperature; then adding a certain amount of ferric trichloride and silver nitrate solution, raising the temperature of the solution to 120-plus-150 ℃, preserving the heat, reacting for 3-5h to obtain Ag nanowires, finally washing with acetone and water for three times, and dispersing the obtained Ag nanowires in water for later use;
(2) synthesis of Ag @ ZIF-8nanowires
Preparing a 2-methylimidazole methanol solution and a zinc nitrate methanol solution with certain concentrations for later use, dispersing a certain amount of Agnanowires in methanol, then adding the prepared 2-methylimidazole methanol solution and the prepared zinc nitrate methanol solution, stirring at room temperature for 2-5h, standing overnight to obtain Ag @ ZIF-8nanowires, then washing with methanol and centrifuging, placing the obtained sample in a vacuum drying oven for drying, and obtaining a solid for later use;
(3) synthesis of Ag @ ZIF-8@ ZIF-67nanowires
Preparing a cobalt chloride methanol solution and a 2-methylimidazole methanol solution with certain concentration for later use, dispersing a certain amount of Ag @ ZIF-8 nanowines prepared in the step (2) in methanol, performing ultrasonic treatment to completely disperse the solution, stirring the solution at room temperature for 20 to 40min, then adding the prepared cobalt chloride methanol solution and the prepared 2-methylimidazole methanol solution, stirring the solution for 5 to 30min, transferring the solution into a hydrothermal kettle, performing hydrothermal reaction at the temperature of 100 ℃ and 120 ℃ for 10 to 15h to obtain Ag @ ZIF-8@ ZIF-67 nanowines, cooling the solution to room temperature, washing and centrifuging the solution by using methanol, drying the obtained sample in a vacuum drying box, and obtaining a solid for later use;
(4) preparation of Ag @ Zn-Co-C nanowires
Placing the dried Ag @ ZIF-8@ ZIF-67nanowires in the step (3) into a tube furnace in an argon (Ar) atmosphere at 2-5 ℃ for min-1The temperature rise rate is increased to 450-DEG, the temperature is kept for 6-10h, and the material is taken out after being cooled to the room temperature, thus obtaining the Ag @ Zn-Co-C nanowines black powder.
In one embodiment of the present invention, the concentration of the 2-methylimidazole methanol solution in the step (2) is in the range of 0.5 to 1M.
In one embodiment of the present invention, the concentration of the zinc nitrate methanol solution in the step (2) is in the range of 0.2 to 0.5M.
In one embodiment of the present invention, the mass ratio of Ag nanowires to zinc nitrate in step (2) is 1: 7 to 18.
In one embodiment of the present invention, the mass ratio of Ag nanowires and 2-methylimidazole in step (2) is 1: 5 to 10.
In one embodiment of the present invention, the concentration of the cobalt chloride methanol solution in step (3) is in the range of 0.4 to 1.0M.
In one embodiment of the present invention, the concentration of the 2-methylimidazolyl alcohol in step (3) ranges from 2.0 to 5.0M.
In one embodiment of the present invention, the ratio of the amounts of Ag @ ZIF-8nanowires and cobalt chloride in step (3) is 30mg: (156-350) mg.
In one embodiment of the present invention, the ratio of the amounts of Ag @ ZIF-8nanowires and 2-methylimidazole in step (3) is 30mg: (492-1230) mg.
In one embodiment of the present invention, the calcination temperature in step (4) is 450 ℃.
The second purpose of the invention is to provide the one-dimensional bimetallic carbide prepared by the preparation method.
The third purpose of the invention is to provide the application of the one-dimensional bimetallic carbide in the catalytic electrolysis water hydrogen evolution reaction.
The invention has the beneficial effects that:
1. the invention provides a novel method for controllably synthesizing a one-dimensional ZIF-8@ ZIF-67nano composite structure by taking Ag nanowires as a template, and then forming a bimetallic carbide by calcining;
2. the carbon-doped material with the hierarchical pore structure prepared by the invention can be used as a catalyst for hydrogen evolution by electrolytic water, has better catalytic activity, and has a current density of 10mA cm when the performance of the electrolytic water is tested in a KOH solution of 1.0M-2The overpotential of the time is only 48.6 mV;
3. this nanowire-oriented templating approach will provide new opportunities for rational design and synthesis of composite MOF structures and their derived porous carbon or metal oxide materials.
Drawings
FIG. 1 is a schematic diagram of the synthesis of Ag @ Zn-Co-C.
FIG. 2 is a graph of the morphology of Ag nanowires in example 1; wherein, (a) a scanning electron microscope image and (b) a transmission electron microscope image.
FIG. 3 is a graph of the morphology of Ag @ ZIF-8nanowires in example 1; wherein, (a) a scanning electron microscope image and (b) a transmission electron microscope image.
FIG. 4 is a graphical representation of Ag @ ZIF-8@ ZIF-67nanowires in example 1; wherein, (a) a scanning electron microscope image and (b) a transmission electron microscope image.
FIG. 5 is a thermogravimetric plot (TGA) of Ag @ ZIF-8@ ZIF-67nanowires in example 1.
FIG. 6 is a transmission electron micrograph of Ag @ Zn-Co-C nanowires in example 1.
FIG. 7 is a graph showing the polarization of Ag @ Zn-Co-C nanowires in example 1 in the hydrogen evolution reaction by electrolysis of water.
FIG. 8 is a graph of the morphology of Ag @ ZIF-8 of example 2; wherein (A) scanning electron micrographs; (B) transmission electron micrographs.
FIG. 9 is a transmission electron micrograph of Ag @ ZIF-8@ ZIF-67nanowires in example 3.
FIG. 10 is a transmission electron micrograph of Ag @ ZIF-8@ ZIF-67nanowires in example 4.
FIG. 11 is a graph showing the polarization of Ag @ Zn-Co nanowires in comparative example 1 in the hydrogen evolution reaction by electrolysis of water.
Detailed Description
Example 1
Synthesis of Ag @ Zn-Co-C nanowires
(1) Synthesis of Ag nanowires
Dissolving 320mg of polyvinylpyrrolidone (PVP) in 44mL of ethylene glycol, violently stirring at about 100 ℃ to completely dissolve the PVP to form a clear and transparent solution, and cooling to room temperature; then adding a certain amount of ferric trichloride (2.5mL, 1.2mM) and silver nitrate (360mg) solution, raising the temperature of the solution to 130 ℃, and preserving the temperature for 3 hours to obtain the Ag nanowires. Finally, washing the mixture for three times by using acetone and water, and finally dispersing the obtained Ag nanowires in water for later use. Fig. 2 is a morphology characterization diagram of the prepared Ag nanowires, and it can be seen that the synthesized Ag nanowires have a uniform morphology and a particle size of about 40 nm.
(2) Synthesis of Ag @ ZIF-8nanowires
A methanol solution of 2-methylimidazole (0.556M,10mL) and a methanol solution of zinc nitrate (0.278M,10mL) at certain concentrations were prepared for further use. And (2) dispersing 80mg of Ag nanowines prepared in the step (1) in 500mL of methanol, then adding the prepared 2-methylimidazole methanol solution and zinc nitrate methanol solution, stirring at room temperature for 3 hours, and standing for 12 hours to obtain Ag @ ZIF-8 nanowines, wherein the dosage ratio of the Ag nanowines to the 2-methylimidazole to the zinc nitrate is 80mg:456mg:826 mg. And washing with methanol, centrifuging, and drying the obtained sample in a vacuum drying oven to obtain powder for later use. From FIG. 3, it can be seen that the Agnanowineres surfaces are all successfully wrapped with ZIF-8 nanoshells and no other structures are formed, demonstrating that the method can be used to synthesize MOF materials with one-dimensional structures.
(3) Synthesis of Ag @ ZIF-8@ ZIF-67nanowires
A methanolic solution of cobalt chloride at a concentration (177mg in 3mL of methanol) and a methanolic solution of 2-methylimidazole (895mg in 3mL of methanol) were prepared for further use. And (3) dispersing 30mg of Ag @ ZIF-8nanowires prepared in the step (2) in 10mL of methanol, performing ultrasonic treatment for 30min to completely disperse the Ag @ ZIF-8nanowires, stirring at room temperature for 20min, then adding the prepared cobalt chloride methanol solution and 2-methylimidazole methanol solution, namely adding 30mg:177mg:895mg of Ag @ ZIF-8nanowires and cobalt chloride and 2-methylimidazole, stirring for 5min, transferring to a hydrothermal kettle, and performing hydrothermal reaction at 100 ℃ for 12h to obtain the Ag @ ZIF-8@ ZIF-67 nanowires. And after the temperature is reduced to room temperature, washing and centrifuging by using methanol, and drying the obtained sample in a vacuum drying oven to obtain powder for later use. From FIG. 4, it can be seen that the nano shell layer on the surface of Ag nanowires is thickened and the surface is relatively rough, and the method is proved to be applicable to synthesis of Ag @ ZIF-8@ ZIF-67nano composite structure.
(4) Calcining to obtain Ag @ Zn-Co-C nanowires
And (3) carrying out a thermal stability test on the Ag @ ZIF-8@ ZIF-67 nanowines synthesized in the step (3), wherein a thermal weight loss curve is shown in figure 5, the calcining temperature of the material is determined to be 450 ℃ according to the thermal weight loss curve, and then the material is calcined to obtain the metal carbide.
Placing the dried Ag @ ZIF-8@ ZIF-67nanowires in a tubular furnace under argon (Ar) atmosphere at 2 deg.C for 2 min-1The temperature rise rate is increased to 450 ℃, the temperature is kept for 8 hours at the temperature, and the black Ag @ Zn-Co-C powder is obtained after the black Ag @ Zn-Co-C powder is cooled to room temperature. As can be seen from fig. 6, a double metal carbide is formed on the Ag nanowires surface.
And (3) testing electrical properties:
electrochemical performance was determined using a conventional three-electrode system: Ag/AgCl is used as a reference electrode, a Pt wire is used as an auxiliary electrode, and a glassy carbon electrode modified with a catalyst is used as a working electrode. Firstly, a working electrode is prepared, 5mg of a sample, 5mg of carbon black, 970 mu L of isopropanol and 30 mu L of naphthol are mixed and subjected to ultrasonic treatment for 1 hour to form a uniform solution. And (3) dropwise adding 21 mu L of the mixed solution on the surface of the glassy carbon electrode, and naturally drying to obtain the working electrode. The electrochemical performance tests all utilized electrochemical tests of model number CHI760EThe study work station (Shanghai Chenghua). Electrical polarity test at a fixed scan rate (10mV s) in a 1.0M KOH solution-1) The process is carried out as follows.
As can be seen from FIG. 7, when the performance of electrolyzed water was tested in a 1.0M KOH solution, the current density was 10mA cm-2Compared with the reported related documents, the overpotential of the material is 48.6mV, and the material has good performance of hydrogen evolution in water electrolysis, thereby proving that the material can be used as an effective electrocatalyst for water electrolysis.
Example 2 changing Ag nanowires, Zinc nitrate (Zn (NO) in step 23)2·6H2O) and 2-methylimidazole.
(1) Synthesis of Ag nanowires: same as in step (1) in example 1;
(2) synthesizing Ag @ ZIF-8 nanowires:
reduction of 2-methylimidazole and Zn (NO)3)2·6H2The dosage of O: a methanol solution of 2-methylimidazole (0.224M, 10mL) and a methanol solution of zinc nitrate (0.112M, 10mL) at a certain concentration were prepared for further use. Dispersing the Ag nanowines 80mg prepared in the step (1) in 500mL of methanol, and then adding the prepared 2-methylimidazole methanol solution and zinc nitrate methanol solution respectively to enable the dosage ratio of the Ag nanowines to the 2-methylimidazole to the zinc nitrate to be 80mg:333mg:184mg respectively. Stirring for 3h at room temperature, and standing for 12h to obtain Ag @ ZIF-8 nanowires. And washing with methanol, centrifuging, and drying the obtained sample in a vacuum drying oven to obtain powder for later use.
FIG. 8 is a graph of Ag @ ZIF-8 morphology in example 2, wherein (A) is a scanning electron micrograph; (B) transmission electron micrographs. It can be seen from the figure that 2-methylimidazole and Zn (NO) are reduced when3)2·6H2When the amount of O is used, Zn wrapping on the surface of the Ag wire is not uniform.
Example 3 variation of Ag @ ZIF-8nanowire, CoCl in step 32And the amount of 2-methylimidazole.
(1) Synthesis of Ag nanowires: same as in step (1) in example 1;
(2) synthesizing Ag @ ZIF-8 nanowires: same as step (2) in example 2;
(3) synthesizing Ag @ ZIF-8@ ZIF-67 nanowires:
the amount of cobalt chloride and 2-methylimidazole was doubled: cobalt chloride methanol solution with certain concentration (354mg, 3ml) and 2-methylimidazole methanol solution (1790mg, 3ml) are prepared for standby. And (3) dispersing the Ag @ ZIF-8nanowires 30mg prepared in the step (2) in 10mL of methanol, performing ultrasonic treatment for 30min to completely disperse the Ag @ ZIF-8nanowires, stirring at room temperature for 20min, then adding the prepared cobalt chloride methanol solution and 2-methylimidazole methanol solution, namely adding the Ag @ ZIF-8nanowires, the cobalt chloride and the 2-methylimidazole in a dosage ratio of 30mg:354mg:1790mg, stirring for 5min, transferring to a hydrothermal kettle, and performing hydrothermal reaction at 100 ℃ for 12h to obtain the Ag @ ZIF-8@ ZIF-67 nanowires. And after the temperature is reduced to room temperature, washing and centrifuging by using methanol, and drying the obtained sample in a vacuum drying oven to obtain Ag @ ZIF-8@ ZIF-67nanowires powder. FIG. 9 is a transmission electron micrograph of Ag @ ZIF-8@ ZIF-67nanowires, and it can be seen from FIG. 9 that the Co coating on the surface is not uniform when the amount of cobalt chloride and 2-methylimidazole are doubled.
Example 4 variation of Ag @ ZIF-8nanowire, CoCl in step (3)2And the amount of 2-methylimidazole.
(1) Synthesis of Ag nanowires: same as in step (1) in example 1;
(2) synthesizing Ag @ ZIF-8 nanowires: same as step (2) in example 2;
(3) synthesizing Ag @ ZIF-8@ ZIF-67 nanowires:
the amount of cobalt chloride and 2-methylimidazole was reduced by one time: a methanol solution of cobalt chloride with a certain concentration (89mg, 3ml) and a methanol solution of 2-methylimidazole (448mg, 3ml) were prepared for further use. And (3) dispersing the Ag @ ZIF-8nanowires 30mg prepared in the step (2) in 10mL of methanol, performing ultrasonic treatment for 30min to completely disperse the Ag @ ZIF-8nanowires, stirring at room temperature for 20min, then adding the prepared cobalt chloride methanol solution and 2-methylimidazole methanol solution, namely adding the Ag @ ZIF-8nanowires, the cobalt chloride and the 2-methylimidazole in a dosage ratio of 30mg:89mg:448mg, stirring for 5min, transferring to a hydrothermal kettle, and performing hydrothermal reaction at 100 ℃ for 12h to obtain the Ag @ ZIF-8@ ZIF-67 nanowires. And after the temperature is reduced to room temperature, washing and centrifuging by using methanol, and drying the obtained sample in a vacuum drying oven to obtain Ag @ ZIF-8@ ZIF-67nanowires powder. FIG. 10 is a transmission electron micrograph of Ag @ ZIF-8@ ZIF-67nanowires, and it can be seen from FIG. 10 that the same uneven surface Co coating occurs when the amount of cobalt chloride and 2-methylimidazole are reduced by one-fold.
Comparative example 1 Synthesis of one-dimensional Mono-metallic carbide Ag @ Zn-Cnanowires
(1) Synthesis of Ag nanowires: same as in step (1) in example 1;
(2) synthesizing Ag @ ZIF-8 nanowires: same as step (2) in example 1;
(3) calcining to obtain Ag @ Zn-C nanowires: same as in step (4) in example 1.
And (3) testing electrical properties:
the test method is the same as example 1, FIG. 11 is a polarization curve diagram of Ag @ Zn-C nanowires in the hydrogen evolution reaction by electrolysis of water, when the performance of electrolysis of water is tested in a 1.0M KOH solution, the current density is 10mA cm-2The overpotential is 362mV, compared with Ag @ Zn-Co-C, the material has poor hydrogen evolution performance, thereby proving that the introduction of Co can improve the water electrolysis performance of the material.
Although the present invention has been described with reference to the preferred embodiments, it should be understood that various changes and modifications can be made therein by those skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (9)
1. The preparation method of the one-dimensional bimetallic carbide is characterized in that the synthetic route of the preparation method is as follows:
(1) synthesizing Ag nano wires Ag nanowires;
(2) coating ZIF-8 on the surface of Ag nanowires by taking the Ag nanowires as a template to synthesize Ag @ ZIF-8 nanowires;
(3) wrapping ZIF-67 on the surface of the Ag @ ZIF-8nanowires synthesized in the step (2) to synthesize Ag @ ZIF-8@ ZIF-67 nanowires;
(4) and (4) calcining the Ag @ ZIF-8@ ZIF-67nanowires synthesized in the step (3) to obtain the Ag @ Zn-Co-C material.
2. The preparation method according to claim 1, wherein the detailed synthesis steps of the preparation method are as follows:
(1) synthesis of Ag nanowires:
dissolving appropriate amount of polyvinylpyrrolidone in ethylene glycol, vigorously stirring at about 90-110 deg.C to dissolve PVP completely to form clear and transparent solution, and cooling to room temperature; then adding a certain amount of ferric trichloride and silver nitrate solution, raising the temperature of the solution to 120-plus-150 ℃, carrying out heat preservation reaction for 3-5h to obtain Ag nanowires, finally washing with acetone and water for three times, and dispersing the obtained Ag nanowires in water for later use;
(2) synthesizing Ag @ ZIF-8 nanowires:
preparing a 2-methylimidazole methanol solution and a zinc nitrate methanol solution with certain concentrations for later use, dispersing a certain amount of Agnanowires in methanol, then adding the prepared 2-methylimidazole methanol solution and the prepared zinc nitrate methanol solution, stirring at room temperature for 2-5h, standing overnight to obtain Ag @ ZIF-8nanowires, then washing with methanol and centrifuging, placing the obtained sample in a vacuum drying oven for drying, and obtaining a solid for later use;
(3) synthesizing Ag @ ZIF-8@ ZIF-67 nanowires:
preparing a cobalt chloride methanol solution and a 2-methylimidazole methanol solution with certain concentration for later use, dispersing a certain amount of Ag @ ZIF-8 nanowines prepared in the step (2) in methanol, performing ultrasonic treatment to completely disperse the solution, stirring the solution at room temperature for 20 to 40min, then adding the prepared cobalt chloride methanol solution and the prepared 2-methylimidazole methanol solution, stirring the solution for 5 to 30min, transferring the solution into a hydrothermal kettle, performing hydrothermal reaction at the temperature of 100 ℃ and 120 ℃ for 10 to 15h to obtain Ag @ ZIF-8@ ZIF-67 nanowines, cooling the solution to room temperature, washing and centrifuging the solution by using methanol, drying the obtained sample in a vacuum drying box, and obtaining a solid for later use;
(4) preparation of Ag @ Zn-Co-C nanowires:
placing the dried Ag @ ZIF-8@ ZIF-67nanowires in the step (3) into a tube furnace at 2-5 ℃ for min in an argon atmosphere-1The temperature rise rate is increased to 450-DEG and 600 ℃ for calcination, the temperature is kept for 6 to 10 hours at the temperature, and the material is taken out after being cooled to the room temperature, so that the black Ag @ Zn-Co-C nanowines powder is obtained.
3. The preparation method according to claim 2, wherein the mass ratio of Ag nanowires to zinc nitrate in step (2) is 1: 7 to 18.
4. The preparation method according to claim 2, wherein the mass ratio of Ag nanowines to 2-methylimidazole in the step (2) is 1: 5 to 10.
5. The preparation method according to claim 2, wherein the ratio of the amount of Ag @ ZIF-8nanowires to the amount of cobalt chloride in step (3) is 30mg: (156-350) mg.
6. The preparation method according to claim 2, wherein the ratio of the amount of Ag @ ZIF-8nanowires to the amount of 2-methylimidazole in step (3) is 30mg: (492-1230) mg.
7. The method according to claim 2, wherein the calcination temperature in the step (4) is 450 ℃.
8. A one-dimensional bimetallic carbide prepared by the preparation method of any one of claims 1 to 7.
9. Use of a one-dimensional bimetallic carbide as described in claim 8 for catalyzing an electrolytic hydrogen evolution reaction.
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