CN114855180B - Preparation method of polyacid-derived low-platinum-load hydrogen evolution electrocatalyst - Google Patents
Preparation method of polyacid-derived low-platinum-load hydrogen evolution electrocatalyst Download PDFInfo
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 32
- 239000001257 hydrogen Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000010411 electrocatalyst Substances 0.000 title claims abstract description 12
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 56
- 229910039444 MoC Inorganic materials 0.000 claims abstract description 36
- 239000003054 catalyst Substances 0.000 claims abstract description 36
- 238000000034 method Methods 0.000 claims abstract description 25
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 22
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000002243 precursor Substances 0.000 claims abstract description 20
- 239000002131 composite material Substances 0.000 claims abstract description 19
- ZMCCBULBRKMZTH-UHFFFAOYSA-N molybdenum platinum Chemical compound [Mo].[Pt] ZMCCBULBRKMZTH-UHFFFAOYSA-N 0.000 claims abstract description 16
- 150000002751 molybdenum Chemical class 0.000 claims abstract description 12
- 150000003057 platinum Chemical class 0.000 claims abstract description 12
- CTENFNNZBMHDDG-UHFFFAOYSA-N Dopamine hydrochloride Chemical compound Cl.NCCC1=CC=C(O)C(O)=C1 CTENFNNZBMHDDG-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229960001149 dopamine hydrochloride Drugs 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims abstract description 8
- 239000002105 nanoparticle Substances 0.000 claims abstract description 5
- 239000002135 nanosheet Substances 0.000 claims abstract description 5
- 239000002994 raw material Substances 0.000 claims abstract description 5
- 238000004132 cross linking Methods 0.000 claims abstract description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 22
- 229910052697 platinum Inorganic materials 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 239000000243 solution Substances 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 6
- 238000006116 polymerization reaction Methods 0.000 claims description 5
- 230000000379 polymerizing effect Effects 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- QKNYBSVHEMOAJP-UHFFFAOYSA-N 2-amino-2-(hydroxymethyl)propane-1,3-diol;hydron;chloride Chemical class Cl.OCC(N)(CO)CO QKNYBSVHEMOAJP-UHFFFAOYSA-N 0.000 claims description 4
- 239000006185 dispersion Substances 0.000 claims description 4
- 238000011068 loading method Methods 0.000 claims description 4
- 239000012266 salt solution Substances 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- 238000007654 immersion Methods 0.000 claims description 3
- KLFRPGNCEJNEKU-FDGPNNRMSA-L (z)-4-oxopent-2-en-2-olate;platinum(2+) Chemical compound [Pt+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O KLFRPGNCEJNEKU-FDGPNNRMSA-L 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 2
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 2
- 239000011609 ammonium molybdate Substances 0.000 claims description 2
- 229940010552 ammonium molybdate Drugs 0.000 claims description 2
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 235000015393 sodium molybdate Nutrition 0.000 claims description 2
- 239000011684 sodium molybdate Substances 0.000 claims description 2
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 2
- 229910003182 MoCx Inorganic materials 0.000 claims 2
- 239000011261 inert gas Substances 0.000 claims 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical group [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims 1
- 238000007605 air drying Methods 0.000 claims 1
- 235000011114 ammonium hydroxide Nutrition 0.000 claims 1
- 238000005119 centrifugation Methods 0.000 claims 1
- 230000005611 electricity Effects 0.000 claims 1
- 239000007789 gas Substances 0.000 claims 1
- 230000001105 regulatory effect Effects 0.000 claims 1
- 230000003068 static effect Effects 0.000 claims 1
- 238000005406 washing Methods 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- QIJNJJZPYXGIQM-UHFFFAOYSA-N 1lambda4,2lambda4-dimolybdacyclopropa-1,2,3-triene Chemical compound [Mo]=C=[Mo] QIJNJJZPYXGIQM-UHFFFAOYSA-N 0.000 abstract description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052593 corundum Inorganic materials 0.000 abstract description 5
- 239000010431 corundum Substances 0.000 abstract description 5
- 238000000197 pyrolysis Methods 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract description 4
- 230000009881 electrostatic interaction Effects 0.000 abstract description 3
- 238000005470 impregnation Methods 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 abstract 1
- 230000010287 polarization Effects 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 6
- 230000002378 acidificating effect Effects 0.000 description 5
- 238000009826 distribution Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005868 electrolysis reaction Methods 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- DSVGQVZAZSZEEX-UHFFFAOYSA-N [C].[Pt] Chemical compound [C].[Pt] DSVGQVZAZSZEEX-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000002159 nanocrystal Substances 0.000 description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229920000557 Nafion® Polymers 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004769 chrono-potentiometry Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 229910021397 glassy carbon Inorganic materials 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000010606 normalization Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000012916 structural analysis Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- 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
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/055—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
- C25B11/057—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material consisting of a single element or compound
- C25B11/065—Carbon
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
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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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Organic Chemistry (AREA)
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Abstract
The invention provides a polyacid-derived low-platinum-load hydrogen evolution electrocatalyst, which is a hollow carbon sphere-loaded low-platinum-load high-efficiency hydrogen evolution electrocatalyst formed by crosslinking and assembling two-dimensional nanosheets embedded with high-density molybdenum carbide nanoparticles, and belongs to the technical field of electrocatalytic material synthesis. The catalyst is prepared by taking molybdenum salt, dopamine hydrochloride and platinum salt as raw materials and comprises the following steps: (1) preparing an organic-inorganic precursor Mo-PDA by a solution method; (2) Pt is loaded on the surface of a precursor containing molybdate through electrostatic interaction by an impregnation method; (3) Preparation of Pt@MoC by heat treatment method x NC composite: and (3) transferring the product obtained by drying in the step (2) into an alumina corundum crucible, and performing pyrolysis to obtain the hollow carbon spheres formed by crosslinking and assembling the two-dimensional nanosheets embedded with the high-density platinum-molybdenum carbide nanoparticles. The preparation method has the advantages of simple raw materials, simple and feasible preparation process, mass production and reduced catalyst cost while achieving industrial production efficiency.
Description
Technical Field
The application relates to the technical field of electrocatalytic material synthesis, in particular to a preparation method of a polyacid-derived low-platinum-load hydrogen evolution electrocatalyst.
Background
Hydrogen fuel is considered to be the cleanest renewable energy source, being the primary alternative fuel for future energy supplies. Sustainable hydrogen production is an important prerequisite for achieving future hydrogen economy. Electrocatalytic Hydrogen Evolution (HER) has been the subject of extensive research over the last decades as a key step in the production of hydrogen from water electrolysis. At present, platinum (Pt) is considered as an optimal electrode material for hydrogen production by water electrolysis, but most commercial platinum-carbon (Pt/C) catalysts comprise 20wt% and 40wt%, have high cost, few exposed reaction active sites, do not show high intrinsic activity, and have the problems of unstable catalyst interface, short service life and the like.
Disclosure of Invention
The technical problem to be solved by the invention is to break through the bottleneck problems of high platinum content, insufficient utilization of active sites, high price, incapability of mass production, limited service life and the like in the commercial platinum-carbon (Pt/C) catalyst, and introduce a preparation method of the polyacid-derived low-platinum-load hydrogen evolution electrocatalyst.
The invention also aims to introduce a structure and components of the novel high-efficiency hydrogen evolution electrocatalyst capable of effectively reducing the platinum loading, wherein the catalyst is obtained by loading platinum on molybdenum carbide/hollow carbon spheres (platinum-molybdenum carbide/hollow carbon spheres) derived from polyacid, so that the high-efficiency hydrogen evolution electrocatalyst with high active site density, low cost and long service life is obtained.
The invention also aims to take the polyacid-derived platinum-molybdenum carbide/hollow carbon spheres as the low-platinum-carrying-capacity high-efficiency electrocatalytic hydrogen evolution catalyst applicable to the full pH range, realize the reduction of the catalyst cost while achieving the industrial production efficiency, have wide application prospect, and are beneficial to improving the market share of the water electrolysis hydrogen production industry in the aspects of energy conversion and storage.
The above object of the present invention is achieved by the following technical scheme:
the preparation method of the polyacid-derived low-platinum-load hydrogen evolution electrocatalyst is characterized by taking molybdenum salt (Mo), dopamine hydrochloride (DA-HCl) and platinum salt as raw materials, and comprises the following steps of:
(1) Preparing Mo-PDA precursor by solution method: firstly, respectively dissolving molybdenum salt and dopamine hydrochloride in water and ethanol, then rapidly mixing the two solutions, adjusting the pH value, and stirring and polymerizing at room temperature;
(2) Platinum is adsorbed by an immersion method to prepare a Pt-Mo-PDA precursor: uniformly dispersing the Mo-PDA precursor obtained in the step (1), adding a proper amount of platinum salt solution, adsorbing platinum through electrostatic interaction, preparing a Pt-Mo-PDA precursor, and then drying;
(3) Preparation of Pt@MoC by heat treatment method x NC composite: transferring the product obtained by drying in the step (2) into an alumina corundum crucible, and pyrolyzing to obtain Pt@MoC x NC catalyst.
Preferably, the molybdenum salt in the step (1) may be ammonium molybdate and sodium molybdate, but is not limited to the two molybdates, wherein the mass ratio of the molybdenum salt to dopamine hydrochloride is 1:x (0 < x < 10), and the volume ratio of ethanol to water is 1:y (0 < y < 4).
Preferably, the system described in step (1) has a pH of 8 to 9, and the pH adjustor can be, but is not limited to, ammonia and Tris (hydroxymethyl) aminomethane hydrochloride (Tris HCl).
Preferably, the polymerization time in the step (1) is 0.5-24 h, after the polymerization is finished, the mixture is centrifugally washed by ethanol for 2-3 times and then dried under vacuum overnight.
Preferably, the dispersion liquid in the step (2) is ethanol or water, and the platinum salt can be chloroplatinic acid salt and hydrate thereof, platinum acetylacetonate, platinum chloride and hydrate thereof, and potassium chloroplatinite, but is not limited to four platinum salts, and the mass of the platinum salt and Mo-PDA precursor is 1:z (0 < z < 0.5).
Preferably, the programmed heating rate in the step (3) is 5-10 ℃/min, and the high-temperature reduction temperature is 650<T 2 <The pyrolysis time is 1-5 h at 950 ℃.
The beneficial results of the invention are: the invention designs a high-efficiency hydrogen evolution electrocatalyst for synthesizing polyacid-derived platinum-molybdenum carbide/hollow carbon spheres, which is prepared by taking hollow carbon spheres formed by crosslinking two-dimensional nanosheets embedded with highly dispersed polyacid-derived molybdenum carbide nano particles as a substrate for dispersing Pt species, and by virtue of an in-situ and limited reaction strategy in a carbonaceous matrix, aggregation of nanocrystals is effectively prevented, more reactive sites are exposed, and close metal-carrier strong interaction is generated between the Pt species and the nanocrystals and conductive carbon nanosheets.
The electrocatalytic hydrogen evolution performance of the catalyst prepared by the invention is superior to the Pt/C performance of commercial 20wt%, the platinum loading is low, the activity is kept high, the cost is reduced, the activity is kept high, and meanwhile, the problems of unstable catalyst interface, short service life and the like are optimally solved.
The preparation method has the advantages of simple raw materials, simple and feasible preparation process, large-scale production, great significance in reducing the cost of the electrolytic water hydrogen-separating catalyst, improving the hydrogen production efficiency and the like, and wider and optimistic application prospect.
Drawings
FIG. 1 is an X-ray powder diffraction pattern (XRD) of a polyacid-derived platinum-molybdenum carbide/hollow carbon sphere composite catalyst in an embodiment of the invention.
FIG. 2 is a projection electron microscope and element distribution diagram of a platinum-molybdenum carbide/hollow carbon sphere composite catalyst synthesized in an embodiment of the invention.
FIG. 3 is a graph showing the comparison of linear scan polarization curves for normalized catalyst electrode areas according to an embodiment of the present invention, wherein (a) is the polarization curve in an acidic system and (b) is the polarization curve in an alkaline system.
Fig. 4 is a linear scan polarization curve of Pt mass normalized for the composite catalyst in an embodiment of the present invention. Wherein (a) is the polarization curve in an acidic system, and (b) is the polarization curve in an alkaline system.
FIG. 5 is a graph showing the stability test of electrocatalytic hydrogen evolution of the platinum-molybdenum carbide/hollow carbon sphere composite catalyst synthesized in the example of the present invention. Wherein (a) is the polarization curve in an acidic system, and (b) is the polarization curve in an alkaline system.
Detailed Description
The invention will be further illustrated with reference to the drawings and specific examples, but the invention is not limited to the following examples. Unless otherwise indicated, all reagents, methods and apparatus employed in the present invention are those conventional in the art
Example 1
Platinum-molybdenum carbide/hollow carbon sphere composite catalystThe preparation method of (a), the first step: preparing Mo-PDA precursor by solution method: firstly, respectively dissolving molybdenum salt and dopamine hydrochloride in water and ethanol, then rapidly mixing the two solutions, adjusting the pH value, and stirring and polymerizing at room temperature; and a second step of: preparing a Pt-Mo-PDA precursor by adsorbing platinum by an immersion method, uniformly dispersing the Mo-PDA precursor obtained in the first step, adding a proper amount of platinum salt solution, adsorbing platinum by electrostatic interaction, and drying the Pt-Mo-PDA precursor; and a third step of: preparation of MoC by heat treatment x Transferring the product obtained by the second step of drying into an alumina corundum crucible, and preparing Pt@MoC by high-temperature pyrolysis x /NC。
Structural analysis
FIG. 1 is a synthetic platinum-molybdenum carbide/hollow carbon sphere composite catalyst (i.e., pt@MoC x X-ray powder diffraction pattern of/NC), the composition of the synthesized catalyst phases was found to be molybdenum carbide (MoC, PDF#08-0384) and molybdenum carbide (Mo) by comparison with the powder diffraction database standard card 2 C, PDF#35-0787) and platinum metal (Pt, PDF#04-0802).
FIG. 2 is a synthetic platinum-molybdenum carbide/hollow carbon sphere composite catalyst (i.e., pt@MoC x According to the X-ray electron energy spectrum of/NC) and the element content and distribution, wherein figures 2c-2h respectively represent the distribution situation of Mo, pt, C, N, O element in the catalyst material, uniform dispersion of Mo and Pt can be obviously observed, large particles which are obviously aggregated are not seen, the dispersion density of active sites in the catalyst is large, more effective catalytic active sites can be provided per unit area, the dosage of Pt is reduced, and meanwhile, high catalytic activity is ensured.
Performance testing
The prepared catalyst sample is prepared into ink with a certain concentration, the catalyst sample is dispersed in a mixed solution of isopropanol and a perfluorinated sulfonic acid resin film solution (5 wt% Nafion), ultrasonic treatment is carried out for 30 minutes, then the uniformly mixed catalyst ink is dripped on a glassy carbon electrode to be used as a working electrode, and then an electrocatalytic hydrogen evolution performance test is carried out on an electrochemical workstation by adopting a three-electrode method (reversible hydrogen is used as a reference electrode and a carbon rod is used as an auxiliary electrode).
At 0.5 and M H respectively 2 SO 4 And electrocatalytic catalyst in 1.0M KOH electrolyte systemThe hydrogen evolution performance was tested. Wherein, FIG. 3a is a polarization curve under an acidic system, and FIG. 3b is a polarization curve under an alkaline acidic system, which shows that the prepared platinum-molybdenum carbide/hollow carbon composite catalyst material has excellent electrocatalytic hydrogen evolution performance.
According to ICP-AES test, the content of platinum in the platinum-molybdenum carbide hollow carbon sphere composite catalyst synthesized in the embodiment 1 is between 0 and 10wt%, which is far smaller than commercial Pt/C of 20wt% of practical application purchased in the market, and after the mass normalization of platinum contained in the catalyst, the electrocatalytic hydrogen evolution performance is far better than commercial Pt/C from FIG. 4, which shows that the prepared platinum-molybdenum carbide/hollow carbon sphere composite catalyst can expose more active sites, so that the utilization rate of noble metal platinum is higher, the cost is lower under the condition of realizing the same electrocatalytic hydrogen production industrial production efficiency, and the requirement of industrial application can be met.
Stability test of electrocatalyst
The stability of the platinum-molybdenum carbide/hollow carbon sphere composite catalyst was tested by chronopotentiometry, as shown in FIG. 5a, at 0.5MH 2 SO 4 10mAcm in electrolyte medium -2 Hydrogen evolution reaction is carried out for 15 hours under the overpotential corresponding to the current density, the current density of the catalyst is basically kept unchanged, and the catalyst has excellent acid corrosion resistance; FIG. 5b likewise shows 20mAcm in alkaline medium 1MKOH electrolyte -2 Hydrogen evolution reactions were carried out for up to 20 hours at overpotential corresponding to current density, with the current density of the catalyst remaining substantially unchanged. The catalyst has excellent stability in the electrocatalytic hydrogen evolution reaction process in acid-base medium.
Example 2
The first step: preparing Mo-PDA precursor by solution method: firstly, respectively dissolving molybdenum salt and dopamine hydrochloride in water and ethanol, then rapidly mixing the two solutions, adjusting pH, and stirring and polymerizing at room temperature to obtain a Mo-PDA precursor; and a second step of: preparation of MoC by heat treatment x Transferring the product obtained by the first step of drying into an alumina corundum crucible, and preparing MoC by pyrolysis x /NC。
Example 3
The first step: preparation of Mo-PDA precursor by solution method: firstly, respectively dissolving molybdenum salt and dopamine hydrochloride in water and ethanol, then rapidly mixing the two solutions, adjusting pH, and stirring and polymerizing at room temperature to obtain a Mo-PDA precursor; and a second step of: preparation of MoC by heat treatment x Transferring the product obtained by the second step of drying into an alumina corundum crucible, and preparing MoC by pyrolysis x /NC. And a third step of: preparation of MoC by platinum adsorption by impregnation method x Weighing a proper amount of MoC obtained in the first step x Uniformly dispersing NC, adding appropriate amount of platinum salt solution, adsorbing platinum by impregnation method, and adding into H 2 The mixed Ar atmosphere is reduced at low temperature and is marked as Pt-MoC x /NC。
Example 4
A commercial Pt/C of 20wt% was tested for electrocatalytic hydrogen evolution performance and, as a comparison, the test procedure was identical to that of example 1, and was designated Pt/C.
Claims (8)
1. The preparation method of the polyacid-derived low-platinum-loading hydrogen evolution electrocatalyst is a platinum-molybdenum carbide/hollow carbon sphere composite catalyst, and is characterized in that: the preparation method takes molybdenum salt, dopamine hydrochloride and platinum salt as raw materials, and comprises the following steps:
step (1): preparing Mo-PDA precursor by solution method: dissolving the molybdenum salt and the dopamine hydrochloride in water and ethanol respectively, then rapidly mixing the two solutions, regulating the pH value and the room temperature
Stirring and polymerizing;
step (2): platinum is adsorbed by an immersion method to prepare a Pt-Mo-PDA precursor: uniformly dispersing the Mo-PDA precursor obtained in the step (1), adding a proper amount of platinum salt solution, and mutually carrying out static electricity
Adsorbing platinum, preparing a Pt-Mo-PDA precursor, and drying;
step (3): preparing Pt@MoCx/NC composite material by a heat treatment method: and (3) preparing the Pt@MoCx/NC composite material by using the sample obtained in the step (2) through a heat treatment method.
2. The method of claim 1, wherein the molybdenum salt in step (1) is ammonium molybdate or sodium molybdate, wherein the mass ratio of the molybdenum salt to the dopamine hydrochloride is 1:x, 0< x <10, and the volume ratio of the ethanol to the water is 1:y, 0< y < 4.
3. The method according to claim 1, wherein the pH of the system in the step (1) is 8 to 9, and the pH adjustor is ammonia water or tris (hydroxymethyl) aminomethane hydrochloride
Salts (Tris HCl).
4. The process according to claim 1, wherein the polymerization time in the step (1) is 0.5 to 24. 24h, and the polymerization is completed by washing with ethanol for 2 to 3 times by centrifugation, and then the polymerization is completed
Air drying overnight.
5. The method according to claim 1, wherein the dispersion in the step (2) is prepared with ethanol or water, and the platinum salt is one of chloroplatinic acid salt and its hydrate, platinum acetylacetonate, platinum chloride and its hydrate, and potassium chloroplatinite, and the platinum salt is mixed with the Mo-PDA precursor
The mass of the body is 1:z, 0< z < 0.5.
6. The method according to claim 1, wherein the temperature rise rate in the process temperature rise in the step (3) is 5 to 10 ℃/min, the temperature is raised to 700 to 900 ℃ under an inert gas or a reducing atmosphere, and the inert gas is Ar or N, and the temperature is kept at 2 to 5h 2 The reducing atmosphere is Ar/H 2 And (3) mixing the gases.
7. The preparation method of any one of claims 1 to 6, wherein the composite material has a structure of a hollow carbon composite material formed by crosslinking and assembling two-dimensional nanosheets embedded with high-density platinum-molybdenum carbide nanoparticles.
8. The method of any one of claims 1 to 6, wherein the platinum is present in the composite material in the form of one or more of a single atom, a cluster, and a nanoparticle.
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