CN110433833A - A kind of base metal Electrocatalytic Activity for Hydrogen Evolution Reaction agent and preparation method thereof based on modified synergic - Google Patents
A kind of base metal Electrocatalytic Activity for Hydrogen Evolution Reaction agent and preparation method thereof based on modified synergic Download PDFInfo
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- CN110433833A CN110433833A CN201910746775.6A CN201910746775A CN110433833A CN 110433833 A CN110433833 A CN 110433833A CN 201910746775 A CN201910746775 A CN 201910746775A CN 110433833 A CN110433833 A CN 110433833A
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- hydrogen evolution
- reaction agent
- evolution reaction
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 239000001257 hydrogen Substances 0.000 title claims abstract description 51
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 51
- 230000000694 effects Effects 0.000 title claims abstract description 41
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 40
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 22
- 239000010953 base metal Substances 0.000 title claims abstract description 21
- 230000002195 synergetic effect Effects 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000003054 catalyst Substances 0.000 claims abstract description 50
- 229910052751 metal Inorganic materials 0.000 claims abstract description 26
- 239000002184 metal Substances 0.000 claims abstract description 26
- 239000011159 matrix material Substances 0.000 claims abstract description 24
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000001301 oxygen Substances 0.000 claims abstract description 10
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 10
- 230000001376 precipitating effect Effects 0.000 claims abstract description 9
- 239000011148 porous material Substances 0.000 claims abstract description 7
- 239000002105 nanoparticle Substances 0.000 claims abstract description 5
- 239000002244 precipitate Substances 0.000 claims abstract description 4
- 229910052723 transition metal Inorganic materials 0.000 claims description 17
- 229910052759 nickel Inorganic materials 0.000 claims description 11
- 150000003624 transition metals Chemical class 0.000 claims description 11
- 239000006260 foam Substances 0.000 claims description 9
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 9
- -1 transition metal salt Chemical class 0.000 claims description 9
- 239000003153 chemical reaction reagent Substances 0.000 claims description 6
- 239000012876 carrier material Substances 0.000 claims description 5
- 230000007704 transition Effects 0.000 claims description 5
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical group FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims description 4
- 229910002651 NO3 Inorganic materials 0.000 claims description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 229910052698 phosphorus Inorganic materials 0.000 claims description 4
- 239000011574 phosphorus Substances 0.000 claims description 4
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 4
- 229910052721 tungsten Inorganic materials 0.000 claims description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 3
- 239000004202 carbamide Substances 0.000 claims description 3
- 229910044991 metal oxide Inorganic materials 0.000 claims description 3
- 150000004706 metal oxides Chemical class 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- LOMVENUNSWAXEN-UHFFFAOYSA-N Methyl oxalate Chemical compound COC(=O)C(=O)OC LOMVENUNSWAXEN-UHFFFAOYSA-N 0.000 claims description 2
- 240000007594 Oryza sativa Species 0.000 claims description 2
- 235000007164 Oryza sativa Nutrition 0.000 claims description 2
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 239000000908 ammonium hydroxide Substances 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 239000012300 argon atmosphere Substances 0.000 claims description 2
- 239000003575 carbonaceous material Substances 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 150000004820 halides Chemical class 0.000 claims description 2
- 239000003456 ion exchange resin Substances 0.000 claims description 2
- 229920003303 ion-exchange polymer Polymers 0.000 claims description 2
- 239000012702 metal oxide precursor Substances 0.000 claims description 2
- 239000002808 molecular sieve Substances 0.000 claims description 2
- 235000009566 rice Nutrition 0.000 claims description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 2
- IIACRCGMVDHOTQ-UHFFFAOYSA-M sulfamate Chemical compound NS([O-])(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-M 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 14
- 239000000463 material Substances 0.000 abstract description 12
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- 238000010438 heat treatment Methods 0.000 abstract description 7
- 239000010970 precious metal Substances 0.000 abstract description 5
- 238000006555 catalytic reaction Methods 0.000 abstract description 4
- 238000006481 deamination reaction Methods 0.000 abstract description 4
- 230000018044 dehydration Effects 0.000 abstract description 4
- 238000006297 dehydration reaction Methods 0.000 abstract description 4
- 230000002153 concerted effect Effects 0.000 abstract description 3
- 238000012546 transfer Methods 0.000 abstract description 3
- 230000009615 deamination Effects 0.000 abstract description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 53
- 239000000047 product Substances 0.000 description 26
- 229910015667 MoO4 Inorganic materials 0.000 description 16
- 229910018864 CoMoO4 Inorganic materials 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 10
- 239000013078 crystal Substances 0.000 description 10
- 238000005868 electrolysis reaction Methods 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 7
- 230000005540 biological transmission Effects 0.000 description 7
- 238000010586 diagram Methods 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 229910005809 NiMoO4 Inorganic materials 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- 230000008859 change Effects 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- 230000010287 polarization Effects 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 230000033228 biological regulation Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 230000005518 electrochemistry Effects 0.000 description 2
- 238000002003 electron diffraction Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 238000001239 high-resolution electron microscopy Methods 0.000 description 2
- 238000001453 impedance spectrum Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 150000002927 oxygen compounds Chemical class 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000001338 self-assembly Methods 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- 229910003208 (NH4)6Mo7O24·4H2O Inorganic materials 0.000 description 1
- 229910004619 Na2MoO4 Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001768 cations Chemical group 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000036647 reaction Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000004098 selected area electron diffraction Methods 0.000 description 1
- 239000011684 sodium molybdate Substances 0.000 description 1
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000010183 spectrum analysis Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 239000000052 vinegar Substances 0.000 description 1
- 235000021419 vinegar Nutrition 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- 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
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
- B01J27/19—Molybdenum
-
- 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
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
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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
-
- 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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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
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Abstract
The invention belongs to hydrogen manufacturing material technical fields, disclose a kind of base metal Electrocatalytic Activity for Hydrogen Evolution Reaction agent and preparation method thereof based on modified synergic.The catalyst is made of metal phosphide activity phase, oxide matrix phase and carrier, and metal phosphide activity is mutually with tiny form of nanoparticles Dispersed precipitate in oxide matrix phase surface, and oxide matrix phase load is on carrier.The present invention constructs concerted catalysis active sites with matrix combination of oxides by phosphating reaction precipitating metal phosphide activity phase；Meanwhile matrix oxide portions restore introduced Lacking oxygen, help to improve the electric conductivity of basis material；In addition, persursor material generates a large amount of nano-pores because of dehydration or deamination during heating, while more active sites are provided, further improve the mass-transfer performance of catalyst.To realize while optimize latent active, active bit quantity, three aspect element of electric conductivity.Catalytic performance is integrated close to precious metals pt catalyst.
Description
Technical field
The invention belongs to hydrogen manufacturing material technical fields, and in particular to a kind of base metal liberation of hydrogen electricity based on modified synergic is urged
Agent and preparation method thereof.
Background technique
Hydrogen be it is a kind of cleaning, efficient energy carrier, scale industry application be expected to essence solve energy shortage, ring
The global problems such as border pollution, thus develop the emphasis that hydrogen utilization technology has become countries in the world energy development strategy.It pushes
Hydrogen Energy industrial application need to construct the complete Hydrogen Energy industrial chain including links such as hydrogen manufacturing, hydrogen storage, hydrogen fuel cells, and wherein hydrogen manufacturing is
Source.In existing hydrogen manufacturing mode, electrolysis water has most long developing history, but couple with renewable energy and will assign it entirely
New vitality.Water is dissociated using the electric energy that the non-renewable energy such as solar energy, wind energy generate, the chemical energy that hydrogen is contained is made
Electric energy can be again converted to hydrogen terminal in fuel cell.In this way, electrolysis water, while providing sustainable hydrogen manufacturing mode, being can
The effective use of the renewable sources of energy provides feasible program.Electrolysis water is related to two half-reactions of cathode hydrogen evolution and Oxygen anodic evolution, reduces
The overpotential of two reactions, i.e. reduction cell reaction energy consumption are to develop the core of electrolysis water technology.
Noble metal platinum (Pt) has excellent evolving hydrogen reaction electro catalytic activity, is acknowledged as most representative electrolysis water yin
Electrode catalyst, but excessively high material cost seriously restricts its practical application.In recent years, your the non-transition gold of research and development efficiently, cheap
Belong to the main trend that elctro-catalyst has become electrolysis water technology.According to the literature, 3d transient metal sulfide, phosphide, nitrogen
The compounds such as compound, carbide have good evolving hydrogen reaction electro catalytic activity, and can be by taking structure nano, ingredient tune
The modification strategies such as system effectively to promote catalytic performance.But in general, the still generally existing liberation of hydrogen of non-noble transition metal elctro-catalyst
The disadvantages of overpotential is higher, and long-term working stability is not good enough is reacted, therefore develops advanced cheap metal Catalyst Design theory
It is still to promote critical issue urgently to be resolved in electrolysis water technical application process with controllable synthesis method.
Summary of the invention
In place of the above shortcoming and defect of the existing technology, it is based on the primary purpose of the present invention is that providing one kind
The base metal Electrocatalytic Activity for Hydrogen Evolution Reaction agent of modified synergic.Catalyst of the present invention has both high intrinsic catalytic activity, active site abundant
It, can efficiently and stably catalytic electrolysis water evolving hydrogen reaction, comprehensive catalytic performance be close under alkaline condition with good electric conductivity
Precious metals pt catalyst.
The preparation for the base metal Electrocatalytic Activity for Hydrogen Evolution Reaction agent based on modified synergic that another object of the present invention is to provide above-mentioned
Method.This method raw material is easy to get, is easy to operate, convenient for volume production.
The object of the invention is achieved through the following technical solutions:
A kind of base metal Electrocatalytic Activity for Hydrogen Evolution Reaction agent based on modified synergic, by metal phosphide activity phase, oxide matrix
Mutually and carrier composition, metal phosphide are active mutually with tiny form of nanoparticles Dispersed precipitate in oxide matrix phase surface, oxygen
Compound matrix phase load is on carrier.
Preferably, the metal phosphide activity is mutually the phosphide of transition metal, and the oxide matrix is mutually transition
The oxide of metal；The transition metal refers at least one of Fe, Co, Ni, W, Mo, Mn.
Preferably, the particle size of the metal phosphide activity phase is 5~15nm.
Preferably, Lacking oxygen is rich in the oxide lattice of the oxide matrix phase, oxide matrix mutually has nanometer
Porous structure, nanoporous size are 1~10nm.
Preferably, the carrier is selected from foam metal, metal mesh, ion exchange resin, molecular sieve or porous carbon materials；
More preferably nickel foam.
The preparation method of the above-mentioned base metal Electrocatalytic Activity for Hydrogen Evolution Reaction agent based on modified synergic, including following preparation step:
Carrier material is added in the aqueous solution containing transition metal salt and precipitating reagent, 90~180 DEG C of hydro-thermal reactions, In
Surfaces of carrier materials grows metal oxide precursor, after cleaning-drying with phosphorus source at a temperature of inert atmosphere and 300~450 DEG C
Phosphating reaction is carried out, in metal oxide surface original position precipitating metal phosphide activity phase, while obtaining and being rich in Lacking oxygen and tool
There is the oxide matrix phase of nano-porous structure, obtains the base metal Electrocatalytic Activity for Hydrogen Evolution Reaction agent based on modified synergic.
Preferably, the transition metal salt refers to halide, nitrate, sulfate, sulfamate, the vinegar of transition metal
Hydrochlorate or transition metal oxygen-containing or not at least one of oxysalt；The transition metal refers to Fe, Co, Ni, W, Mo or Mn.
Preferably, the precipitating reagent is in urea, ammonium hydroxide, hexa, dimethyl oxalate, diethy-aceto oxalate
It is at least one；More preferably urea.
Preferably, the concentration of the transition metal salt is 0.01~0.2M, and the concentration of precipitating reagent is 0~0.3M.
Preferably, the time of the hydro-thermal reaction is 4~20h.
Preferably, phosphorus source is sodium hypophosphite.
Preferably, the inert atmosphere refers to argon atmosphere.
Preferably, the time of the phosphating reaction is 1~3h.
The principle of the present invention are as follows: for elctro-catalyst, three elements for influencing its apparent catalytic activity are: latent active,
Active bit quantity, electric conductivity.Traditional elctro-catalyst often pays close attention to merely one or two aspects therein, provided by the present invention
Catalyst optimizes these three elements simultaneously in mentality of designing, and provides simple and easy preparation method and realized.Firstly,
Using hydrothermal method before surfaces of carrier materials is grown containing catalyst activity component and has the metal oxide of high-specific surface area
Body is driven, establishes material composition and structure basis for synthesized high-performance catalyst；Then, by regulation phosphating reaction treatment conditions come
Selective separation-out metal phosphide activity phase, is allowed to tiny form of nanoparticles Dispersed precipitate in oxide surface, and realize
The In-situ reaction of two-phase.The metal phosphide being precipitated in situ is combined with oxide matrix constructs concerted catalysis active sites, wherein oxygen
Compound promotes hydrone dissociation, and metal phosphide mutually provides hydrogen atom compound Detachment Activity position, the intrinsic catalysis of synergistic catalyst
Activity is significantly higher than Single Phase Metal phosphide catalyst；Metallic atom precipitation or metal cation part occur in parkerizing process also
Original causes Lacking oxygen in oxide lattice to generate, and the generation of a large amount of lattice defects helps to improve the electric conductivity of basis material；
In addition, the persursor material of hydrothermal synthesis contains the crystallization water or ammonia root, the dehydration occurred during heating or deamination reaction meeting
Cause a large amount of nano-pores to generate, the specific surface area of material is further increased, to provide more active sites.To sum up, this hair
Electrocatalytic Activity for Hydrogen Evolution Reaction agent provided by bright has both high intrinsic activity, active sites abundant and good electric conductivity.
Compared with the existing technology, the invention has the following advantages and beneficial effects:
(1) present invention is by regulation phosphating reaction treatment conditions come Selective separation-out metal phosphide activity phase, Jin Eryu
Matrix combination of oxides constructs concerted catalysis active sites；Meanwhile matrix oxide portions restore introduced Lacking oxygen, facilitate
Improve the electric conductivity of basis material；In addition, persursor material generates a large amount of nano-pores because of dehydration or deamination during heating,
While more active sites are provided, further improve the mass-transfer performance of catalyst.To realize while optimize latent active, work
Property bit quantity, three aspect element of electric conductivity.
(2) preparation method raw material of the invention is easy to get, simple process, is convenient for volume production.
(3) the base metal Electrocatalytic Activity for Hydrogen Evolution Reaction agent of present invention gained can under alkaline condition efficient catalytic electrolysis water liberation of hydrogen it is anti-
It answers, and has excellent stability and durability, integrate catalytic performance close to precious metals pt catalyst.
Detailed description of the invention
Fig. 1 is gained hydro-thermal aspect product (NH in the embodiment of the present invention 14)HNi2(OH)2(MoO4)2/ NF (a) and phosphorating treatment
Sample Ni2-xMoxP/NiMoO4-yThe scanning electron microscope shape appearance figure of/NF (b).
Fig. 2 is gained hydro-thermal aspect product (NH in the embodiment of the present invention 14)HNi2(OH)2(MoO4)2/ NF (a), phosphorating treatment
Sample Ni2-xMoxP/NiMoO4-yThe X-ray diffractogram of/NF and its 500 DEG C of heat treatment crystallization sample (b).
Fig. 3 is gained hydro-thermal aspect product (NH in the embodiment of the present invention 14)HNi2(OH)2(MoO4)2(a) with phosphorating treatment sample
Product Ni2-xMoxP/NiMoO4-y(b) transmission electron microscope shape appearance figure；Phosphorating treatment sample Ni2-xMoxP/NiMoO4-yHigh resolution electron microscopy
Photo figure (c), selective electron diffraction figure (d) and linear scan energy spectrum diagram (e), illustration are angle of elevation annular dark field scanning transmission electron microscope
Figure.
Fig. 4 is gained (NH in the embodiment of the present invention 14)HNi2(OH)2(MoO4)2/ NF (hydro-thermal sample) and Ni2-xMoxP/
NiMoO4-yThe x-ray photoelectron spectroscopy figure of/NF sample (phosphatization sample): (a) Mo 3d is composed；(b) Ni 2p is composed；(c)Ni2- xMoxP/NiMoO4-yThe x-ray photoelectron spectroscopy figure of/NF sample in the region P 2p；(d)(NH4)HNi2(OH)2(MoO4)2/ NF with
Ni2-xMoxP/NiMoO4-yThe XPS spectrum figure of the O 1s of/NF sample.
Fig. 5 is gained Ni in the embodiment of the present invention 12-xMoxP/NiMoO4-yThe evolving hydrogen reaction of/NF and Pt/C/NF catalyst
Polarization curve comparison diagram.
Fig. 6 is gained Ni in the embodiment of the present invention 12-xMoxP/NiMoO4-y/ NF and (NH4)HNi2(OH)2(MoO4)2/ NF sample
Product capacitance current density and current potential under open circuit potential sweep the relational graph (a) of speed；Ni2-xMoxP/NiMoO4-y/ NF and (NH4)HNi2
(OH)2(MoO4)2The impedance spectrum test result figure (b) under -0.05V (vs. reversible hydrogen electrode) current potential of/NF sample.
Fig. 7 is gained Ni in the embodiment of the present invention 12-xMoxP/NiMoO4-yThe durability test result figure of/NF catalyst
(chronoptentiometry).
Fig. 8 is gained Ni in the embodiment of the present invention 12-xMoxP/NiMoO4-y/ NF catalyst is after 80 hours durability tests
Scanning electron microscope shape appearance figure.
Fig. 9 is gained hydro-thermal aspect product CoMoO in the embodiment of the present invention 24·nH2O (a) and phosphorating treatment sample Co3P/
CoMoO4(b) X-ray diffractogram.
Figure 10 is gained hydro-thermal aspect product CoMoO in the embodiment of the present invention 24·nH2O/NF (a) and phosphatization heat treated sample
Co3P/CoMoO4The scanning electron microscope pattern comparison diagram of/NF (b).
Figure 11 is gained hydro-thermal aspect product CoMoO in the embodiment of the present invention 24·nH2O (a) and phosphatization heat treated sample
Co3P/CoMoO4(b) transmission electron microscope pattern comparison diagram.
Figure 12 is gained Co in the embodiment of the present invention 23P/CoMoO4The evolving hydrogen reaction of/NF and Pt/C/NF catalyst polarizes bent
Line comparison diagram (a) and in 10mA/cm2Stability test result figure (b) under current density.
Specific embodiment
Present invention will now be described in further detail with reference to the embodiments and the accompanying drawings, but embodiments of the present invention are unlimited
In this.
Embodiment 1
(1) with nickel foam (NF) for carrier, with a thickness of 1.85mm, surface density is 620 ± 30g/m2, aperture be 0.20~
0.80mm.Nickel foam (1 × 4cm2) activated after ten minutes through EtOH Sonicate cleaning 10 minutes with 3M hydrochloric acid solution, contain together with 30mL
There is Ni (NO3)2·6H2O(0.1M)、(NH4)6Mo7O24·4H2O(0.025M)、(NH2)2The deionized water solution of CO (0.25M) is set
In the hydro-thermal axe that volume is 50mL, sample is made through sufficiently clear in the cooled to room temperature after 150 DEG C of constant temperature are handled 18 hours
Vacuum drying 1 hour is carried out in room temperature after washing, obtains hydro-thermal aspect product (NH4)HNi2(OH)2(MoO4)2/NF。
(2) it by the sodium hypophosphite of about 1g and 1 centimetre of hydro-thermal aspect product interval placement quartz boat, heats under an argon
To 300 DEG C, 2 DEG C/min of heating rate, it is cooled to room temperature after 3 hours constant temperature is handled, final catalyst Ni is made2-xMoxP/
NiMoO4-y/NF。
Hydro-thermal aspect product (NH obtained by the present embodiment step (1)4)HNi2(OH)2(MoO4)2/ NF (a) and step (2) gained mesh
Mark catalyst n i2-xMoxP/NiMoO4-yThe scanning electron microscope (SEM) photograph of/NF (b) is as shown in Figure 1.
Hydro-thermal aspect product (NH obtained by the present embodiment step (1)4)HNi2(OH)2(MoO4)2/ NF (a), step (2) gained mesh
Mark catalyst n i2-xMoxP/NiMoO4-y/ NF and final catalyst are through 500 DEG C of heat treatment crystallization sample Ni2-xMoxP/NiMoO4-y/
NF-500 DEG C (b) of X-ray diffractogram is as shown in Figure 2.
Fig. 3 is hydro-thermal aspect product (NH obtained by the present embodiment step (1)4)HNi2(OH)2(MoO4)2(a) and final catalyst
Ni2-xMoxP/NiMoO4-yThe transmission electron microscope shape appearance figure of/NF (b)；Final catalyst Ni2-xMoxP/NiMoO4-yThe high-resolution electricity of/NF
Mirror photo figure (c), selective electron diffraction map (d) and linear scan energy spectrum diagram (e), illustration are angle of elevation annular dark field scanning transmission
Electron microscope.
Fig. 4 is hydro-thermal aspect product (NH obtained by the present embodiment step (1)4)HNi2(OH)2(MoO4)2/ NF and final catalyst
Ni2-xMoxP/NiMoO4-yThe x-ray photoelectron spectroscopy figure of/NF: (a) Mo 3d is composed；(b) Ni 2p is composed.(c)Ni2-xMoxP/
NiMoO4-yThe x-ray photoelectron spectroscopy figure of/NF sample in the region P 2p.(d)(NH4)HNi2(OH)2(MoO4)2/ NF and Ni2- xMoxP/NiMoO4-yThe XPS spectrum of the O 1s of/NF sample.
Scanning electron microscopic observation (a in Fig. 1) discovery, is handled through hydro-thermal reaction, and foam nickel surface grown a large amount of nanometer sheets, and
It is self-assembly of 3D nanometer flower structure；According to XRD analysis (a in Fig. 2), these nanometer sheet materials are (NH4)HNi2(OH)2
(MoO4)2Crystal phase；Hydro-thermal aspect product through 300 DEG C phosphorating treatment 3 hours, sample topography, which has no, substantially change (b in Fig. 1).
Transmission electron microscope observing (a, b in Fig. 3) further confirms receiving for hydro-thermal aspect product and phosphorating treatment final catalyst
Rice chip architecture, while finding there are a large amount of newly-generated nano particles and nano-pore in the nanometer sheet of phosphorating treatment sample,
Particle size is 5~15 nanometers, pore size is 1~10 nanometer；(c in Fig. 3) is analyzed according to high resolution electron microscopy, newly-generated nanometer
Particle is Ni2P nanometers of crystal phases, around there are a large amount of amorphous phases；Selected area electron diffraction analysis confirms Ni2P nanometers of crystal phases and
The generation of amorphous phase.
XRD analysis (b in Fig. 2) show hydro-thermal aspect product through 300 DEG C phosphorating treatment 3 hours, (NH4)HNi2(OH)2
(MoO4)2Crystal transition is unique nanometer crystal phase Ni2P.But carefully analyze XRD as a result, it has been found that, newly-generated Ni2The diffraction maximum of P
Than original Ni2The diffraction maximum of P is slightly biased to move on to lower angle, (Mo a) is detected in XPS, Fig. 4 in conjunction with x-ray photoelectron spectroscopy0
Signal as a result, clearly illustrate Mo doping Ni2The generation of P nanometers of crystal phases；Linear scan energy spectrum analysis (e in Fig. 3) is into one
Step confirms Ni2-xMoxThe generation of P nanometers of crystal phases.The XRD result of the phosphatization sample of 500 DEG C of high-temperature calcination 2h detects NiMoO4
The generation of crystal phase shows that the amorphous phase in phosphatization sample is NiMoO4Amorphous phase (b in Fig. 2).
According to X-ray photoelectron spectroscopic analysis (Fig. 4), hydro-thermal aspect product only have Mo6+And Ni2+Signal；Through 300 DEG C of phosphatizations
After processing 3 hours, additional Ni is presented in sample0、Mo0、Mo4+And Mo5+Signal, and the P element in phosphorating treatment sample is deposited
In P0And POxSignal；Observe Mo0、Ni0、P0The Ni of signal and Mo doping2P generates consistent, the PO observedxIt may be derived from
Partial oxidation occurs for catalyst surface in air exposure, and observes Mo simultaneously4+、Mo5+、Mo6+Signal then illustrates matrix
NiMoO4In there are a large amount of vacancy O, the XPS map of O 1s further confirms this point.
Final catalyst Ni obtained by the present embodiment2-xMoxP/NiMoO4-yThe electrocatalysis characteristic of/NF is tested:
Evolving hydrogen reaction polarization curve test result (Fig. 5) shows Ni2-xMoxP/NiMoO4-y/ NF catalyst has excellent
Evolving hydrogen reaction electro catalytic activity only needs the overpotential of hydrogen evolution of 36mV to can reach 10mA/cm in 1.0M lye2Electric current it is close
Degree, catalytic activity is close to precious metals pt/C catalyst.
A gives Ni in Fig. 62-xMoxP/NiMoO4-y/ NF and (NH4)HNi2(OH)2(MoO4)2/ NF sample is in open circuit potential
Under the capacitance current density that measures and current potential sweep fast relational graph, compared to hydro-thermal aspect product, through 300 DEG C after phosphorating treatment 3 hours
The electric double layer capacitance of gained sample improves nearly 30 times, i.e. electrochemistry specific surface area improves nearly 30 times, and electrochemistry specific surface area is shown
It writes and improves the dehydration that should occur in Phosphating Treatment Process, deamination reaction；According to impedance spectrum test result (b in Fig. 6), reduction
The load transfer resistance of aspect product is greatly lowered compared with hydro-thermal aspect product, should be derived from metallic character Ni2-xMoxP phase it is in situ be precipitated and
NiMoO4The vacancy O in matrix generates.
Fig. 7 gives Ni2-xMoxP/NiMoO4-yThe stability test of/NF catalyst through constant current in 80 hours as a result, measure
(10mA/cm2、50mA/cm2Each 40 hours under current density), catalyst activity does not fail now, and it is good to illustrate that catalyst has
Stability.
Fig. 8 gives Ni2-xMoxP/NiMoO4-yThe scanning electron microscope pattern of/NF catalyst after 80 hours durability tests,
The result shows that the pattern and classification nanostructure feature of catalyst have no and substantially change, it is steady to illustrate that catalyst has good structure
It is qualitative.
Embodiment 2
(1) with nickel foam (NF) for carrier, with a thickness of 1.85mm, surface density is 620 ± 30g/m2, aperture be 0.20~
0.80mm.Nickel foam (1 × 4cm2) activated after ten minutes through EtOH Sonicate cleaning 10 minutes with 3M hydrochloric acid solution, contain together with 30mL
There is Co (NO3)2·6H2O(0.02M)、Na2MoO4·2H2The deionized water solution of O (0.01M) is placed in the hydro-thermal that volume is 50mL
In axe, the cooled to room temperature after 150 DEG C of constant temperature are handled 6 hours is made sample and carries out vacuum in room temperature after sufficiently cleaning
It is 1 hour dry, obtain hydro-thermal aspect product CoMoO4·nH2O。
(2) it by the sodium hypophosphite of about 1g and 1 centimetre of hydro-thermal aspect product interval placement quartz boat, heats under an argon
To 300 DEG C, 2 DEG C/min of heating rate, it is cooled to room temperature after 3 hours constant temperature is handled, final catalyst Co is made3P/
CoMoO4/NF。
Hydro-thermal aspect product CoMoO obtained by the present embodiment step (1)4·nH2O (a) and step (2) gained final catalyst
Co3P/CoMoO4The XRD diagram of/NF (b) is as shown in Figure 9.The result shows that: CoMoO is generated in hydrothermal reaction process4·nH2O is brilliant
Phase；Through 300 DEG C phosphorating treatment 3 hours, CoMoO4·nH2O crystal transition is Co3P and CoMoO4Nanometer crystal phase.
Hydro-thermal aspect product CoMoO obtained by the present embodiment step (1)4·nH2O (a) and step (2) gained final catalyst
Co3P/CoMoO4The scanning electron microscope (SEM) photograph of/NF (b) is as shown in Figure 10.The result shows that: in hydrothermal reaction process, the growth of foam nickel surface
A large amount of nanometer sheets, part nanometer sheet are self-assembly of 3D nanometer flower structure (a in Figure 10)；Through 300 DEG C phosphorating treatment 3 hours
Afterwards, the pattern of sample, which has no, substantially change (b in Figure 10).
Hydro-thermal aspect product CoMoO obtained by the present embodiment step (1)4·nH2O (a) and step (2) gained final catalyst
Co3P/CoMoO4The transmission electron microscope picture of/NF (b) is as shown in figure 11.The result shows that: hydro-thermal sample is after phosphorating treatment, in nanometer sheet
A large amount of nano-pores are generated, aperture is about 8 nanometers.
Final catalyst Co obtained by the present embodiment3P/CoMoO4The electrocatalysis characteristic of/NF is tested:
Evolving hydrogen reaction polarization curve test result (a in Figure 12) shows Co3P/CoMoO4/ NF catalyst has excellent analysis
Hydrogen reacts electro catalytic activity, only needs the overpotential of hydrogen evolution of 41mV to can reach 10mA/cm in 1.0M lye2Electric current it is close
Degree, catalytic activity is close to precious metals pt/C catalyst.In 10mA/cm2It is tested 22 hours under current density, Co3P/CoMoO4/
NF catalyst activity does not fail now, shows that catalyst has good stability (b in Figure 12).
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present invention,
It should be equivalent substitute mode, be included within the scope of the present invention.
Claims (10)
1. a kind of base metal Electrocatalytic Activity for Hydrogen Evolution Reaction agent based on modified synergic, it is characterised in that: the catalyst is by metal phosphorizing
Object activity phase, oxide matrix phase and carrier composition, metal phosphide activity mutually with tiny form of nanoparticles Dispersed precipitate in
Oxide matrix phase surface, oxide matrix phase load is on carrier.
2. a kind of base metal Electrocatalytic Activity for Hydrogen Evolution Reaction agent based on modified synergic according to claim 1, it is characterised in that: institute
Stating metal phosphide activity mutually is the phosphide of transition metal, and the oxide matrix is mutually the oxide of transition metal；It is described
Transition metal refers at least one of Fe, Co, Ni, W, Mo, Mn.
3. a kind of base metal Electrocatalytic Activity for Hydrogen Evolution Reaction agent based on modified synergic according to claim 1 or 2, feature exist
In: the particle size of the metal phosphide activity phase is 5~15nm.
4. a kind of base metal Electrocatalytic Activity for Hydrogen Evolution Reaction agent based on modified synergic according to claim 1 or 2, feature exist
In: Lacking oxygen is rich in the oxide lattice of the oxide matrix phase, oxide matrix mutually has nano-porous structure, nanometer
Pore size is 1~10nm.
5. a kind of base metal Electrocatalytic Activity for Hydrogen Evolution Reaction agent based on modified synergic according to claim 1, it is characterised in that: institute
The carrier stated is selected from foam metal, metal mesh, ion exchange resin, molecular sieve or porous carbon materials.
6. the preparation method of the described in any item base metal Electrocatalytic Activity for Hydrogen Evolution Reaction agent based on modified synergic of Claims 1 to 5,
It is characterized in that including following preparation step:
Carrier material is added in the aqueous solution containing transition metal salt and precipitating reagent, 90~180 DEG C of hydro-thermal reactions, in carrier
Material surface grows metal oxide precursor, carries out at a temperature of inert atmosphere and 300~450 DEG C after cleaning-drying with phosphorus source
Phosphating reaction in metal oxide surface original position precipitating metal phosphide activity phase, while being obtained to be rich in Lacking oxygen and have and be received
The oxide matrix phase of rice porous structure, obtains the base metal Electrocatalytic Activity for Hydrogen Evolution Reaction agent based on modified synergic.
7. the preparation method of the base metal Electrocatalytic Activity for Hydrogen Evolution Reaction agent according to claim 6 based on modified synergic, feature
Be: the transition metal salt refers to halide, nitrate, sulfate, sulfamate, acetate or the transition of transition metal
Metal oxygen-containing or not at least one of oxysalt, the concentration of transition metal salt are 0.01~0.2M；The transition metal is
Refer to Fe, Co, Ni, W, Mo or Mn.
8. the preparation method of the base metal Electrocatalytic Activity for Hydrogen Evolution Reaction agent according to claim 6 based on modified synergic, feature
Be: the precipitating reagent is selected from least one of urea, ammonium hydroxide, hexa, dimethyl oxalate, diethy-aceto oxalate,
The concentration of precipitating reagent is 0~0.3M.
9. the preparation method of the base metal Electrocatalytic Activity for Hydrogen Evolution Reaction agent according to claim 6 based on modified synergic, feature
Be: the time of the hydro-thermal reaction is 4~20h, and the time of the phosphating reaction is 1~3h.
10. the preparation method of the base metal Electrocatalytic Activity for Hydrogen Evolution Reaction agent according to claim 6 based on modified synergic, feature
Be: phosphorus source is sodium hypophosphite, and the inert atmosphere refers to argon atmosphere.
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