CN109621998B - Three-dimensional mesoporous carbon loaded molybdenum carbide and preparation method and application thereof - Google Patents
Three-dimensional mesoporous carbon loaded molybdenum carbide and preparation method and application thereof Download PDFInfo
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- CN109621998B CN109621998B CN201811487558.1A CN201811487558A CN109621998B CN 109621998 B CN109621998 B CN 109621998B CN 201811487558 A CN201811487558 A CN 201811487558A CN 109621998 B CN109621998 B CN 109621998B
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- 229910039444 MoC Inorganic materials 0.000 title claims abstract description 81
- QIJNJJZPYXGIQM-UHFFFAOYSA-N 1lambda4,2lambda4-dimolybdacyclopropa-1,2,3-triene Chemical compound [Mo]=C=[Mo] QIJNJJZPYXGIQM-UHFFFAOYSA-N 0.000 title claims abstract description 78
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 61
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 37
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 36
- 238000003756 stirring Methods 0.000 claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 17
- 150000002751 molybdenum Chemical class 0.000 claims abstract description 13
- 238000002791 soaking Methods 0.000 claims abstract description 13
- 238000003763 carbonization Methods 0.000 claims abstract description 11
- 239000007789 gas Substances 0.000 claims abstract description 11
- 239000002253 acid Substances 0.000 claims abstract description 6
- 239000000463 material Substances 0.000 claims abstract description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 32
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 14
- 239000000377 silicon dioxide Substances 0.000 claims description 14
- 235000012239 silicon dioxide Nutrition 0.000 claims description 14
- 239000001257 hydrogen Substances 0.000 claims description 13
- 229910052739 hydrogen Inorganic materials 0.000 claims description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 12
- 230000009467 reduction Effects 0.000 claims description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 7
- 239000011609 ammonium molybdate Substances 0.000 claims description 7
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 7
- 229940010552 ammonium molybdate Drugs 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 7
- 238000000227 grinding Methods 0.000 claims description 6
- 239000000395 magnesium oxide Substances 0.000 claims description 6
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 6
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 5
- 229910052786 argon Inorganic materials 0.000 claims description 4
- KLOIYEQEVSIOOO-UHFFFAOYSA-N carbocromen Chemical compound CC1=C(CCN(CC)CC)C(=O)OC2=CC(OCC(=O)OCC)=CC=C21 KLOIYEQEVSIOOO-UHFFFAOYSA-N 0.000 claims description 4
- 230000018044 dehydration Effects 0.000 claims description 2
- 238000006297 dehydration reaction Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 abstract description 9
- 229910052750 molybdenum Inorganic materials 0.000 abstract description 6
- 238000001704 evaporation Methods 0.000 abstract description 5
- 239000011733 molybdenum Substances 0.000 abstract description 5
- 230000008569 process Effects 0.000 abstract description 5
- 239000011261 inert gas Substances 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 4
- 238000010000 carbonizing Methods 0.000 abstract description 3
- 238000003837 high-temperature calcination Methods 0.000 abstract description 3
- 239000002086 nanomaterial Substances 0.000 abstract description 3
- 238000001354 calcination Methods 0.000 abstract 1
- 239000003054 catalyst Substances 0.000 description 13
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- 239000013078 crystal Substances 0.000 description 7
- 238000002441 X-ray diffraction Methods 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 230000010287 polarization Effects 0.000 description 6
- 229910052723 transition metal Inorganic materials 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- 239000002131 composite material Substances 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 229910000510 noble metal Inorganic materials 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 229910021607 Silver chloride Inorganic materials 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 238000005868 electrolysis reaction Methods 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- -1 transition metal carbides Chemical class 0.000 description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000011684 sodium molybdate Substances 0.000 description 3
- 235000015393 sodium molybdate Nutrition 0.000 description 3
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 239000008103 glucose Substances 0.000 description 2
- 238000003780 insertion Methods 0.000 description 2
- 230000037431 insertion Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
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- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 238000005498 polishing Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- YXVFQADLFFNVDS-UHFFFAOYSA-N diammonium citrate Chemical compound [NH4+].[NH4+].[O-]C(=O)CC(O)(C(=O)O)CC([O-])=O YXVFQADLFFNVDS-UHFFFAOYSA-N 0.000 description 1
- 229910021397 glassy carbon Inorganic materials 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000009396 hybridization Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- PDKHNCYLMVRIFV-UHFFFAOYSA-H molybdenum;hexachloride Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Mo] PDKHNCYLMVRIFV-UHFFFAOYSA-H 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
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Images
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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
-
- 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
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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 belongs to the field of nano material preparation, and discloses three-dimensional mesoporous carbon loaded molybdenum carbide and preparation and application thereof. Dissolving soluble molybdenum salt in water, adding an organic carbon source and a template agent, adjusting the pH value of the solution to 0-7.0, stirring and evaporating to dryness to obtain gel, further dehydrating the gel to obtain dried gel, calcining the dried gel at high temperature in the atmosphere of inert gas or reducing gas, carbonizing the organic carbon source to obtain carbon, reducing and carbonizing molybdenum by using reducing substances generated in the carbonization process of the organic carbon source to obtain nano molybdenum carbide, and soaking and removing the nano molybdenum carbide by using dilute acid to obtain a target product. Compared with a bulk molybdenum carbide material, the three-dimensional mesoporous carbon loaded molybdenum carbide has a conductive three-dimensional carbon network structure, a larger specific surface area and more reaction active sites, and the carbon loaded structure prevents the molybdenum carbide from agglomerating during high-temperature calcination, so the three-dimensional mesoporous carbon loaded molybdenum carbide has excellent electrocatalytic performance.
Description
Technical Field
The invention belongs to the technical field of nano material preparation, and particularly relates to three-dimensional mesoporous carbon loaded molybdenum carbide and a preparation method and application thereof.
Background
With the development of water electrolysis hydrogen production technology, the demand of electrode catalysts used in the method for producing hydrogen by water electrolysis with low cost and high efficiency is more and more obvious. Due to the characteristics of high cost and low reserves of noble metals such as Pt and the like as the water electrolysis catalyst, the development of a novel non-noble metal catalyst becomes a hotspot of the current research, wherein transition metal carbides attract wide attention in the research process of water electrolysis. Transition metal carbides are formed by insertion of carbon atoms into the transition metal lattice and formation of chemical bonds. Transition metal carbides can exhibit very different physical and chemical properties compared to their parent metals as well as metal oxides. The transition metal carbide not only has high melting point, high hardness and high tensile strength, but also has high electrical conductivity and thermal conductivity. Recent studies have shown that transition metal carbides exhibit catalytic properties similar to noble metals, and that these unique catalytic properties and their electronic structure are closely related to the crystal structure. For molybdenum carbide, due to the unique interstitial structure of molybdenum carbide, insertion of carbon atoms into the molybdenum atom lattice causes expansion of the molybdenum metal lattice, resulting in an increase in the distance between the molybdenum metal atoms. This increase in metal-to-metal atom spacing causes the d-band of the molybdenum atoms to contract, resulting in an increase in the d-band density of the molybdenum. On the other hand, the s-p orbital of carbon in molybdenum carbide and the d orbital of molybdenum produce hybridization, and the produced hybrid d orbital can exhibit an electronic structure similar to that of noble metal Pt. According to band theory, the electronic properties of the d band significantly affect the adsorption and activation of reactants. Therefore, the molybdenum carbide is expected to obtain the catalytic property similar to that of the noble metal Pt and has important research value.
Carbon materials have the potential to be highly efficient and stable HER catalysts due to their resistance to acids and bases, high conductivity, etc., whereas poor hydrogen adsorption capacity (Gibbs free energy of hydrogen adsorption Δ GH: -1.3 eV; excellent HER catalysts often have Δ GH values of-0 eV) leads to very slow catalytic kinetics. In contrast, carbon supported metal/alloy catalysts (catalytically active sites are considered to be on the surface carbon layer and are referred to as "armor" catalysts due to their excellent catalytic activity and stability) have received much attention in recent years. Therefore, the development of carbon composite catalysts is of great interest for the development of HER catalysts with platinum-like properties. On the other hand, nanomaterials having a three-dimensional (3-D) network structure are receiving attention due to their versatility, such as a large specific surface area, a three-dimensional porous structure, which are important factors affecting the electrocatalytic performance of the composite, and they are advantageous to adsorption of protons, exposure of active sites, flow of an electrolyte, and the like.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention mainly aims to provide a preparation method of three-dimensional mesoporous carbon loaded molybdenum carbide.
The invention also aims to provide the three-dimensional mesoporous carbon loaded molybdenum carbide prepared by the method.
The invention further aims to provide application of the three-dimensional mesoporous carbon loaded molybdenum carbide.
The purpose of the invention is realized by the following scheme:
a preparation method of three-dimensional mesoporous carbon loaded molybdenum carbide comprises the following steps:
(1) preparing a gel: dissolving soluble molybdenum salt in water, adding an organic carbon source and a template agent, uniformly mixing the mixture solution, adjusting the pH value of the mixture solution to 0-7, heating and stirring the mixture solution to evaporate the mixture solution to dryness to obtain gel, and further heating and dehydrating the gel to obtain dry gel;
(2) preparing three-dimensional mesoporous carbon loaded molybdenum carbide: and (2) uniformly grinding the dried gel obtained in the step (1), putting the dried gel into a tubular furnace for high-temperature carbonization and reduction, introducing inert gas or reducing gas in the reaction process, and soaking the obtained product with acid after the reaction is finished to obtain the target product, namely the three-dimensional mesoporous carbon loaded molybdenum carbide.
The soluble molybdenum salt in the step (1) comprises but is not limited to ammonium molybdate, molybdenum chloride, sodium molybdate and the like;
the organic carbon source in step (1) includes, but is not limited to, citric acid, diammonium hydrogen citrate, glucose, dicyandiamide, cyanamide, and the like.
The template agent in the step (1) is silicon dioxide or magnesium oxide, and the particle size of the template agent is 10-1000 nm;
the template agent in the step (1) is preferably added in the form of aqueous dispersion, and the mass concentration of the template agent in the aqueous dispersion of the template agent is preferably 40%;
the dosage of the soluble molybdenum salt, the organic carbon source and the template agent in the step (1) meets the following requirements: the mass ratio of the organic carbon source to the soluble molybdenum salt is (0.5-10) to 1; the mass ratio of the organic carbon source to the template agent is (0.2-5): 1.
Preferably, the soluble molybdenum salt, the organic carbon source and the template agent in the step (1) are used in amounts that: the mass ratio of the organic carbon source to the soluble molybdenum salt is (2.5-4) to 1; the mass ratio of the organic carbon source to the template agent is (1-3) to 1.
The water described in step (1) is used only as a reaction medium, so that the amount thereof is only required to be such that it can completely dissolve the added soluble molybdenum salt and organic carbon source.
The heating and stirring in the step (1) are heating to 60-80 ℃, stirring and reacting for 4-24 hours, and stirring is performed to fully mix the raw materials, so that the conventional stirring speed in the field can be realized;
the step (1) of further heating for dehydration refers to heating to 100-200 ℃ for reaction for 4-24 hours;
the high-temperature carbonization reduction in the step (2) is carried out for 2-12 hours at the temperature of 600-1200 ℃;
the inert gas or reducing gas in the step (2) includes but is not limited to nitrogen, argon, hydrogen, argon/hydrogen mixed gas;
the acid in the step (2) is one of hydrofluoric acid and hydrochloric acid with the concentration of 2-8 wt%;
the soaking in the step (2) is soaking for 1-48 hours, preferably soaking for 2-8 hours;
the method is carried out at room temperature which is 20-30 ℃;
the three-dimensional mesoporous carbon loaded molybdenum carbide prepared by the method.
The three-dimensional mesoporous carbon loaded molybdenum carbide prepared by the method is applied as an electrocatalytic material, in particular to the application of the electrocatalytic material in hydrogen production by catalyzing water decomposition.
The mechanism of the invention is as follows:
dissolving soluble molybdenum salt in water, adding an organic carbon source such as citric acid, diammonium hydrogen citrate, glucose, dicyandiamide, cyanamide and the like, adding template agent silicon dioxide or magnesium oxide, uniformly stirring, adjusting the pH value of the solution to 0-7.0 by using ammonia water to promote the combination of organic carbon source molecules and molybdenum elements, stirring at 60-80 ℃ to evaporate water to obtain gel, further dehydrating the gel at 100-200 ℃ to obtain dry gel, reacting the dry gel at 600-1200 ℃ in an inert gas or reducing gas atmosphere, carbonizing the organic carbon source to obtain carbon in a high-temperature calcination process, and reducing substances such as carbon monoxide, carbon dioxide, methane, carbon and the like generated in the organic carbon source carbonization process can reduce and carbonize the molybdenum to obtain nano molybdenum carbide, thus obtaining the silicon dioxide (magnesium oxide)/molybdenum carbide/carbon composite material after the reaction is finished, and then soaking and removing the silicon dioxide (magnesium oxide) by using dilute hydrofluoric acid (dilute hydrochloric acid) to obtain the target product, namely the three-dimensional mesoporous carbon loaded molybdenum carbide (silicon dioxide or magnesium oxide is used as a pore-forming sacrificial agent). Compared with a bulk molybdenum carbide material, the three-dimensional mesoporous carbon loaded molybdenum carbide has a conductive three-dimensional carbon network structure, has a larger specific surface area and more reaction active sites, and the carbon loaded structure prevents the molybdenum carbide from agglomerating during high-temperature calcination, so the three-dimensional mesoporous carbon loaded molybdenum carbide has excellent electrocatalytic performance.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) the invention realizes the controllable synthesis of the three-dimensional mesoporous carbon loaded molybdenum carbide.
(2) The three-dimensional mesoporous carbon loaded molybdenum carbide synthesized by the method has a novel structure, and the hydrogen production performance by electrocatalytic decomposition of water is stable.
(3) The process is simple and controllable, and can be rapidly amplified and industrialized.
Drawings
FIG. 1 is an XRD pattern of molybdenum carbide supported on three-dimensional mesoporous carbon prepared in example 1;
FIG. 2 is an XRD pattern of the three-dimensional mesoporous carbon supported molybdenum carbide prepared in example 2;
FIG. 3 is an XRD pattern of the three-dimensional mesoporous carbon supported molybdenum carbide prepared in example 3;
FIG. 4 is an SEM image of three-dimensional mesoporous carbon supported molybdenum carbide prepared in example 3;
FIG. 5 is a polarization curve of the three-dimensional mesoporous carbon supported molybdenum carbide prepared in example 3;
FIG. 6 is an SEM image of three-dimensional mesoporous carbon supported molybdenum carbide prepared in example 4;
FIG. 7 is a TEM image of the three-dimensional mesoporous carbon supported molybdenum carbide prepared in example 4;
FIG. 8 is a polarization plot of the three-dimensional mesoporous carbon supported molybdenum carbide prepared in example 4;
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but the embodiments of the present invention are not limited thereto.
The reagents used in the examples are commercially available without specific reference.
The polarization curve test method in this example is as follows:
preparing an electrode: first, a polishing powder (Al) for a Glassy Carbon Electrode (GCE) having a diameter of 3mm was used2O3) Grinding and polishing, and cleaning with ethanol and deionized water for later use. Secondly, weighing 4mg of catalyst into a centrifuge tube, adding 750m L deionized water, 250 μ L of ethanol and 30 μ L of Nafion solution, ultrasonically dispersing uniformly, transferring 5 μ L of the solution to a GCE, and irradiating and drying under an infrared lamp. The calculated catalyst loading was 0.285mg cm-2。
Electrochemical testing: all electrochemical data were measured on CHI 660E electrochemical workstation using a 1.0M KOH solution in N2And (5) purifying. In a typical three-electrode test system, the graphite rod electrode is the counter electrode, the GCE with catalyst is the working electrode, and the Ag/AgCl electrode is the reference electrode. After the catalyst was stabilized in the electrolyte, at 5 mVs-1The polarization curve (LSV) test was performed, all potentials are expressed in Reversible Hydrogen Electrode (RHE), the formula is converted:
ERHE＝EAg/AgCl+0.059pH+Eθ Ag/AgCl
Eθ Ag/AgCl＝0.198V
example 1
The preparation method of the three-dimensional mesoporous carbon supported molybdenum carbide of the embodiment includes the following specific preparation steps:
dissolving 6.0g of soluble ammonium molybdate in deionized water, adding 15.0g of diammonium hydrogen citrate, adding 40g of silicon dioxide dispersion liquid (the content of silicon dioxide is 40 wt%, and the particle size of the silicon dioxide is 15 +/-5 nm) after the ammonium hydrogen citrate is completely dissolved, adjusting the pH value of the solution to 6.0 by using ammonia water, stirring and evaporating at 70 ℃ for 12 hours to obtain gel, further dehydrating the gel at 200 ℃ for 12 hours to obtain dried gel, uniformly grinding the dried gel, putting the dried gel into a tubular furnace for carbonization reduction at 900 ℃ for 2 hours, and introducing 5% (v/v) H in the reaction process2And soaking and stirring the reaction product in excessive 4.0 wt% hydrofluoric acid for 4 hours after the reaction of the/Ar mixed gas is finished, filtering, and naturally drying to obtain the target product, namely the three-dimensional mesoporous carbon loaded molybdenum carbide.
The XRD pattern of the three-dimensional mesoporous carbon supported molybdenum carbide obtained in this example is shown in fig. 1, and the characteristic peaks of XRD of the three-dimensional mesoporous carbon supported molybdenum carbide are 36.9 °, 42.8 °, 62.7 ° and 75.3 °, corresponding to the (111), (200), (220) and (311) crystal planes of α -MoC, respectively. The characteristic peak of 24.9 ° corresponds to the (002) crystal face of graphitized carbon.
The scanning electron microscope is used for detecting the molybdenum carbide loaded on the three-dimensional mesoporous carbon prepared in the embodiment, and the result shows that the molybdenum carbide has an obvious ordered mesoporous structure, which indicates that the embodiment successfully synthesizes a target product of three-dimensional mesopores.
Example 2
The preparation method of the three-dimensional mesoporous carbon supported molybdenum carbide of the embodiment includes the following specific preparation steps:
dissolving 6.0g of soluble sodium molybdate in deionized water, adding 20.0g of cyanamide, adding 40g of silicon dioxide dispersion liquid (the content of silicon dioxide is 40 wt%, and the particle size of the silicon dioxide is 15 +/-5 nm) after the soluble sodium molybdate is completely dissolved, adjusting the pH value of the solution to 7 by using nitric acid, stirring and evaporating at 70 ℃ for 12 hours to obtain gel, then putting the gel into a tubular furnace for carbonization and reduction at 700 ℃ for 2 hours, and introducing 5% (v/v) H in the reaction process2And soaking and stirring the reaction product in excessive 2.0 wt% hydrofluoric acid for 8 hours after the reaction of the/Ar mixed gas, filtering, and naturally drying to obtain the target product, namely the three-dimensional mesoporous carbon loaded molybdenum carbide.
The XRD pattern of the three-dimensional mesoporous carbon supported molybdenum carbide obtained in this example is shown in fig. 2, and the characteristic peaks of XRD of the three-dimensional mesoporous carbon supported molybdenum carbide are 36.9 °, 42.8 °, 62.7 ° and 75.3 °, corresponding to the (111), (200), (220) and (311) crystal planes of α -MoC, respectively. The characteristic peak of 24.9 ° corresponds to the (002) crystal face of graphitized carbon.
The scanning electron microscope is used for detecting the molybdenum carbide loaded on the three-dimensional mesoporous carbon prepared in the embodiment, and the result shows that the molybdenum carbide has an obvious ordered mesoporous structure, which indicates that the embodiment successfully synthesizes a target product of three-dimensional mesopores.
Example 3
The preparation method of the three-dimensional mesoporous carbon supported molybdenum carbide of the embodiment includes the following specific preparation steps:
dissolving 6.0g of soluble ammonium molybdate in deionized water, adding 18.0g of dicyanodiamide, adding 40g of silicon dioxide dispersion liquid (the content of silicon dioxide is 40 wt%, and the particle size of the silicon dioxide is 15 +/-5 nm) after the ammonium molybdate is completely dissolved, adjusting the pH of the solution to be 4.5 by using nitric acid, stirring and evaporating at 80 ℃ for 12 hours to obtain gel, further dehydrating the gel at 180 ℃ for 12 hours to obtain dried gel, uniformly grinding the dried gel, putting the dried gel into a tubular furnace for carbonization reduction at 900 ℃ for 2 hours, and introducing 10% (v/v) H in the reaction process2And soaking and stirring the reaction product in excessive 4.0 wt% hydrofluoric acid for 2 hours after the reaction of the/Ar mixed gas, filtering, and naturally drying to obtain the target product, namely the three-dimensional mesoporous carbon loaded molybdenum carbide.
An XRD pattern of the three-dimensional mesoporous carbon supported molybdenum carbide obtained in this example is shown in fig. 3, and characteristic peaks of XRD of the three-dimensional mesoporous carbon supported molybdenum carbide are 34.3 °, 37.7 °, 39.3 °, 52.1 °, 61.5 °, 69.4 °, 72.4 °, 74.6 ° and 75.5 °, which correspond to β -Mo, respectively2The (100), (002), (101), (102), (110), (103), (200), (112) and (201) crystal planes of C. The characteristic peak of 24.9 ° corresponds to the (002) crystal face of graphitized carbon.
An SEM image of the three-dimensional mesoporous carbon-supported molybdenum carbide obtained in this example is shown in fig. 4, and the three-dimensional mesoporous carbon-supported molybdenum carbide composite material has an obvious ordered mesoporous structure.
The polarization curve of the three-dimensional mesoporous carbon loaded molybdenum carbide obtained in this example is shown in fig. 5, and the current generated by the three-dimensional mesoporous carbon loaded molybdenum carbide is-10 mA cm-2The corresponding bias voltage was-193 mV.
Example 4
The preparation method of the three-dimensional mesoporous carbon supported molybdenum carbide of the embodiment includes the following specific preparation steps:
dissolving 5.0g of soluble ammonium molybdate in deionized water, adding 20.0g of citric acid, adding 40g of silicon dioxide dispersion liquid (the content of silicon dioxide is 40 wt%, and the particle size of the silicon dioxide is 15 +/-5 nm) after the ammonium molybdate is completely dissolved, adjusting the pH value of the solution to be 1.5 by using ammonia water, stirring and evaporating at 70 ℃ for 12 hours to obtain gel, further dehydrating the gel at 200 ℃ for 12 hours to obtain dried gel, uniformly grinding the dried gel, putting the dried gel into a tubular furnace for carbonization reduction at 900 ℃ for 4 hours, and introducing 10% (v/v) H in the reaction process2And soaking and stirring the reaction product in excessive 4.0 wt% hydrofluoric acid for 4 hours after the reaction of the/Ar mixed gas is finished, filtering, and naturally drying to obtain the target product, namely the three-dimensional mesoporous carbon loaded molybdenum carbide.
An SEM image of the three-dimensional mesoporous carbon-supported molybdenum carbide obtained in this example is shown in fig. 6, and the three-dimensional mesoporous carbon-supported molybdenum carbide composite material has an obvious ordered mesoporous structure.
The TEM image of the molybdenum carbide supported by the three-dimensional mesoporous carbon obtained in this example is shown in FIG. 7, and the particle size of the molybdenum carbide supported by the three-dimensional mesoporous carbon is about 2-4 nm.
The polarization curve of the three-dimensional mesoporous carbon loaded molybdenum carbide obtained in this example is shown in fig. 8, and the current generated by the three-dimensional mesoporous carbon loaded molybdenum carbide is-10 mA cm-2The corresponding bias was-167 mV.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (7)
1. A preparation method of three-dimensional mesoporous carbon loaded molybdenum carbide is characterized by comprising the following steps:
(1) preparing a gel: dissolving soluble molybdenum salt in water, adding an organic carbon source and a template agent, uniformly mixing to obtain a mixed solution, adjusting the pH value of the mixed solution to 0-7, heating and stirring to evaporate the mixed solution to dryness to obtain gel, and further heating and dehydrating the gel to obtain dry gel;
(2) preparing three-dimensional mesoporous carbon loaded molybdenum carbide: uniformly grinding the xerogel obtained in the step (1), putting the xerogel into a tubular furnace for high-temperature carbonization and reduction, introducing argon/hydrogen mixed gas in the reaction process, and soaking the obtained product with acid after the reaction is finished to obtain a target product, namely the three-dimensional mesoporous carbon loaded molybdenum carbide; the molybdenum carbide in the three-dimensional mesoporous carbon-loaded molybdenum carbide is MoC;
the organic carbon source in the step (1) is diammonium hydrogen citrate;
the template agent in the step (1) is silicon dioxide or magnesium oxide;
the soluble molybdenum salt in the step (1) is ammonium molybdate;
the dosage of the soluble molybdenum salt, the organic carbon source and the template agent in the step (1) meets the following requirements: the mass ratio of the organic carbon source to the soluble molybdenum salt is 2.5: 1; the mass ratio of the organic carbon source to the template agent is (1-3) to 1;
the high-temperature carbonization reduction in the step (2) refers to carbonization reduction at 900 ℃ for 2 h;
the volume content of hydrogen in the argon/hydrogen mixed gas in the step (2) is 5%.
2. The method for preparing the three-dimensional mesoporous carbon supported molybdenum carbide according to claim 1, wherein the method comprises the following steps:
the particle size of the template agent in the step (1) is 10-1000 nm.
3. The method for preparing the three-dimensional mesoporous carbon supported molybdenum carbide according to claim 1, wherein the method comprises the following steps:
the heating and stirring in the step (1) are heating to 60-80 ℃, and stirring for reaction for 4-24 hours;
the step (1) of further heating for dehydration refers to heating to 100-200 ℃ for reaction for 4-24 hours.
4. The method for preparing the three-dimensional mesoporous carbon supported molybdenum carbide according to claim 1, wherein the method comprises the following steps:
the acid in the step (2) is one of hydrofluoric acid and hydrochloric acid with the concentration of 2-8 wt%;
the soaking in the step (2) refers to soaking for 1-48 hours.
5. The three-dimensional mesoporous carbon supported molybdenum carbide prepared by the method according to any one of claims 1 to 4.
6. Use of the three-dimensional mesoporous carbon supported molybdenum carbide according to claim 5 as an electrocatalytic material.
7. The application of the three-dimensional mesoporous carbon supported molybdenum carbide of claim 5 as an electrocatalytic material in catalyzing water to produce hydrogen.
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| CN113731466B (en) * | 2021-08-31 | 2024-01-05 | 岭南师范学院 | MoC/nitrogen doped carbon/g-C 3 N 4 Composite photocatalyst, preparation and application thereof |
| CN114733540B (en) * | 2022-03-30 | 2023-06-06 | 华南农业大学 | Nanoscale carbon-coated Mo-Mo 2 Heterogeneous nanoparticle of C and preparation method and application thereof |
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