CN114457375A - Phosphorus-doped molybdenum carbide composite catalyst, preparation method thereof and application of phosphorus-doped molybdenum carbide composite catalyst in electrocatalytic hydrogen evolution - Google Patents
Phosphorus-doped molybdenum carbide composite catalyst, preparation method thereof and application of phosphorus-doped molybdenum carbide composite catalyst in electrocatalytic hydrogen evolution Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 69
- 239000002131 composite material Substances 0.000 title claims abstract description 61
- QIJNJJZPYXGIQM-UHFFFAOYSA-N 1lambda4,2lambda4-dimolybdacyclopropa-1,2,3-triene Chemical compound [Mo]=C=[Mo] QIJNJJZPYXGIQM-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 229910039444 MoC Inorganic materials 0.000 title claims abstract description 55
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 21
- 239000001257 hydrogen Substances 0.000 title claims abstract description 21
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 150000002751 molybdenum Chemical class 0.000 claims abstract description 8
- 239000002028 Biomass Substances 0.000 claims abstract description 7
- 239000000463 material Substances 0.000 claims description 39
- 238000001035 drying Methods 0.000 claims description 11
- 239000007787 solid Substances 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- DSVGQVZAZSZEEX-UHFFFAOYSA-N [C].[Pt] Chemical compound [C].[Pt] DSVGQVZAZSZEEX-UHFFFAOYSA-N 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 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
- 239000000126 substance Substances 0.000 claims description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 238000010000 carbonizing Methods 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
- 239000002002 slurry Substances 0.000 claims description 4
- QGAVSDVURUSLQK-UHFFFAOYSA-N ammonium heptamolybdate Chemical compound N.N.N.N.N.N.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.[Mo].[Mo].[Mo].[Mo].[Mo].[Mo].[Mo] QGAVSDVURUSLQK-UHFFFAOYSA-N 0.000 claims description 3
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 3
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 3
- 239000011609 ammonium molybdate Substances 0.000 claims description 3
- 229940010552 ammonium molybdate Drugs 0.000 claims description 3
- 239000011230 binding agent Substances 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 235000015393 sodium molybdate Nutrition 0.000 claims description 3
- 239000011684 sodium molybdate Substances 0.000 claims description 3
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 3
- 239000002699 waste material Substances 0.000 claims description 3
- 229920000557 Nafion® Polymers 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 239000003792 electrolyte Substances 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 238000011056 performance test Methods 0.000 claims description 2
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 claims 2
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 claims 1
- XBMOWLAOINHDLR-UHFFFAOYSA-N dipotassium;hydrogen phosphite Chemical compound [K+].[K+].OP([O-])[O-] XBMOWLAOINHDLR-UHFFFAOYSA-N 0.000 claims 1
- ZRRLFMPOAYZELW-UHFFFAOYSA-N disodium;hydrogen phosphite Chemical compound [Na+].[Na+].OP([O-])[O-] ZRRLFMPOAYZELW-UHFFFAOYSA-N 0.000 claims 1
- 239000000203 mixture Substances 0.000 claims 1
- 229910001380 potassium hypophosphite Inorganic materials 0.000 claims 1
- 229910000160 potassium phosphate Inorganic materials 0.000 claims 1
- 235000011009 potassium phosphates Nutrition 0.000 claims 1
- CRGPNLUFHHUKCM-UHFFFAOYSA-M potassium phosphinate Chemical compound [K+].[O-]P=O CRGPNLUFHHUKCM-UHFFFAOYSA-M 0.000 claims 1
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims 1
- 239000001488 sodium phosphate Substances 0.000 claims 1
- 229910000162 sodium phosphate Inorganic materials 0.000 claims 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims 1
- 229910052751 metal Inorganic materials 0.000 abstract description 8
- 239000002184 metal Substances 0.000 abstract description 8
- 238000003763 carbonization Methods 0.000 abstract description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052799 carbon Inorganic materials 0.000 abstract description 5
- 230000001360 synchronised effect Effects 0.000 abstract description 4
- 239000002253 acid Substances 0.000 abstract description 3
- 239000010796 biological waste Substances 0.000 abstract description 3
- 239000002243 precursor Substances 0.000 abstract description 3
- 239000012265 solid product Substances 0.000 abstract description 3
- 238000004132 cross linking Methods 0.000 abstract 1
- 238000007711 solidification Methods 0.000 abstract 1
- 230000008023 solidification Effects 0.000 abstract 1
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- 229910052698 phosphorus Inorganic materials 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 238000005406 washing Methods 0.000 description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 239000011574 phosphorus Substances 0.000 description 7
- 230000005540 biological transmission Effects 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000007772 electrode material Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 241000251468 Actinopterygii Species 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000001075 voltammogram Methods 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 239000010431 corundum Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 239000011267 electrode slurry Substances 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 229910021642 ultra pure water Inorganic materials 0.000 description 2
- 239000012498 ultrapure water Substances 0.000 description 2
- 108091005658 Basic proteases Proteins 0.000 description 1
- 229910003178 Mo2C Inorganic materials 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- AAMATCKFMHVIDO-UHFFFAOYSA-N azane;1h-pyrrole Chemical compound N.C=1C=CNC=1 AAMATCKFMHVIDO-UHFFFAOYSA-N 0.000 description 1
- DLGYNVMUCSTYDQ-UHFFFAOYSA-N azane;pyridine Chemical compound N.C1=CC=NC=C1 DLGYNVMUCSTYDQ-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000011263 electroactive material Substances 0.000 description 1
- 239000010411 electrocatalyst Substances 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000000413 hydrolysate Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Inorganic materials O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 1
- 239000002127 nanobelt Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000002074 nanoribbon Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- -1 phosphides Chemical class 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000010301 surface-oxidation reaction Methods 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 150000003623 transition metal compounds Chemical class 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
Images
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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
-
- 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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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a phosphorus-doped molybdenum carbide composite catalyst, a preparation method thereof and application of electrocatalytic hydrogen evolution. The invention takes biological waste as a carbon source and molybdenum salt as a metal source, and obtains a solid product through coordination crosslinking and solidification and synchronous phosphating-carbonization treatment. The preparation method comprises the following steps: after treatment, the biomass is matched and crosslinked with molybdenum salt; obtaining a metal-carbon source precursor through microwave-assisted curing treatment; and carrying out synchronous phosphating-carbonization treatment to obtain the composite material. The results of the examples show that in an alkaline medium, HER of the catalyst provided by the invention only needs 118 mV overpotential to reach 10 mA cm‑2Current density; the overpotential of 172mV required in an acid medium can reach 10 mA cm‑2The current density.
Description
Technical Field
The invention belongs to the technical field of electrocatalysis hydrogen evolution technology, and relates to a phosphorus-doped molybdenum carbide composite catalyst, a preparation method and an electrocatalysis application thereof.
Background
Hydrogen (H)2) Energy source due to itHigh energy density, renewability and zero pollution are considered as the most promising alternatives to fossil fuels. The existing hydrogen energy preparation method mainly comprises coal gasification hydrogen production, industrial byproduct hydrogen production, photocatalytic hydrogen production, electrocatalytic hydrogen production and the like, wherein the electrocatalytic hydrogen production is considered as the most effective and environment-friendly hydrogen production mode. Although electrocatalytic Hydrogen Evolution (HER) reaction is an effective hydrogen production method, there is an urgent need to develop electrocatalysts with excellent performance and high stability in order to improve the economy of hydrogen fuel production. Researchers have been searching for catalysts with performance and stability comparable to those of non-noble metal catalysts to replace platinum-based noble metal catalysts, thereby reducing cost and realizing industrialization.
Transition metal compounds, such as carbides, sulfides, phosphides, nitrides, and the like, have been widely used as electroactive materials in HER electrodes due to their platinum-like d-charge electronic structures. Molybdenum carbide (Mo)2C) Has huge application potential due to the wide pH stability and component adjustability. Increase Mo2Common methods of C performance include increasing active sites and conductivity. To improve Mo2The conductivity of C is usually supported on a conductive support with a high specific surface area. Porous carbon and graphene-based materials are often used as supports to avoid Mo2C nanoparticles aggregate and increase the conductivity of the catalyst. In addition, metals such as Fe, Co, Ni, etc. are usually selected to be doped to improve the conductivity of the catalyst. Another purpose of metal doping is to promote Mo2Electron transfer between C and the doping metal to further enhance HER. On the other hand, Mo2The empty d-orbital band of C strengthens the Mo-H bond and limits its intrinsic activity. In the presence of Mo2The C crystal lattice is doped with non-metal heteroatoms with electronegativity (such as N, S and P) to increase active sites, and especially P doping can reduce Mo2The density of the empty d bands in C weakens the strength of Mo-H bonds to enhance the catalytic activity of the catalyst.
Disclosure of Invention
In view of the above, the invention provides a phosphorus-doped molybdenum carbide composite catalyst, a preparation method thereof and an application of electrocatalytic hydrogen evolution, the composite catalyst provided by the invention takes waste biomass as a carbon source and cheap and abundant metal as a metal source, has simple preparation process, easy operation and economy, and has excellent catalytic performance, higher stability and wider pH range when being used as a HER catalyst.
The invention provides a phosphorus-doped molybdenum carbide composite catalyst material, which has a porous structure; the molybdenum carbide in the phosphorus-doped molybdenum carbide composite catalyst material has low crystallinity and is in a band-shaped structure.
Preferably, the specific surface area of the phosphorus-doped molybdenum carbide composite catalyst is 150-350 m2 g-1。
Preferably, the molybdenum carbide in the phosphorus-doped molybdenum carbide composite catalyst is in an amorphous state and is in a strip shape.
The invention provides a preparation method of the phosphorus-doped molybdenum carbide composite catalyst in the technical scheme, which comprises the following steps: (1) sequentially treating waste fish scales with strong acid and strong alkali solution to remove inorganic substances, washing with secondary water to be neutral, naturally drying, adding alkaline protease and ultrapure water for enzymolysis for 24 hours, and concentrating to obtain concentrated solution; (2) mixing the concentrated solution with molybdenum salt to obtain transparent and clear solution; (3) drying the solution obtained in the step 2 to obtain a solid substance; (4) and (4) synchronously phosphorizing and carbonizing the solid obtained in the step (3) in a high-temperature inert atmosphere to obtain a black product.
Preferably, the molybdenum salt is phosphomolybdic acid, ammonium heptamolybdate, ammonium molybdate, sodium molybdate and the like.
Preferably, the carbonization temperature is 700-900 ℃, the time is 2-5 h, and the temperature rise rate of raising the temperature to the carbonization temperature is 4-12 ℃ min-1。
The invention provides the application of the phosphorus-doped molybdenum carbide composite catalyst material in the technical scheme or the phosphorus-doped molybdenum carbide composite catalyst prepared by the preparation method in the technical scheme in electrocatalysis of HER.
The phosphorus-doped molybdenum carbide composite catalyst material provided by the invention is in a uniform nanoribbon structure, wherein the molybdenum carbide has low crystallinity and large specific surface area. As shown by the results of the examples, the present invention provides phosphorusThe molybdenum carbide doped composite catalyst modified platinum-carbon electrode can reach 10 mA cm in acidic medium by only 172mV of overpotential-2Current density, in alkaline medium, only 118 mV overpotential is needed to reach 10 mA cm-2And the current density is stable after 24-hour durability test.
Drawings
Fig. 1 is a transmission electron microscope image and a scanning electron microscope image of the phosphorus-doped molybdenum carbide composite catalyst material prepared in example 1.
Fig. 2 is an X-ray diffraction pattern of the phosphorus-doped molybdenum carbide composite catalyst material prepared in example 1.
Fig. 3 is a core level region XPS spectrum of Mo 4f of the phosphorus doped molybdenum carbide composite catalyst material prepared in example 1.
Fig. 4 is a core level region XPS spectrum of P2P in a phosphorus doped molybdenum carbide composite catalyst material prepared in example 1.
Fig. 5 is a core level region XPS spectrum of C1s in a phosphorus doped molybdenum carbide composite catalyst material prepared in example 1.
Fig. 6 is a core level region XPS spectrum of N1s in a phosphorus doped molybdenum carbide composite catalyst material prepared in example 1.
FIG. 7 is a plot of a voltammetric sweep using a phosphorus doped molybdenum carbide composite catalyst material of example 1.
Fig. 8 is a Tafel plot of a phosphorus doped molybdenum carbide composite catalyst material of application example 1.
FIG. 9 is a linear voltammogram scan of the phosphorus-doped molybdenum carbide composite catalyst material of application example 2.
FIG. 10 is a Tafel diagram of a phosphorus-doped molybdenum carbide composite catalyst material in application example 2.
Detailed Description
The invention provides a phosphorus-doped molybdenum carbide composite catalyst material, a preparation method thereof and application of electro-catalysis hydrogen evolution. When used as HER catalyst, it has excellent catalytic activity and stability.
The specific surface area of the phosphorus-doped molybdenum carbide composite catalyst provided by the invention is 150-350 m2 g-1。
Preferably, the phosphorus-doped molybdenum carbide composite catalyst is in a nano-belt structure.
In the present invention, the preparation method of the phosphorus-doped molybdenum carbide composite catalyst material preferably comprises the following steps.
Firstly, the biological waste raw materials are sequentially treated by acid and alkali, and then the liquefied biomass is obtained by enzymolysis.
In the invention, the biological waste raw material is preferably fish scales; in the invention, the biomass raw material is sequentially washed, dried, subjected to acid treatment, subjected to alkali treatment and subjected to enzymolysis to obtain a concentrated solution. In the present invention, the washing is preferably water washing, and the present invention has no particular requirement for the specific implementation of the drying.
Dissolving metal molybdenum salt to obtain a transparent and clear solution, adding the transparent and clear solution into the obtained enzymolysis biomass, drying, and performing high-temperature synchronous phosphating-carbonization treatment to obtain a black solid substance; and grinding the obtained solid matter, washing with ultrapure water and ethanol, and drying to obtain the phosphorus-doped molybdenum carbide composite catalyst material.
In the invention, the metal molybdenum salt comprises phosphomolybdic acid, ammonium heptamolybdate, ammonium molybdate, sodium molybdate and the like, the synchronous phosphorization-carbonization process is a two-step temperature programming process, the first step temperature is preferably 300-450 ℃, the duration is 2-4 h, and the temperature rise speed is preferably 1-10 ℃ for min-1More preferably 2 to 5 ℃ min-1(ii) a The temperature of the second step is preferably 800-1050 ℃, the duration is 2-4 h, and the heating speed is preferably 1-15 ℃ min-1More preferably 5 to 10 ℃ min-1. In the present invention, the protective gas is preferably any one of nitrogen gas and argon gas, or a mixed gas thereof, and more preferably nitrogen gas. The flow rate of the protective atmosphere in the two-step constant temperature process is preferably 80-120 mL min-1More preferably 100 to 115 mL min-1。
The invention preferably carries out post-treatment on the solid product obtained after carbonization, and the washing is preferably water washing, and the invention has no special requirement on the washing times so as to wash the solid product to be neutral.
In the present invention, the hydrogen evolution reaction electrode is prepared as follows.
3-10 mg of phosphorus-doped molybdenum carbide composite catalyst material; 0.5-8 ml of solvent; 10-100 mu L of binder;
the HER electrode material comprises 3-10 mg of phosphorus-doped molybdenum carbide composite catalyst material by mass, preferably 5 mg of phosphorus-doped molybdenum carbide composite catalyst material.
The HER electrode material provided by the invention comprises 0.5-8 ml of solvent, preferably 1 ml. In the present invention, the solvent is an ethanol solution, wherein the volume ratio of ethanol to water is 1: 1.
the HER electrode material provided by the invention comprises 10-100 mu L of adhesive, preferably 25 mu L. In the present invention, the binder is preferably a 5 wt% Nafion solution.
The invention provides a preparation method for preparing a super HER electrode by using the HER electrode material in the technical scheme, which comprises the following steps: mixing a phosphorus-doped molybdenum carbide composite catalyst material, an adhesive and a solvent, and ultrasonically stirring to obtain electrode slurry; and dripping the electrode slurry on the surface of an electrode, and drying to obtain the HER electrode. In the present invention, the electrode is preferably a platinum carbon electrode, the diameter of which is preferably 3 mm; the volume of the slurry dripped by the invention is 1-10 mu L, preferably 5 mu L; in the invention, the drying temperature is preferably 4-60 ℃, and more preferably 20-30 ℃; the drying time is preferably 1-10 h, and more preferably 2 h.
In order to further illustrate the present invention, the following embodiments are described in detail, but they should not be construed as limiting the scope of the present invention.
Example 1
Firstly, fish scales are decomposed to extract hydrolysate as a biomass precursor solution. Dissolving 0.002 mol phosphomolybdic acid in 10 ml water, after completely dissolving, adding the phosphomolybdic acid into 20 ml of precursor solutionStirring uniformly in the solution; transferring the liquid into a corundum boat for microwave drying for 120 s to obtain a solid substance; placing in the downstream of the tube furnace, placing the corundum boat added with phosphate in the upstream of the tube furnace, and heating at 2 deg.C for min-1Heating to 400 deg.C at a heating rate, maintaining the temperature for 2 hr, and heating at 5 deg.C for 5 min-1Raising the temperature to 900 ℃ at the heating rate, preserving the heat for 2 hours, and naturally cooling to room temperature to obtain a black solid substance. Grinding the black solid matter, washing the ground black solid matter with ethanol and water to be neutral, centrifuging the washed black solid matter, and drying the washed black solid matter at 80 ℃ to obtain the phosphorus-doped molybdenum carbide composite catalyst material.
FIG. 1 is a transmission electron microscope representation of the prepared phosphorus-doped molybdenum carbide composite catalyst material, wherein (a) in FIG. 1 is a transmission electron microscope photograph at a scale of 100 nm, and (b) in FIG. 1 is a transmission electron microscope photograph at a scale of 50 nm; (c) is a transmission electron microscope photograph when the scale is 20 nm, and (d) in fig. 1 is a transmission electron microscope photograph when the scale is 50 nm, and it can be obtained from fig. 1 that the material prepared by the embodiment has a band-shaped structure and can clearly see the lattice fringe phase of carbon;
FIG. 2 is an X-ray diffraction spectrum diagram of the prepared phosphorus-doped molybdenum carbide composite catalyst material, and the relatively wide diffraction peaks at 36 degrees, 64 degrees and 75 degrees are obviously Mo in FIG. 22Characteristic diffraction peak of C. The peak shape is wider and the strength is weaker, which indicates Mo in the material2C has low crystallinity.
FIG. 3 is a XPS spectrum of the core energy level region of Mo3d in the prepared phosphorus-doped molybdenum carbide composite catalyst material, and peaks of 228.7 eV and 231.8 eV are assigned to Mo2+While the peaks at 232.3 eV and 235.0 eV originate from MoO3Possibly due to surface oxidation of the material in air.
FIG. 4 is a XPS spectrum of the core energy level region of P2P in the prepared phosphorus-doped molybdenum carbide composite catalyst material, and the peak at 133.7 eV in FIG. 4 is assigned to P-C P3/2The peak at 134.5 eV is assigned to P-C P1/2。
Fig. 5 is a XPS spectrum of the core level region of C1s in the prepared phosphorus doped molybdenum carbide composite catalyst material, in which the peak of C-N/C-P (286.6 eV) of C-C/C = C (284.7 eV) can be seen.
FIG. 6 is a XPS spectrum of a core level region of N1s in the prepared phosphorus-doped molybdenum carbide composite catalyst material, which is divided into three peaks at 398.2 eV, 399.7 eV and 401.5 eV, and is attributed to pyridine nitrogen and pyrrole nitrogen graphitized nitrogen; the peak at 395.2 eV is assigned to M3 p.
Application example 1
The phosphorus-doped molybdenum carbide composite catalyst material prepared in example 1 was prepared into slurry, which was drop-coated on the surface of a platinum-carbon electrode, and dried at 30 ℃ for two hours to obtain an HER working electrode.
Test example 1
The phosphorus-doped molybdenum carbide composite catalyst material prepared in application example 1 is dropwise coated on the surface of a platinum-carbon electrode to serve as a working electrode, a saturated calomel electrode serves as a reference electrode, a graphite rod serves as a counter electrode, and the three electrodes are placed in a volume of 1mol L-1And performing electrochemical performance tests such as linear voltammetric scanning and cyclic voltammetric testing in the KOH solution.
FIG. 7 shows a platinum-carbon electrode coated with a phosphorus-doped molybdenum carbide composite catalyst material of example 1 as a working electrode, with a scan rate of 5 mV s in a voltage range of-0.4 to 0V (vs. RHE)-1The linear voltammogram of the time can be obtained from FIG. 7, and the phosphorus-doped molybdenum carbide composite catalyst prepared in application example 1 only needs 118 mV overpotential to reach 10 mA cm-2The current density of (1).
FIG. 8 is a Tafel curve of the working electrode made of the phosphorus-doped molybdenum carbide composite catalyst material in application example 1, which can be obtained from FIG. 8, and the Tafel slope of application example 1 is only 97 mV dec-1。
Test example 2
The difference from test example 1 was only that the electrolyte used in the test was 0.5M H2SO4。
FIG. 9 shows that the platinum-carbon electrode coated with the phosphorus-doped molybdenum carbide composite catalyst material in test example 2 was a working electrode with a scan rate of 5 mV s in a voltage range of-0.4 to 0V (vs. RHE)-1The linear voltammogram of the time can be obtained from FIG. 9, and the phosphorus-doped molybdenum carbide composite catalyst prepared in application example 1 only needs 172mV overpotential to reach 10 mA cm-2The current density of (1).
FIG. 10 is a Tafel curve of the phosphorus-doped molybdenum carbide composite catalyst material as a working electrode in test example 2, and it can be obtained from FIG. 10 that the Tafel slope of application example 1 is only 89 mV dec-1。
Examples 2, 3 and 4
Differs from example 1 only in that the amount of phosphomolybdic acid added is 0.001mol L-1，0.003mol L-1And 0.004mol L-1。
Example 5
The difference from example 1 is that the phosphating-carbonizing treatment is carried out directly at 5 ℃ for min-1The temperature is raised to 900 ℃ at the heating rate, and the temperature is kept for 2 hours.
Although the present invention has been described in detail with reference to the above embodiments, it is only a part of the embodiments of the present invention, not all of the embodiments, and other embodiments can be obtained without inventive step according to the embodiments, and all of the embodiments are protected by the present invention.
Claims (9)
1. A phosphorus-doped molybdenum carbide composite catalyst, a preparation method thereof and an application of electrocatalytic hydrogen evolution are characterized by comprising the following steps: (1) liquefying the waste biomass to obtain a concentrated solution, and adding molybdenum salt into the solution; (2) curing the liquid obtained in the step 1; (3) synchronously phosphorizing and carbonizing the solid obtained in the step 2 at a certain temperature under certain inert atmosphere conditions to obtain a black product; (4) preparing the product obtained in the step (3) into slurry, and dripping a certain amount of slurry on the surface of a platinum-carbon electrode to form a working electrode; (5) and (4) constructing a three-electrode system, and carrying out an electro-catalytic hydrogen evolution performance test on the electrode obtained in the step (4).
2. Composite catalyst according to claims 1 and 2, characterized in that the molybdenum salt used in step 1 comprises: phosphomolybdic acid, ammonium heptamolybdate, ammonium molybdate, sodium molybdate and the like.
3. The composite catalyst according to claim 1 or 2, wherein the gas used in step 3 is nitrogen, argon or a mixture of both.
4. The composite catalyst of claim 1, 2 or 3, wherein the temperature of phosphating-carbonizing in step 3 is from 700 ℃ to 900 ℃.
5. The composite catalyst according to claim 1, 2, 3 or 4, characterized in that the phosphating agent in step 3 comprises: sodium hydrogen phosphite, sodium hypophosphite, sodium phosphate, potassium hydrogen phosphite, potassium hypophosphite, potassium phosphate, and the like.
6. The composite catalyst according to claim 1, 2, 3, 4 or 5, characterized in that the working electrode is prepared in step 4 by: and (3) taking 5-10 mg of the black substance prepared in the step (3), adding 0.5-10 ml of ethanol solution, taking 5-10 mu L of the solution to be dripped on the surface of the platinum-carbon electrode, and drying at 20-60 ℃ to obtain the working electrode.
7. The composite catalyst according to claim 1, wherein the specific surface area of the material is 150 to 350 m2 g-1。
8. Use of a composite catalyst according to any one of claims 1 to 7 in the electrocatalytic evolution of hydrogen with a binder of 5 wt% Nafion solution.
9. Use of a composite catalyst according to claim 1, 8, 9 or 10 in electrocatalysis, wherein the electrolyte is 1.0 mol L-1KOH solution or 0.5 mol L-1 H2SO4。
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| ZA2022/07699A ZA202207699B (en) | 2022-02-18 | 2022-07-12 | A phosphorus-doped molybdenum carbide composite catalyst and its preparation method and electrocatalytic hydrogen evolution application |
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