CN110560094A - preparation method of 3D porous cobalt-tin-molybdenum trimetal catalyst - Google Patents
preparation method of 3D porous cobalt-tin-molybdenum trimetal catalyst Download PDFInfo
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- CN110560094A CN110560094A CN201910945297.1A CN201910945297A CN110560094A CN 110560094 A CN110560094 A CN 110560094A CN 201910945297 A CN201910945297 A CN 201910945297A CN 110560094 A CN110560094 A CN 110560094A
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- tin
- molybdenum
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- 239000003054 catalyst Substances 0.000 title claims abstract description 47
- NHPWJPGNEGTOLM-UHFFFAOYSA-N [Mo].[Sn].[Co] Chemical compound [Mo].[Sn].[Co] NHPWJPGNEGTOLM-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910019043 CoSn Inorganic materials 0.000 claims abstract description 25
- 239000002243 precursor Substances 0.000 claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- ZKKLPDLKUGTPME-UHFFFAOYSA-N diazanium;bis(sulfanylidene)molybdenum;sulfanide Chemical compound [NH4+].[NH4+].[SH-].[SH-].S=[Mo]=S ZKKLPDLKUGTPME-UHFFFAOYSA-N 0.000 claims abstract description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 11
- 239000001257 hydrogen Substances 0.000 claims abstract description 11
- 229910052982 molybdenum disulfide Inorganic materials 0.000 claims abstract description 11
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims abstract description 6
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 claims abstract description 4
- XUKVMZJGMBEQDE-UHFFFAOYSA-N [Co](=S)=S Chemical compound [Co](=S)=S XUKVMZJGMBEQDE-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000007772 electrode material Substances 0.000 claims abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 33
- 239000008367 deionised water Substances 0.000 claims description 22
- 229910021641 deionized water Inorganic materials 0.000 claims description 22
- GFHNAMRJFCEERV-UHFFFAOYSA-L cobalt chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Co+2] GFHNAMRJFCEERV-UHFFFAOYSA-L 0.000 claims description 11
- KHMOASUYFVRATF-UHFFFAOYSA-J tin(4+);tetrachloride;pentahydrate Chemical compound O.O.O.O.O.Cl[Sn](Cl)(Cl)Cl KHMOASUYFVRATF-UHFFFAOYSA-J 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 10
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 10
- 229960000999 sodium citrate dihydrate Drugs 0.000 claims description 10
- 238000009826 distribution Methods 0.000 claims description 9
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 9
- 239000011148 porous material Substances 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 8
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 7
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 7
- 229910017052 cobalt Inorganic materials 0.000 claims description 7
- 239000010941 cobalt Substances 0.000 claims description 7
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- 229910052750 molybdenum Inorganic materials 0.000 claims description 7
- 239000011733 molybdenum Substances 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- 239000002135 nanosheet Substances 0.000 claims description 4
- 230000002902 bimodal effect Effects 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 238000000975 co-precipitation Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000004729 solvothermal method Methods 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 239000001509 sodium citrate Substances 0.000 claims 1
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 claims 1
- 238000001291 vacuum drying Methods 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 abstract description 22
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 230000002378 acidificating effect Effects 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- 239000002086 nanomaterial Substances 0.000 abstract description 2
- 230000002195 synergetic effect Effects 0.000 abstract description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 abstract 1
- 238000001354 calcination Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 41
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 23
- 239000010411 electrocatalyst Substances 0.000 description 11
- 239000000047 product Substances 0.000 description 10
- -1 transition metal sulfide Chemical class 0.000 description 8
- 238000005119 centrifugation Methods 0.000 description 7
- 238000001027 hydrothermal synthesis Methods 0.000 description 7
- 229910052961 molybdenite Inorganic materials 0.000 description 7
- 238000004806 packaging method and process Methods 0.000 description 7
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 7
- 239000004810 polytetrafluoroethylene Substances 0.000 description 7
- 239000002244 precipitate Substances 0.000 description 7
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 230000010287 polarization Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229920000557 Nafion® Polymers 0.000 description 1
- 229910008957 Sn—Mo Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- DERZBLKQOCDDDZ-JLHYYAGUSA-N cinnarizine Chemical compound C1CN(C(C=2C=CC=CC=2)C=2C=CC=CC=2)CCN1C\C=C\C1=CC=CC=C1 DERZBLKQOCDDDZ-JLHYYAGUSA-N 0.000 description 1
- 229960000876 cinnarizine Drugs 0.000 description 1
- WDHWFGNRFMPTQS-UHFFFAOYSA-N cobalt tin Chemical compound [Co].[Sn] WDHWFGNRFMPTQS-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910021397 glassy carbon Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000005078 molybdenum compound Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 239000012085 test solution Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
Classifications
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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
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/047—Sulfides with chromium, molybdenum, tungsten or polonium
- B01J27/051—Molybdenum
- B01J27/0515—Molybdenum with iron group metals or platinum group metals
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/613—10-100 m2/g
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
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- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
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- 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
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Abstract
The invention belongs to the technical field of inorganic nano material preparation, and particularly relates to a preparation method of a 3D porous cobalt-tin-molybdenum trimetal catalyst. Which is CoSn (OH)6The precursor and ammonium tetrathiomolybdate are dispersed in water, and the 3D porous cobalt-tin-molybdenum trimetal catalyst is prepared through hydrothermal and calcination reactions. The catalyst is a porous cubic structure consisting of cobalt disulfide, tin dioxide and molybdenum disulfide. The method has simple synthesis and low cost, and the prepared 3D porous cobalt-tin-molybdenum trimetal compound combines the sulfide with high catalytic activity and the oxide with good conductivity, and can exert the functions between the compoundsThe synergistic effect of (1) and the improvement of various performances. The catalyst is used as an electrode material for preparing hydrogen by catalyzing and electrolyzing water under an acidic condition, and has a good application prospect.
Description
Technical Field
The invention belongs to the technical field of inorganic nano material preparation, and particularly relates to a preparation method of a 3D porous cobalt-tin-molybdenum trimetal catalyst.
background
Hydrogen energy is one of the most promising and clean energy sources to replace fossil fuels because of its high energy density, environmental friendliness and renewability. Wherein, the hydrogen production by water electrolysis is a convenient hydrogen production method, which does not pollute the environment and the obtained hydrogen product has high purity. At present, the best electro-catalyst for catalyzing and electrolyzing water to prepare hydrogen is platinum and platinum-based materials, but the electro-catalyst has high cost, scarce resources and poor durability, and greatly hinders the wide application of the electro-catalyst. Therefore, it is urgent to find a non-noble metal electrocatalyst with high efficiency, low cost and abundant reserves.
As a typical transition metal sulfide material, MoS2The catalyst is considered to be one of the most promising catalysts in electrocatalytic Hydrogen Evolution (HER) due to the characteristics of low price, high stability, good catalytic performance and the like. Theoretical calculation and experiment prove that MoS2Mainly present in the MoS alone2The position of the edges of a small part of the body greatly limits its electrocatalytic activity. Furthermore, MoS2Conductivity also limits its electrocatalytic properties. Increase of MoS2The intrinsic activity and the number of active sites of (A) is to increase the MoS2Two effective ways of electrocatalytic efficiency, namely constructing a heterostructure, is an effective way to improve MoS2A method of electrocatalytic activity. For example, in the lugguan CN 201910480011.7 patent, which relates to the preparation of a nickel-doped molybdenum disulfide electrocatalyst, the doping of nickel can improve the electrical conductivity of the material, and thus improve its HER catalytic performance. But the heterostructures constructed by this method are limited to the introduction of only highly conductive species. Further, in the cinnarizine, xijimin CN 201810461343.6, CN 201711024065, X patents, heterostructures containing not only a highly conductive composition but also a highly catalytic composition were constructed, but also the present inventors constructed heterostructuresThe synthesized compound is mainly obtained by physical mixing, the synthesis steps are complicated, and an additional sulfur source is needed. Therefore, designing the composition and morphology of the material by a proper synthesis method to increase the number of active sites and the conductivity of the material, thereby effectively improving the performance of the catalyst is a hot spot of current research.
Disclosure of Invention
the invention aims to solve the defects in the prior art, and provides a preparation method of a 3D porous cobalt-tin-molybdenum trimetal catalyst with low cost and good performance, which is simple to synthesize and low in cost, and the prepared 3D porous cobalt-tin-molybdenum trimetal catalyst has excellent HER performance under an acidic condition.
the 3D porous cobalt ~ tin ~ molybdenum trimetal catalyst has a bimodal pore size distribution, the pore size distribution is 3 ~ 5 nm and 10 ~ 20 nm, and the specific surface area of the 3D porous cobalt ~ tin ~ molybdenum trimetal catalyst is 50 ~ 80 m2 g−1。
The preparation method comprises the following steps:
1) Dissolving cobalt chloride hexahydrate, tin chloride pentahydrate and sodium citrate dihydrate in a water-alcohol solution with a volume ratio of 7:1, then dropwise adding a sodium hydroxide solution, stirring at room temperature for 0.5h for coprecipitation reaction, centrifuging, washing, and drying in vacuum to obtain cubic CoSn (OH)6A precursor;
2) Mixing the obtained CoSn (OH)6mixing the precursor and ammonium tetrathiomolybdate according to the mass ratio of 1:0.5 ~ 2, dispersing the mixture in deionized water to enable the concentration of a solute to be 2.5 ~ 5 g/L, carrying out thermal reaction on the mixture for a period of time, centrifuging, washing, and drying in vacuum to obtain a dried product;
3) preserving the heat of the dried product obtained in the step 2) for 2 hours at 350-450 ℃ in a nitrogen atmosphere to obtain the 3D porous cobalt-tin-molybdenum trimetal catalyst.
in the step 1), the molar ratio of cobalt chloride hexahydrate, tin chloride pentahydrate and sodium citrate dihydrate is = 1:0.5 ~ 1.
the volume of the added sodium hydroxide in the step 1) is 20 ~ 30 mL, and the molar concentration is 2 mol/L.
Step 2) CoSn (OH)6the mass ratio of the precursor to the ammonium tetrathiomolybdate is 1:0.5 ~ 2.
in the step 2), the temperature of the solvothermal reaction is 160 ℃, and the reaction time is 6 ~ 12 h.
Furthermore, the 3D porous cobalt-tin-molybdenum trimetal catalyst disclosed by the invention is applied to preparation of an electrode material for catalyzing hydrogen evolution, and the 3D porous cobalt-tin-molybdenum trimetal catalyst has excellent performance in preparation of hydrogen by electrolyzing water under an acidic condition.
The invention has the following beneficial effects:
(1) The method has the advantages of wide raw material source, low cost, simple synthesis steps, short experimental period and good repeatability, and is beneficial to wide application.
(2) In the three-metal catalyst of the 3D porous cobalt-tin-molybdenum provided by the invention, high-conductivity SnO2With highly catalytically active CoS2and MoS2The heterostructure of (a) can exert a synergistic effect and increase the conductivity of the compound, and can improve the catalytic efficiency of the compound.
(3) The 3D porous cobalt-tin-molybdenum trimetal catalyst provided by the invention is internally formed by stacking particles, is mainly covered by short nanosheets on the outside, has two specific surface areas with relatively high pore size distribution, and is favorable for the diffusion of electrolyte and gas desorption.
(4) When the 3D porous cobalt-tin-molybdenum trimetal catalyst provided by the invention is tested in an acidic test solution for 8 hours, the current density is basically kept unchanged, and the 3D porous cobalt-tin-molybdenum trimetal catalyst has excellent stability.
Drawings
FIG. 1 shows CoSn (OH) produced under the conditions of example 36and SEM images of cobalt tin molybdenum trimetal compounds: wherein (a) and (b) CoSn (OH)6SEM pictures of (a), (c) and (d) cobalt tin molybdenumSEM image of trimetallic compound.
FIG. 2 is a TEM image of a cobalt tin molybdenum trimetallic compound prepared under the conditions of example 3.
Figure 3 is an XRD profile of the cobalt tin molybdenum trimetallic compound prepared under the conditions of example 3.
FIG. 4 is a nitrogen adsorption-desorption curve of the cobalt-tin-molybdenum trimetal compound prepared under the conditions of example 3
FIG. 5 is a plot of the pore size distribution of the cobalt tin molybdenum trimetallic compound prepared under the conditions of example 3.
FIG. 6 shows that the cobalt-tin-molybdenum trimetal compound prepared under the conditions of Pt/C and example 3 is used as an electrocatalyst at 0.5M H2SO4Linear scan polarization curve of (1).
FIG. 7 is a Tafel curve fitted to a polarization curve of a cobalt tin molybdenum oxy trimetal compound prepared under Pt/C and example 3 as an electrocatalyst.
FIG. 8 is a chronoamperometric curve of a cobalt tin molybdenum oxy trimetal compound prepared under the conditions of example 3 as an electrocatalyst at an overpotential of 201 mV.
Detailed Description
For better understanding of the present invention, the present invention will be described in detail below with reference to specific examples, but the present invention is not limited thereto.
Example 1:
1 mmol of cobalt chloride hexahydrate and 0.5 mmol of sodium citrate dihydrate were dissolved in 35 mL of deionized water and stirred for several minutes. Then, 5mL of an ethanol solution containing 1 mmol of tin chloride pentahydrate was added thereto and stirred until the solution was sufficiently mixed. Subsequently, 30 mL of 2M sodium hydroxide solution was added dropwise. The reaction was stirred at room temperature for 0.5 h. Finally, the final pink precipitate was collected by centrifugation and washed several times with deionized water and absolute ethanol, respectively, and then dried under vacuum at 50 ℃ for 12h to give cubic CoSn (OH)6And (3) precursor. 50 mg of the above cubic CoSn (OH)6Dispersing the precursor and 25 mg ammonium tetrathiomolybdate in 30 mL deionized water, packaging the solution in a polytetrafluoroethylene reaction kettle after the solution is sufficiently dispersed, carrying out hydrothermal reaction at 160 ℃ for 8 hours, centrifuging, washing,And (5) drying in vacuum. And (3) preserving the obtained dried product for 2 hours at 350 ℃ in a nitrogen atmosphere to obtain the 3D porous cobalt-tin-molybdenum trimetal catalyst.
Example 2:
1 mmol of cobalt chloride hexahydrate and 0.75 mmol of sodium citrate dihydrate were dissolved in 35 mL of deionized water and stirred for several minutes. Then, 5mL of an ethanol solution containing 1 mmol of tin chloride pentahydrate was added thereto and stirred until the solution was sufficiently mixed. Subsequently, 25 mL of 2M sodium hydroxide solution was added dropwise. The reaction was stirred at room temperature for 0.5 h. Finally, the final pink precipitate was collected by centrifugation and washed several times with deionized water and absolute ethanol, respectively, and then dried under vacuum at 50 ℃ for 12h to give cubic CoSn (OH)6And (3) precursor. 50 mg of the above cubic CoSn (OH)6Dispersing the precursor and 25 mg ammonium tetrathiomolybdate in 30 mL deionized water, packaging the solution in a polytetrafluoroethylene reaction kettle after the solution is sufficiently dispersed, carrying out hydrothermal reaction at 160 ℃ for 10 hours, centrifuging, washing and drying in vacuum. And (3) preserving the obtained dried product for 2 hours at the temperature of 400 ℃ in a nitrogen atmosphere to obtain the 3D porous cobalt-tin-molybdenum trimetal catalyst.
example 3:
1 mmol of cobalt chloride hexahydrate and 1 mmol of sodium citrate dihydrate were dissolved in 35 mL of deionized water and stirred for several minutes. Then, 5mL of an ethanol solution containing 1 mmol of tin chloride pentahydrate was added thereto and stirred until the solution was sufficiently mixed. Subsequently, 20 mL of 2M sodium hydroxide solution was added dropwise. The reaction was stirred at room temperature for 0.5 h. Finally, the final pink precipitate was collected by centrifugation and washed several times with deionized water and absolute ethanol, respectively, and then dried under vacuum at 50 ℃ for 12h to give cubic CoSn (OH)6And (3) precursor. 50 mg of the above cubic CoSn (OH)6Dispersing the precursor and 50 mg ammonium tetrathiomolybdate in 30 mL deionized water, packaging the solution in a polytetrafluoroethylene reaction kettle after the solution is sufficiently dispersed, carrying out hydrothermal reaction at 160 ℃ for 6 hours, centrifuging, washing and drying in vacuum. Keeping the obtained dried product at 450 ℃ for 2h in a nitrogen atmosphere to obtain the 3D porous cobalt-tinmolybdenum trimetallic catalysts.
preparing an electrocatalyst working electrode:
2 mg of catalyst and 40 mL of Nafion membrane solution (5 wt%) were dispersed in 460 mL of water/ethanol (II) ((III))v/v= 4: 1), and then sonicated for 30 min to form a uniform ink-like solution. Subsequently, 5. mu.L of the mixture was dropped onto a glassy carbon electrode having a diameter of 3 mm (the electrode was polished with a polishing powder before use), and air-dried at room temperature. The loading of the catalyst was about 0.283 mgcm–2。
And (3) electrochemical performance testing:
The performance test of the electrocatalyst adopts a three-electrode system, and the electrolyte is 0.5M H2SO4And (3) solution. The test instrument used the Shanghai Chenghua electrochemical workstation (CHI 660E).
In FIG. 1, (a) and (b) are CoSn (OH)6Can be seen CoSn (OH)6is a nano cube with uniform distribution and smooth surface. (c) And (d) is an SEM image of the cobalt tin molybdenum trimetal compound, and it can be seen that the cobalt tin molybdenum trimetal compound can still maintain the cubic morphology, and the surface is covered by the rough nanosheets.
FIG. 2 is a TEM image of a cobalt-tin-molybdenum trimetal compound, and it can be seen that the cobalt-tin-molybdenum trimetal compound has an internal structure in which a porous structure is formed by stacking a plurality of particles.
Fig. 3 is an XRD pattern of the cobalt tin molybdenum trimetal compound, which can be seen to be a heterostructure of cobalt disulfide, tin dioxide and molybdenum disulfide, indicating successful synthesis of the compound with good crystallinity.
FIG. 4 is a graph showing the adsorption-desorption curves of nitrogen gas for a trimetallic cobalt-tin-molybdenum compound at a relative pressure of 0.5 to 1.0 p/p0And the sample has a type-H3 hysteresis loop which can be classified as a type IV curve, and the existence of a mesoporous structure in the sample is shown. Furthermore, it can be seen that the cobalt tin molybdenum trimetallic compound has a relatively high specific surface area.
FIG. 5 is a pore size distribution curve of cobalt ~ tin ~ molybdenum trimetal, and it can be seen that the cobalt ~ tin ~ molybdenum trimetal compound has a bimodal pore size distribution with pore size distributions of 3 ~ 5 nm and 10 ~ 20 nm.
FIG. 6 shows that the 3D porous Co-Sn-Mo trimetallic catalyst is at 0.5M H2SO4Linear scan polarization curve of (1). The figure shows that: the 3D porous cobalt-tin-molybdenum trimetal compound has hydrogen evolution electrocatalytic performance. Only 201 mV of overpotential is needed to reach 10 mA cm-2The current density of (1).
Fig. 7 is a Tafel slope curve of the 3D porous cobalt tin molybdenum trimetallic catalyst as an electrocatalyst. The figure shows that: the Tafel slope of the 3D porous cobalt-tin-molybdenum trimetallic catalyst is 69 mV dec-1It is demonstrated to have faster catalytic kinetics.
FIG. 8 is a chronoamperometric curve of the 3D porous cobalt tin molybdenum trimetallic catalyst at an overpotential of 201 mV. In the continuous polarization process for 8 hours under the constant overpotential, the polarization current is basically kept unchanged, which shows that the 3D porous cobalt-tin-molybdenum trimetal catalyst has higher electrocatalytic activity and stability in an acid solution.
Example 4:
1 mmol of cobalt chloride hexahydrate and 1 mmol of sodium citrate dihydrate were dissolved in 35 mL of deionized water and stirred for several minutes. Then, 5mL of an ethanol solution containing 1 mmol of tin chloride pentahydrate was added thereto and stirred until the solution was sufficiently mixed. Subsequently, 20 mL of 2M sodium hydroxide solution was added dropwise. The reaction was stirred at room temperature for 0.5 h. Finally, the final pink precipitate was collected by centrifugation and washed several times with deionized water and absolute ethanol, respectively, and then dried under vacuum at 50 ℃ for 12h to give cubic CoSn (OH)6And (3) precursor. 50 mg of the above cubic CoSn (OH)6dispersing the precursor and 50 mg ammonium tetrathiomolybdate in 30 mL deionized water, packaging the solution in a polytetrafluoroethylene reaction kettle after the solution is sufficiently dispersed, carrying out hydrothermal reaction at 160 ℃ for 12h, centrifuging, washing and drying in vacuum. And (3) preserving the obtained dried product for 2h at 450 ℃ in a nitrogen atmosphere to obtain the 3D porous cobalt-tin-molybdenum trimetal catalyst.
Example 5:
1 mmol of cobalt chloride hexahydrate and 1 mmol of sodium citrate dihydrate were dissolved in 35 mL of deionized waterAnd stirred for several minutes. Then, 5mL of an ethanol solution containing 1 mmol of tin chloride pentahydrate was added thereto and stirred until the solution was sufficiently mixed. Subsequently, 20 mL of 2M sodium hydroxide solution was added dropwise. The reaction was stirred at room temperature for 0.5 h. Finally, the final pink precipitate was collected by centrifugation and washed several times with deionized water and absolute ethanol, respectively, and then dried under vacuum at 50 ℃ for 12h to give cubic CoSn (OH)6And (3) precursor. 50 mg of the above cubic CoSn (OH)6Dispersing the precursor and 50 mg ammonium tetrathiomolybdate in 30 mL deionized water, packaging the solution in a polytetrafluoroethylene reaction kettle after the solution is sufficiently dispersed, carrying out hydrothermal reaction at 160 ℃ for 12h, centrifuging, washing and drying in vacuum. And (3) preserving the obtained dried product for 2h at 450 ℃ in a nitrogen atmosphere to obtain the 3D porous cobalt-tin-molybdenum trimetal catalyst.
Example 6:
1 mmol of cobalt chloride hexahydrate and 1 mmol of sodium citrate dihydrate were dissolved in 35 mL of deionized water and stirred for several minutes. Then, 5mL of an ethanol solution containing 1 mmol of tin chloride pentahydrate was added thereto and stirred until the solution was sufficiently mixed. Subsequently, 20 mL of 2M sodium hydroxide solution was added dropwise. The reaction was stirred at room temperature for 0.5 h. Finally, the final pink precipitate was collected by centrifugation and washed several times with deionized water and absolute ethanol, respectively, and then dried under vacuum at 50 ℃ for 12h to give cubic CoSn (OH)6And (3) precursor. 50 mg of the above cubic CoSn (OH)6Dispersing the precursor and 100 mg ammonium tetrathiomolybdate in 30 mL deionized water, packaging the solution in a polytetrafluoroethylene reaction kettle after the solution is sufficiently dispersed, carrying out hydrothermal reaction at 160 ℃ for 8 hours, centrifuging, washing and drying in vacuum. And (3) preserving the obtained dried product for 2 hours at the temperature of 400 ℃ in a nitrogen atmosphere to obtain the 3D porous cobalt-tin-molybdenum trimetal catalyst.
Example 7:
1 mmol of cobalt chloride hexahydrate and 1 mmol of sodium citrate dihydrate were dissolved in 35 mL of deionized water and stirred for several minutes. Then, 5mL of an ethanol solution containing 1 mmol of tin chloride pentahydrate was added thereto and stirred until the solution was sufficiently mixed. Then, one by one25 mL of 2M sodium hydroxide solution was added dropwise. The reaction was stirred at room temperature for 0.5 h. Finally, the final pink precipitate was collected by centrifugation and washed several times with deionized water and absolute ethanol, respectively, and then dried under vacuum at 50 ℃ for 12h to give cubic CoSn (OH)6And (3) precursor. 50 mg of the above cubic CoSn (OH)6dispersing the precursor and 100 mg ammonium tetrathiomolybdate in 30 mL deionized water, packaging the solution in a polytetrafluoroethylene reaction kettle after the solution is sufficiently dispersed, carrying out hydrothermal reaction at 160 ℃ for 10 hours, centrifuging, washing and drying in vacuum. And (3) preserving the obtained dried product for 2h at 450 ℃ in a nitrogen atmosphere to obtain the 3D porous cobalt-tin-molybdenum trimetal catalyst.
Although the present invention has been described in the above-mentioned embodiments, it is to be understood that the present invention may be further modified and changed without departing from the spirit of the present invention, and that such modifications and changes are within the scope of the present invention.
Claims (8)
1. the three ~ metal catalyst is characterized by being of a 3D porous structure consisting of cobalt disulfide, tin dioxide and molybdenum disulfide, the particle size of the three ~ metal catalyst is 200 ~ 250 nm, the three ~ metal catalyst is formed by stacking particles inside the three ~ metal catalyst, the particle size of the three ~ metal catalyst is 10 ~ 20 nm, the outside of the three ~ metal catalyst is wound and covered by nanosheets, and the thickness of the nanosheets is 20 ~ 25 nm.
2. the 3D porous cobalt ~ tin ~ molybdenum trimetal catalyst according to claim 1, wherein the 3D porous cobalt ~ tin ~ molybdenum trimetal catalyst has a bimodal pore size distribution, the pore size distribution is 3 ~ 5 nm and 10 ~ 20 nm, and the specific surface area of the 3D porous cobalt ~ tin ~ molybdenum trimetal catalyst is 50 ~ 80 m2 g−1。
3. A method of preparing a 3D porous cobalt tin molybdenum trimetallic catalyst according to claim 1, comprising the steps of:
1) Cobalt chloride hexahydrate, tin chloride pentahydrate and dihydrateDissolving sodium citrate in water-alcohol solution with volume ratio of 7:1, adding sodium hydroxide solution dropwise, stirring at room temperature for 0.5h for coprecipitation reaction, centrifuging, washing, and vacuum drying to obtain cubic CoSn (OH)6A precursor;
2) Mixing the obtained CoSn (OH)6mixing the precursor and ammonium tetrathiomolybdate according to the mass ratio of 1:0.5 ~ 2, dispersing the mixture in deionized water to enable the concentration of a solute to be 2.5 ~ 5 g/L, carrying out thermal reaction on the mixture for a period of time, centrifuging, washing, and drying in vacuum to obtain a dried product;
3) preserving the heat of the dried product obtained in the step 2) for 2 hours at 350-450 ℃ in a nitrogen atmosphere to obtain the 3D porous cobalt-tin-molybdenum trimetal catalyst.
4. the preparation method of claim 3, wherein the molar ratio of cobalt chloride hexahydrate, tin chloride pentahydrate and sodium citrate dihydrate in step 1) is = 1:0.5 ~ 1.
5. the preparation method according to claim 3, wherein the volume of the sodium hydroxide added in step 1) is 20-30 mL, and the molar concentration is 2 mol/L.
6. the production method according to claim 3, characterized in that: step 2) CoSn (OH)6the mass ratio of the precursor to the ammonium tetrathiomolybdate is 1:0.5 ~ 2.
7. the preparation method according to claim 3, wherein the temperature of the solvothermal reaction in the step 2) is 160 ℃ and the reaction time is 6-12 h.
8. Use of a 3D porous cobalt tin molybdenum trimetallic catalyst according to claim 1 in the preparation of an electrode material for catalysing hydrogen evolution.
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