CN114522706A - Carbide-supported noble metal monatomic catalyst, and preparation and application thereof - Google Patents
Carbide-supported noble metal monatomic catalyst, and preparation and application thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 57
- 229910000510 noble metal Inorganic materials 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000001257 hydrogen Substances 0.000 claims abstract description 26
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 21
- 239000002253 acid Substances 0.000 claims abstract description 19
- 239000012621 metal-organic framework Substances 0.000 claims abstract description 18
- 239000002243 precursor Substances 0.000 claims abstract description 17
- 230000000694 effects Effects 0.000 claims abstract description 16
- 239000011964 heteropoly acid Substances 0.000 claims abstract description 14
- 238000010438 heat treatment Methods 0.000 claims abstract description 7
- 238000004519 manufacturing process Methods 0.000 claims abstract description 7
- 238000005530 etching Methods 0.000 claims abstract description 6
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims description 12
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- 150000001879 copper Chemical class 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 235000001014 amino acid Nutrition 0.000 claims description 6
- 150000001413 amino acids Chemical class 0.000 claims description 6
- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical compound O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
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- 229910052786 argon Inorganic materials 0.000 claims description 4
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 4
- 235000013922 glutamic acid Nutrition 0.000 claims description 4
- 239000004220 glutamic acid Substances 0.000 claims description 4
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- XUJNEKJLAYXESH-REOHCLBHSA-N L-Cysteine Chemical compound SC[C@H](N)C(O)=O XUJNEKJLAYXESH-REOHCLBHSA-N 0.000 claims description 2
- WHUUTDBJXJRKMK-VKHMYHEASA-N L-glutamic acid Chemical compound OC(=O)[C@@H](N)CCC(O)=O WHUUTDBJXJRKMK-VKHMYHEASA-N 0.000 claims description 2
- KDXKERNSBIXSRK-YFKPBYRVSA-N L-lysine Chemical compound NCCCC[C@H](N)C(O)=O KDXKERNSBIXSRK-YFKPBYRVSA-N 0.000 claims description 2
- KDXKERNSBIXSRK-UHFFFAOYSA-N Lysine Natural products NCCCCC(N)C(O)=O KDXKERNSBIXSRK-UHFFFAOYSA-N 0.000 claims description 2
- 239000004472 Lysine Substances 0.000 claims description 2
- 229910021604 Rhodium(III) chloride Inorganic materials 0.000 claims description 2
- 239000012298 atmosphere Substances 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 2
- 235000018417 cysteine Nutrition 0.000 claims description 2
- XUJNEKJLAYXESH-UHFFFAOYSA-N cysteine Natural products SCC(N)C(O)=O XUJNEKJLAYXESH-UHFFFAOYSA-N 0.000 claims description 2
- 238000003837 high-temperature calcination Methods 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 235000018977 lysine Nutrition 0.000 claims description 2
- 150000002736 metal compounds Chemical class 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 238000005580 one pot reaction Methods 0.000 claims description 2
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 claims description 2
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 claims description 2
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims description 2
- DANYXEHCMQHDNX-UHFFFAOYSA-K trichloroiridium Chemical compound Cl[Ir](Cl)Cl DANYXEHCMQHDNX-UHFFFAOYSA-K 0.000 claims description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims 3
- 238000000354 decomposition reaction Methods 0.000 claims 1
- 238000003487 electrochemical reaction Methods 0.000 claims 1
- 230000001747 exhibiting effect Effects 0.000 claims 1
- 239000002105 nanoparticle Substances 0.000 abstract description 14
- 229910052751 metal Inorganic materials 0.000 abstract description 8
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- 238000001338 self-assembly Methods 0.000 abstract description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 22
- 229910052697 platinum Inorganic materials 0.000 description 9
- 229910039444 MoC Inorganic materials 0.000 description 8
- QIJNJJZPYXGIQM-UHFFFAOYSA-N 1lambda4,2lambda4-dimolybdacyclopropa-1,2,3-triene Chemical compound [Mo]=C=[Mo] QIJNJJZPYXGIQM-UHFFFAOYSA-N 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 5
- 238000005470 impregnation Methods 0.000 description 4
- 238000011065 in-situ storage Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 229910052723 transition metal Inorganic materials 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 239000012300 argon atmosphere Substances 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 239000013110 organic ligand Substances 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- 150000003624 transition metals Chemical class 0.000 description 3
- 238000004873 anchoring Methods 0.000 description 2
- 238000000840 electrochemical analysis Methods 0.000 description 2
- 229910021397 glassy carbon Inorganic materials 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
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- 238000009827 uniform distribution Methods 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- YZCKVEUIGOORGS-UHFFFAOYSA-N Hydrogen atom Chemical compound [H] YZCKVEUIGOORGS-UHFFFAOYSA-N 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
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- 230000005518 electrochemistry Effects 0.000 description 1
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- 229910002804 graphite Inorganic materials 0.000 description 1
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- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 238000005381 potential energy Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000000851 scanning transmission electron micrograph Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- -1 transition metal carbides Chemical class 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
- 238000005406 washing Methods 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—
-
- B01J35/61—
-
- 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
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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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
- Y02P20/133—Renewable energy sources, e.g. sunlight
Abstract
The invention relates to a preparation method of a carbide supported noble metal single-atom catalyst, belonging to the technical field of electrocatalytic materials. Solves the technical problems of high preparation cost and low metal utilization rate of the prior noble metal catalyst for electrochemical hydrogen production reaction. In the synthesis process of the metal organic framework precursor, noble metal ions are introduced to be complexed with heteropoly acid, the heteropoly acid is embedded into the organic framework pore canal in a self-assembly mode, and the precursor is subjected to high-temperature heat treatment and acid etching to obtain the carbide supported noble metal monatomic catalyst. The result shows that the supported noble metal is uniformly dispersed on the carbide nano-particles in a monoatomic form. The catalyst shows good activity in alkaline electrochemical hydrogen evolution reaction. The preparation process of the catalyst provided by the invention is simple and easy to implement, the utilization rate of noble metal is obviously improved, the cost of the electrocatalyst is effectively reduced, and the catalyst has wide application prospect.
Description
Technical Field
The invention belongs to the technical field of catalyst preparation and electrochemistry, relates to a preparation method of an electrocatalyst applied to an electrochemical hydrogen evolution reaction, and particularly relates to a preparation method of a carbide supported noble metal monatomic catalyst.
Background
Currently, the development and utilization of clean energy is greatly promoted by energy and environmental issues, and the renewable hydrogen energy with high energy density is a potential energy carrier capable of replacing the traditional fossil fuel. Hydrogen energy will play an important role in the future energy landscape, and its development and application have great strategic significance. Among a plurality of hydrogen production technologies, the water electrolysis hydrogen production is environment-friendly and has high product purity, and is one of the best ways to lead to the future 'hydrogen economy'. At present, a platinum-based catalyst is still the optimal choice for the industrial electrocatalytic hydrogen production reaction, but a noble metal catalyst inevitably faces the problems of low natural reserves, high price and the like. To meet this challenge, development and research of low-cost and high-activity electrocatalytic hydrogen evolution reaction catalysts have been layered in recent years. Among them, noble metals (Pt, Pd, Rh) and transition metal carbides (MoC)x、WCx、TiCx) The bimetallic catalyst formed is considered to be one of the most promising hydrogen-producing catalysts, which can realize high activity under the condition of greatly reducing the loading of noble metals. However, in most cases, the preparation process of the carbide is harsh and easy to aggregate, the noble metal is also more prone to form nano particles, more electrochemically active sites are difficult to expose, and the improvement of hydrogen production activity and stability are seriously influenced.
In recent years, monatomic catalysts have become one of the effective strategies to maximize the utilization of noble metals. Because the noble metal and the carbide have stronger interaction, the carbide becomes an ideal carrier for dispersing the single atoms of the noble metal. Through the unsaturated environment of the metal active sites and the strong interaction between the metal and the carrier, the transition metal carbide promoted by the noble metal monoatomic atoms becomes the excellent choice of the novel hydrogen-producing electrocatalyst with low cost and high activity. However, the practical application still highly depends on the development of a new synthesis method, which can realize the preparation of highly dispersed carbide and stably anchor the noble metal monoatomic atom on the carbide without the need of a tedious preparation process.
It is worth noting that Metal-organic Frameworks (MOFs) have specific topology and porous structure and large specific surface area, the selection range for preparing Metal ions and organic ligands of the MOFs is wide, and various functional composite materials derived by taking the MOFs as a precursor have wide application prospects. By utilizing the MOFs derivation auxiliary method, the catalyst can inherit the hierarchical nano-geometric structure and the higher specific surface area of the MOFs, can realize the uniform distribution of active sites, and has great potential in the field of energy catalysis application.
Disclosure of Invention
The invention aims to realize a preparation method of a carbide supported noble metal monatomic catalyst.
The invention is realized by the following technical scheme:
the preparation method comprises the steps of taking heteropoly acid, copper salt, amino acid, trimesic acid and noble metal salt as raw materials, synthesizing a metal organic framework/noble metal compound precursor by a one-pot method, treating at the high temperature of 700-1000 ℃ for 1-8 h under the protection of inert gas, cooling to room temperature, and etching away Cu by acid to obtain the carbide supported noble metal monoatomic hydrogen evolution electrocatalyst.
In the technical scheme, the heteropoly acid is one or two of phosphotungstic acid and phosphomolybdic acid.
In the above technical solution, the copper salt may be any one or more than two of copper chloride, copper nitrate and copper acetate.
In the above technical scheme, the amino acid may be any one or more than two of glutamic acid, lysine and cysteine.
In the above technical scheme, the noble metal salt may be any one of chloroplatinic acid, iridium chloride, palladium nitrate, palladium chloride, ruthenium trichloride, and rhodium trichloride.
In the technical scheme, the molar ratio of the copper salt to the amino acid to the trimesic acid is 500:300: 1-2000: 100:1, and the preferable range is 600:300: 1-900: 300: 1; the molar ratio of the heteropoly acid to the noble metal salt is 1: 1-30: 1, and the preferable range is 1: 1-15: 1.
In the technical scheme, the preferred temperature range of high-temperature calcination is 700-900 ℃; the preferable time is 2-6 h; the atmosphere is any one or more than two of nitrogen or argon.
In the above technical scheme, the acid used for acid etching may be any one of nitric acid, sulfuric acid and hydrochloric acid, and the acid concentration is 0.1-2M, preferably 0.5-1M.
In the technical scheme, the acid used for acid washing can be any one of nitric acid, sulfuric acid and hydrochloric acid, the acid concentration is 0.1-2M, and the preferable acid concentration is 0.5-1M; the temperature is 30-80 ℃, and the preferred range is 50-70 ℃; the time is 1-5 h, and the preferable time is 1-4 h.
The multi-metal organic framework NENU-5 not only has rich pore structures and higher specific surface area, but also can be converted into carbide nanoparticles with ultra-small size and uniform dispersion in situ by the nanometer confinement effect of MOFs organic ligands when the heteropoly acid introduced into the pore channels is calcined at high temperature. Meanwhile, under the strong anchoring action of heteropoly acid in the NENU-5 pore canal, noble metal can be converted into monoatomic atoms in situ during high-temperature heat treatment and uniformly dispersed on carbide nanoparticles, so that a three-dimensional conductive carbon matrix structure derived from MOFs is embedded on the transition metal carbide nanoparticles together with the monoatomic atoms of the noble metal, and the preparation of the hydrogen evolution electrocatalyst with uniformly dispersed electrochemical active sites is realized. The preparation method has the advantages of simple synthetic process, good repeatability and certain application prospect.
Compared with the prior art, the invention has the following advantages and effects:
1) the invention prepares the carbide-supported noble metal monoatomic electrocatalyst by taking a multi-element metal organic framework as a precursor for the first time, and the catalyst can inherit the hierarchical nano-geometric structure and the higher specific surface area of MOFs and is beneficial to the uniform distribution of active sites.
2) The heteropoly acid introduced into the precursor pore channel can be converted into uniformly dispersed carbide nano particles in situ through the confinement effect of MOFs organic ligand in the high-temperature heat treatment process, and the structural stability of the carbide nano particles can be effectively improved.
3) The strong anchoring effect of the heteropoly acid promotes the in-situ conversion of the noble metal into the monoatomic metal which is uniformly dispersed on the carbide nano-particles to obtain the three-dimensional conductive carbon matrix structure which is derived by the co-embedding of the noble metal monoatomic metal dispersed on the transition metal carbide nano-particles and the MOFs, thereby realizing the successful preparation of the electrochemical hydrogen evolution catalyst with low cost and high activity.
4) The invention has the advantages of simple synthesis process, good repeatability, large specific surface area of the obtained material, developed pores and universal expansibility.
5) The catalyst shows higher electrocatalytic hydrogen evolution activity in an alkaline electrolyte, and is expected to replace commercial 20% Pt/C to realize large-scale production and application in the future.
In summary, the preparation method of the carbide supported noble metal monatomic electrochemical hydrogen evolution catalyst provided by the patent is a very practical and inventive method for preparing the electrocatalytic hydrogen evolution catalyst. Solves the technical problems of high preparation cost and low metal utilization rate of the prior noble metal catalyst for electrochemical hydrogen production reaction. The preparation process of the catalyst provided by the invention is simple and easy to implement, the utilization rate of noble metal is obviously improved, and the cost of the electrocatalyst is effectively reduced. In the synthesis process of the metal organic framework precursor, noble metal ions are introduced to be complexed with heteropoly acid, the complex is embedded into an organic framework pore canal in a self-assembly mode, and the precursor is subjected to high-temperature heat treatment and acid etching to obtain carbide supported noble metal monatomic, so that the efficient electrochemical hydrogen evolution catalyst is created. The preparation method has simple process, greatly limits the agglomeration of carbide nano particles and noble metal single atoms, promotes the uniform dispersion of electrochemical active sites, has good repeatability and is easy for batch production; the result shows that the supported noble metal is uniformly dispersed on the carbide nano-particles in a monoatomic form. The catalyst shows good activity in alkaline electro-catalytic hydrogen evolution reaction and has certain application prospect.
Drawings
FIG. 1.03X-ray diffraction pattern of the catalyst.
FIG. 2.03 scanning transmission electron micrographs of catalysts.
FIGS. 3.03, 10, 12 catalysts and 20% Pt/C and prepared by post-impregnation with 03 catalyst and 0.7 wt% platinum catalyst at 10mV s-1Polarization curve under argon atmosphere at sweep speed。
FIG. 4.15 catalyst, Pd-Mo obtained by impregnation2C-C and 20% Pt/C at 10mVs-1Polarization curve under argon atmosphere at sweep speed.
Detailed Description
The present invention will be described in detail below with reference to specific examples. It is to be understood that the described embodiments are merely exemplary of some, and not necessarily all, embodiments of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments of the present invention without making any creative effort, shall fall within the protection scope of the present invention.
The chemical reagents used in the examples of the present invention are all chemically pure and freely available in the market.
EXAMPLES 01-12 preparation of a platinum monatomic catalyst loaded with molybdenum carbide Using Pt-NENU-5 as a precursor
1) Uniformly mixing phosphomolybdic acid with a certain mass, 0.3g of copper acetate, 0.1g of glutamic acid, 0.2g of trimesic acid and chloroplatinic acid with a certain mass, and stirring to obtain a Pt-NENU-5 precursor;
2) carrying out heat treatment on the Pt-NENU-5 precursor obtained in the step 1) in a tube furnace at the temperature of 2 ℃ for min-1The temperature rising rate is increased to 800 ℃, and the mixture is calcined for 6 hours in the argon atmosphere and naturally cooled to the room temperature;
3) dispersing the catalyst obtained in 2) in 0.5M H2SO4Stirring for 1h at 50 ℃ to prepare Pt1-Mo2The amounts of C-C catalyst, phosphomolybdic acid and chloroplatinic acid used are shown in Table 1.
4) Electrochemical test, adding 4mg of the catalyst prepared in the step 3) into 460. mu.l of alcohol, 500. mu.l of water and 40. mu.l of Nafion mixed solution with the mass concentration of 0.05 percent, carrying out ultrasonic treatment for 30 minutes, dropping 20. mu.l of the catalyst on a glassy carbon electrode, and drying at room temperature. The catalyst loading was 0.4mg cm-2. The glassy carbon electrode is used as a working electrode, the graphite electrode and the silver/silver chloride electrode are respectively used as a counter electrode and a reference electrode, argon is introduced into a 1M KOH solution until the solution is saturated, and the solution is heated to 50mV s-1The scanning speed is circularly scanned for 100 circles in a voltage window of-0.9 to-1.4V, and after a passivation layer on the surface of the electrode is removed, 10mVs is adopted-1The sweep speed of the voltage is in a voltage window of-1.0 to-1.6VPolarization curve testing under argon was performed.
5) The species existence form of the obtained 03 catalyst is characterized by an X-ray diffraction analyzer, as shown in figure 1, wherein the abscissa is diffraction angle, the ordinate is diffraction peak intensity, and no diffraction peak of other metals and related species except the characteristic diffraction peaks of carbon and molybdenum carbide appears. The 03 was characterized by high power transmission electron microscopy, and as shown in fig. 2, the result showed that the molybdenum carbide nanoparticles were uniformly dispersed on the carbon matrix, and no Pt nanoparticles and clusters existed on the surface, indicating that Pt existed in the form of monoatomic or quasi-monoatomic, and the platinum content was 0.7 wt%. The characterization results for the remaining examples are the same as above, all showing that the noble metal is dispersed in the form of a single atom on the carbide nanoparticles. As shown in FIG. 3, the result of the electrocatalytic hydrogen evolution test showed that the initial potential of the 03 catalyst was-0.033V and reached 10mA cm-2The overpotential required for the current density was 0.188V, and compared to the 10(0.3 wt% Pt) and 12(1.2 wt% Pt) samples, examples 01-12 exhibited HER activities that were all far superior to those of the catalyst prepared by the impregnation method with the same platinum content of 0.7 wt%.
TABLE 1 preparation method of molybdenum carbide supported platinum monatomic catalyst using Pt-NENU-5 as precursor
EXAMPLES 13-24 preparation of Pd-NENU-5-PRECURSOR-MOLYBDENUM CARBIDE-SUPPORTED PALLADIUM MONO-ATOMIC CATALYST
1) Uniformly mixing a certain amount of phosphomolybdic acid and palladium chloride, 0.3g of copper acetate, 0.15g of glutamic acid and 0.2g of trimesic acid, and stirring to obtain Pd-NENU-5;
2) carrying out heat treatment on the Pd-NENU-5 precursor obtained in the step 1) in a tube furnace at the temperature of 2 ℃ for min-1The temperature rising rate is increased to 700 ℃, the mixture is calcined for 6 hours in the nitrogen atmosphere, and the temperature is naturally reduced to the room temperature;
3) dispersing the catalyst obtained in 2) in 0.5M H2SO4And stirring for 1h at 50 ℃ to prepare the catalyst. The amounts of phosphomolybdic acid and palladium chloride used are shown in Table 2.
4) The electrochemical test method was the same as in examples 01-12. As shown in FIG. 4, the initial potential of the 15 catalyst was-0.1V, reaching 10mA cm-2The overpotential required was 0.181V and the HER activities of examples 13-24 were all close to commercial 20% Pt/C and superior to the Pd-Mo2C-C catalyst obtained by the impregnation method.
And (3) characterizing the 15 catalysts by using an X-ray diffraction analyzer, wherein the obtained XRD spectrum is the same as that in figure 1, and no characteristic diffraction peaks of other metals and related species appear except the characteristic diffraction peaks of carbon and molybdenum carbide. The X-ray analysis results for all the examples described below were the same as described above.
TABLE 2 preparation method of Pd-NENU-5 precursor-based molybdenum carbide supported palladium single-atom catalyst
The embodiment shows that the molybdenum carbide supported noble metal monatomic electrochemical hydrogen evolution catalyst can be prepared by taking the metal organic framework as the precursor, the construction of the catalyst with low cost, high dispersion and high activity is realized, and the potential industrial application value of the catalyst is fully displayed.
Claims (10)
1. A preparation method of a carbide supported noble metal monatomic catalyst is characterized by comprising the following steps:
the method comprises the steps of taking heteropoly acid, copper salt, amino acid, trimesic acid and noble metal salt as raw materials, synthesizing a metal organic framework/noble metal compound precursor by a one-pot method, carrying out heat treatment on the precursor for 1-8 h at the high temperature of 700-1000 ℃ under the protection of inert gas, cooling to room temperature, and etching Cu by acid to obtain the carbide supported noble metal monoatomic electrochemical hydrogen evolution catalyst.
2. The method of claim 1, wherein: the heteropoly acid is one or two of phosphotungstic acid and phosphomolybdic acid.
3. The method of claim 1, wherein: the copper salt can be any one or more than two of copper chloride, copper nitrate or copper acetate.
4. The method of claim 1, wherein: the amino acid can be any one or more than two of glutamic acid, lysine and cysteine.
5. The method of claim 1, wherein: the noble metal salt can be one or more than two of chloroplatinic acid, iridium chloride, palladium nitrate, palladium chloride, ruthenium trichloride and rhodium trichloride.
6. The production method according to any one of claims 1 to 5, characterized in that: the molar ratio of the copper salt to the amino acid to the trimesic acid is 500:300: 1-2000: 100:1, and the preferable range is 600:300: 1-900: 300: 1; the molar ratio of the heteropoly acid to the copper salt is 10: 1-1: 1, preferably 5: 1-2: 1, and the molar ratio of the heteropoly acid to the noble metal salt is 1: 1-30: 1, preferably 1: 1-15: 1.
7. The method of claim 1, wherein: the preferred temperature range of high-temperature calcination is 700-900 ℃; the preferable time is 2-6 h; the atmosphere is any one or more than two of nitrogen or argon.
8. The method of claim 1, wherein: the acid used for acid etching can be any one of nitric acid, sulfuric acid and hydrochloric acid, the concentration of the acid is 0.1-2M, and the preferable concentration of the acid is 0.5-1M; the temperature is 30-80 ℃, and the preferred range is 50-70 ℃; the time is 1-5 h, and the preferable time is 1-4 h.
9. A catalyst prepared by the method of any one of claims 1 to 8.
10. Use of the catalyst of claim 9 as an electrochemical hydrogen evolution catalyst in electrochemical reactions exhibiting excellent electrocatalytic decomposition water hydrogen evolution activity under alkaline conditions of 0.1-1M KOH and/or NaOH.
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| CN113842936A (en) * | 2021-10-22 | 2021-12-28 | 四川大学华西医院 | Platinum-based single-atom electro-catalytic material and preparation method and application thereof |
| CN115044927A (en) * | 2022-06-18 | 2022-09-13 | 福州大学 | Preparation method and application of carbide-supported metal catalyst |
| CN115259297A (en) * | 2022-09-01 | 2022-11-01 | 国能长源武汉青山热电有限公司 | Electro-catalytic hydrogen evolution catalyst and preparation method and application thereof |
| CN115282997A (en) * | 2022-07-28 | 2022-11-04 | 广州大学 | Carbon-nitrogen material loaded monoatomic copper catalyst and synthesis method and application thereof |
| CN115558953A (en) * | 2022-12-05 | 2023-01-03 | 四川大学 | Molybdenum-based carrier-loaded rhodium metal cluster and preparation method and application thereof |
| CN115807244A (en) * | 2023-02-09 | 2023-03-17 | 四川大学 | Copper-modified ruthenium nanocluster catalytic material and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113842936A (en) * | 2021-10-22 | 2021-12-28 | 四川大学华西医院 | Platinum-based single-atom electro-catalytic material and preparation method and application thereof |
| CN115044927A (en) * | 2022-06-18 | 2022-09-13 | 福州大学 | Preparation method and application of carbide-supported metal catalyst |
| CN115044927B (en) * | 2022-06-18 | 2024-04-05 | 福州大学 | Preparation method and application of carbide supported metal catalyst |
| CN115282997A (en) * | 2022-07-28 | 2022-11-04 | 广州大学 | Carbon-nitrogen material loaded monoatomic copper catalyst and synthesis method and application thereof |
| CN115259297A (en) * | 2022-09-01 | 2022-11-01 | 国能长源武汉青山热电有限公司 | Electro-catalytic hydrogen evolution catalyst and preparation method and application thereof |
| CN115259297B (en) * | 2022-09-01 | 2023-10-03 | 国能长源武汉青山热电有限公司 | Electrocatalytic hydrogen evolution catalyst and preparation method and application thereof |
| CN115558953A (en) * | 2022-12-05 | 2023-01-03 | 四川大学 | Molybdenum-based carrier-loaded rhodium metal cluster and preparation method and application thereof |
| CN115558953B (en) * | 2022-12-05 | 2023-03-24 | 四川大学 | Molybdenum-based carrier-loaded rhodium metal cluster and preparation method and application thereof |
| CN115807244A (en) * | 2023-02-09 | 2023-03-17 | 四川大学 | Copper-modified ruthenium nanocluster catalytic material and preparation method and application thereof |
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