CN108212157A - Metal boride water-splitting catalyst, preparation method and its application in terms of electro-catalysis water-splitting - Google Patents
Metal boride water-splitting catalyst, preparation method and its application in terms of electro-catalysis water-splitting Download PDFInfo
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 180
- 239000002184 metal Substances 0.000 title claims abstract description 180
- 239000003054 catalyst Substances 0.000 title claims abstract description 54
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 31
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 24
- 150000003624 transition metals Chemical class 0.000 claims abstract description 24
- 239000012190 activator Substances 0.000 claims abstract description 19
- 239000000945 filler Substances 0.000 claims abstract description 17
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Substances [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 105
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 94
- 229910052796 boron Inorganic materials 0.000 claims description 93
- 229910052760 oxygen Inorganic materials 0.000 claims description 18
- 239000001301 oxygen Substances 0.000 claims description 18
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 17
- 238000001354 calcination Methods 0.000 claims description 15
- 239000010935 stainless steel Substances 0.000 claims description 12
- 229910001220 stainless steel Inorganic materials 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 9
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 8
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 238000012545 processing Methods 0.000 claims description 6
- 238000010792 warming Methods 0.000 claims description 6
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 5
- 229910052700 potassium Inorganic materials 0.000 claims description 5
- 239000011591 potassium Substances 0.000 claims description 5
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 239000002609 medium Substances 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- 230000007704 transition Effects 0.000 claims description 4
- 229910020440 K2SiF6 Inorganic materials 0.000 claims description 3
- 239000003610 charcoal Substances 0.000 claims description 3
- 229910002804 graphite Inorganic materials 0.000 claims description 3
- 239000010439 graphite Substances 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- 229910020261 KBF4 Inorganic materials 0.000 claims description 2
- 229910004835 Na2B4O7 Inorganic materials 0.000 claims description 2
- 239000012670 alkaline solution Substances 0.000 claims description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- 235000019270 ammonium chloride Nutrition 0.000 claims description 2
- UQGFMSUEHSUPRD-UHFFFAOYSA-N disodium;3,7-dioxido-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane Chemical compound [Na+].[Na+].O1B([O-])OB2OB([O-])OB1O2 UQGFMSUEHSUPRD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 239000010931 gold Substances 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 229910010271 silicon carbide Inorganic materials 0.000 claims 2
- MPPQGYCZBNURDG-UHFFFAOYSA-N 2-propionyl-6-dimethylaminonaphthalene Chemical compound C1=C(N(C)C)C=CC2=CC(C(=O)CC)=CC=C21 MPPQGYCZBNURDG-UHFFFAOYSA-N 0.000 claims 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims 1
- 229910001495 sodium tetrafluoroborate Inorganic materials 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 18
- 230000003197 catalytic effect Effects 0.000 abstract description 15
- 229910000510 noble metal Inorganic materials 0.000 abstract description 6
- 239000007790 solid phase Substances 0.000 abstract description 4
- 238000005271 boronizing Methods 0.000 abstract description 3
- 239000007788 liquid Substances 0.000 abstract description 3
- 230000001590 oxidative effect Effects 0.000 abstract description 3
- 238000004140 cleaning Methods 0.000 abstract description 2
- 238000010438 heat treatment Methods 0.000 abstract description 2
- 238000002474 experimental method Methods 0.000 description 35
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 35
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 34
- 229910015346 Ni2B Inorganic materials 0.000 description 21
- WRLJWIVBUPYRTE-UHFFFAOYSA-N [B].[Ni].[Ni] Chemical compound [B].[Ni].[Ni] WRLJWIVBUPYRTE-UHFFFAOYSA-N 0.000 description 21
- 238000002441 X-ray diffraction Methods 0.000 description 18
- 230000000694 effects Effects 0.000 description 8
- 239000012071 phase Substances 0.000 description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- 229910000831 Steel Inorganic materials 0.000 description 6
- 230000008901 benefit Effects 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 238000011160 research Methods 0.000 description 6
- 239000010959 steel Substances 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 5
- 229910000480 nickel oxide Inorganic materials 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 230000005611 electricity Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical group [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 4
- 229910052753 mercury Inorganic materials 0.000 description 4
- 230000010287 polarization Effects 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 238000010189 synthetic method Methods 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 3
- 229910000000 metal hydroxide Inorganic materials 0.000 description 3
- 239000010970 precious metal Substances 0.000 description 3
- 229910000314 transition metal oxide Inorganic materials 0.000 description 3
- 229910000863 Ferronickel Inorganic materials 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- XGCTUKUCGUNZDN-UHFFFAOYSA-N [B].O=O Chemical compound [B].O=O XGCTUKUCGUNZDN-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 239000003708 ampul Substances 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 229910000712 Boron steel Inorganic materials 0.000 description 1
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 description 1
- 206010054949 Metaplasia Diseases 0.000 description 1
- 229910002640 NiOOH Inorganic materials 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- JZJNHPJBZWEHPD-UHFFFAOYSA-N [F].[Na] Chemical compound [F].[Na] JZJNHPJBZWEHPD-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical group 0.000 description 1
- 239000000443 aerosol Substances 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- HTXDPTMKBJXEOW-UHFFFAOYSA-N iridium(IV) oxide Inorganic materials O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000015689 metaplastic ossification Effects 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- VGTPKLINSHNZRD-UHFFFAOYSA-N oxoborinic acid Chemical compound OB=O VGTPKLINSHNZRD-UHFFFAOYSA-N 0.000 description 1
- 125000001820 oxy group Chemical group [*:1]O[*:2] 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000009790 rate-determining step (RDS) Methods 0.000 description 1
- 230000002468 redox effect Effects 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
- 235000019795 sodium metasilicate Nutrition 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002195 synergetic effect Effects 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/745—Iron
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/28—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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/30—Tungsten
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/75—Cobalt
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
-
- B01J35/33—
-
- 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
-
- 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
Abstract
Metal boride water-splitting catalyst, preparation method and its application in terms of electro-catalysis water-splitting, belong to elctro-catalyst preparing technical field.Metal boride catalyst of the present invention is prepared by solid phase boronising, is coated transition metal using pack boronizing medium, and ramped heating schedule carries out Bononizing pretreatment.Boriding medium is made of required boriding medium and nonessential activator and nonessential filler.Relative to liquid boriding, pack boriding method boronising rear surface cleaning difficulty is low, low for equipment requirements, suitable for the Bononizing pretreatment of various transition metal.Catalyst of the present invention has fabulous intrinsic catalytic activity and stability under alkaline condition：Current density is 10mA cm‑2When, required overpotential is 300mV~400mV；And electro-catalysis water crack parsing oxidative stability is at least 100h, and performance and unattenuated, alternative noble metal promote electro-catalysis water-splitting commercial applications.
Description
Technical field
The invention belongs to elctro-catalyst preparing technical fields, and in particular to a series of efficient metal boride water-splitting catalysis
Agent, preparation method and its application in terms of electro-catalysis water-splitting.
Background technology
In the developmental research of new energy, hydrogen is due to fuel value is high, product is pollution-free and utilizes diversification of forms
Many advantages, such as and be widely noticed.21st century, China, the U.S., Japan, Canada, European Union and Australia etc. all formulates
Hydrogen Energy development plan, and various progress are obtained in the field.The renewable new energy production and storage developed at present
Deposit in technology, the energy such as electro-chemical water cracking hydrogen production, fuel cell, metal-air battery conversion and storage device with it is efficient,
Simple in structure, environmental-friendly and the advantages that having a wide range of application, receives significant attention.In the near future, Hydrogen Technology and application have
Prestige becomes a reality, and hydrogen fuel cell and hydrogen energy automobile industrialization and the marketization are considered the important symbol of energy development.Wherein analyse
Oxygen reacts (OER) and plays key player in these energy convert and store.But because its slow kinetic reaction seriously limits
The electrolytic efficiency of dampening processed, good catalyst can reduce the overpotential of oxygen evolution reaction, accelerate its kinetic reaction.At present, property
Excellent noble metal catalyst (the RuO of energy2、IrO2Deng) with high costs and reserves are rare, significantly limit its large-scale production with
Using.Therefore, people are exploring alternative non-precious metal catalyst material always.
In recent years, transition metal oxide and hydroxide have been carried out extensively as the OER alternative catalysts reacted
Research.Wherein, T.F.Jaramillo etc. has studied a series of non-precious metal catalysts, it is indicated that ferronickel composite oxides are opposite
There is higher water oxidation catalytic activity (J.Am.Chem.Soc., 2013 volume 135 page 16977) for other oxides.
Optical drive method is respectively adopted in Berlinguette and Geng researchers and aerosol spray method has synthesized unbodied ferronickel
Oxide, possess relatively low water oxygen overpotential (Science, 2013 volume 340 page 60；Angew.Chem.Int.Ed.,
2014 volume 126 page 7677).The iron-doped nickel oxide nano-particle that the size that W.Li et al. is prepared for carbon load is 4nm finds to work as
When the content of iron accounts for 31%, i.e. Ni0.69Fe0.31Ox/ C is demonstrated by most excellent water oxidation catalytic property, when current density is 10mA
cm-2When, overpotential is only 280mV (Langmuir, 2014 volume 30 page 7893).J.R.Kitchin be utilized respectively natural evaporation,
The iron-doped nickel oxide and single-element oxide that hard template and the method for dip-coating synthesize, and have studied its water oxygen catalytic
Can, single-element oxide will be better than, and propose that Fe may be in bimetallic oxide by finding the performance of iron-doped nickel oxide
Active site (ACS Catal., 2012 volume 2 page 1793).It is a series of heavy by electricity systematically to be had studied in A.T.Bell articles
Relationship between iron-doped nickel oxide membrane structure and electro-catalysis water oxidation susceptibility that product method obtains, author think iron-doped nickel oxide
The active site that catalytic action is played in film is Ni, and the presence of Fe is to change the redox property of Ni, causes Ni
(OH)2The current potential forward direction movement of/NiOOH reduces the average valence of Ni, improves activity (J.Am.s of the Ni in catalysis is reacted
Chem.Soc., volume 135 page 12329 in 2013).But in most research, researchers are usually by increasing to fixed electrode
On active site quantity, improve dispersion degree, increase active site exposure number, to improve the catalytic activity of catalyst.And
Increase the latent active of each catalytic site, be only the key of catalyticing research.Increasing latent active leads to the direct of electrode activity
It improves, mitigates the transportation problem as caused by high load amount, under equal conditions, the dosage of catalyst can be reduced, save catalyst
Cost.The latent active of catalyst has broader room for promotion.
Regarding to the issue above we there is an urgent need to find and develop with high intrinsic activity, can replace noble metal, can promote
The non-precious metal catalyst of water-splitting commercial applications.Research based on non-noble transition metal, we are closed by pervasive method
Into a series of transition metal borides, compared to transition metal oxide/hydroxide, metal boride, which has, preferably leads
Electrical and higher latent active.The synthetic method has energy consumption more compared to the boride synthetic method of conventional high-temperature high pressure
It is low, take shorter, operability is stronger etc. advantage.All the advantages make it be more advantageous to scale and industrialized production.
Invention content
The purpose of the present invention is to provide it is a series of have high intrinsic activity, can replace noble metal, water-splitting quotient can be promoted
Base metal boride (M-B) catalyst of industryization application.Compared to transition metal oxide/hydroxide, metal boride
With better electric conductivity and higher latent active.Under alkaline condition and oxidizing condition, the boride of transition metal is formed
Metaboric acid is with (BO2 -), three metaboric acids form a boron oxygen hexatomic ring, which has certain weak armaticity, electronics
It is that delocalization is conjugated.The electronics of its delocalization of boron oxygen hexatomic ring can feed back to the d tracks of transition metal, in electrochemical process
Transition metal is reduced with binding ability hydroxy, reduces the activation energy of transition state, promotes the formation of M-OOH, and this
One step is that the rate determining step of production oxygroup elementary reaction is rapid, so as to accelerate reaction rate, improves catalytic activity.Meanwhile based on before
Research, the synergistic effect of transition metal can further improve its catalytic activity.Under alkaline condition, stainless steel is industrially used
As the catalyst of electro-catalysis water-splitting, the invention is in order to more close to industrial applications, carry out iron-nickel alloy and stainless steel
Boronation further improves the catalytic activity of its OER.The synthetic method is compared to the boride synthetic method of conventional high-temperature high pressure
There is energy consumption lower, take shorter, operability is stronger etc. advantage.All the advantages make it be more advantageous to scale and work
Industry metaplasia is produced.
Metal boride catalyst of the present invention is prepared by solid phase boronising, using pack boronizing medium that transition is golden
Belong to cladding, ramped heating schedule carries out Bononizing pretreatment, and boronising temperature is not less than 530 DEG C.Boriding medium by required boriding medium and
Nonessential activator and nonessential filler composition.It usually requires to add in suitable filler and activation in boronizing process
Agent, the main function of filler are to maintain the laxity of boriding medium, prevent boriding medium from luming.Activator promotees with boriding medium effect
Into generation activated boron atoms, boronising ability is improved.Relative to liquid boriding, pack boriding method boronising rear surface cleaning difficulty is low,
It is low for equipment requirements, suitable for the Bononizing pretreatment of various transition metal.By solid phase boronising, the present invention has synthesized a series of gold
Belong to boride, mainly there are three categories according to the molar ratio of metal and boron atom：One, metal and boron atom molar ratio 1：1 (MB), such as
FeB、 CoB、MoB；Two, metal and boron atom molar ratio 2：1(M2B), such as Fe2B、Co2B、Ni2B；Three, metal rubs with boron atom
That ratio 3：1(M3B), such as Ni3B.The quality of required boriding medium is denoted as (m by wea), the quality of activator is denoted as (mb), filling
The quality of agent is (mc)。
One, metal of the present invention and boron atom molar ratio 1：The system of the metal boride water-splitting catalyst of 1 (MB)
Preparation Method, its step are as follows：
(1) boriding medium and activator, mass ratio m are weigheda：mb=(4~19)：1, it is fully ground uniformly mixed, obtains
To boriding medium；
(2) what transition-metal Fe, Co, Mo or W etc. or dilval, stainless steel etc. be embedded to step (1) obtains respectively oozes
In boron agent, in transition metal and boriding medium boron atom and molar ratio be 1：1；
(3) product that step (2) obtains is warming up to 530 DEG C~1100 DEG C calcination processings under conditions of steam is completely cut off
0.5h~4h, so as to obtain metal and boron atom molar ratio 1：1 (MB is by XRD analysis using dilval and stainless steel
FeB, but because have the presence of Ni it is considered that be Ni doping FeB) metal boride water-splitting catalyst.
Two, metal of the present invention and boron atom molar ratio 2：1(M2B the system of metal boride water-splitting catalyst)
Preparation Method, its step are as follows：
(1) boriding medium, activator and filler, mass ratio m are weigheda：mb：mc=(9~1)：(0~1)：(0~
18) it, is fully ground uniformly mixed, obtains boriding medium；
(2) transition-metal Fe, Co or Ni etc. or dilval are embedded to respectively in the boriding medium that step (1) obtains, transition
In metal and boriding medium boron atom and molar ratio be 2：1；
(3) product that step (2) obtains is warming up to 530 DEG C~1100 DEG C calcination processings under conditions of steam is completely cut off
0.5h~4h, so as to obtain metal and boron atom molar ratio 2：1(M2B by XRD analysis is Fe using dilval2B, still
Because the presence of Ni is it is considered that be the Fe of Ni doping2B metal boride water-splitting catalyst).
Three, metal of the present invention and boron atom molar ratio 3：1(M3B) the preparation of metal boride water-splitting catalyst
Method, its step are as follows：
(1) boriding medium and filler, mass ratio m are weigheda：mc=1：(9~1), are fully ground uniformly mixed, obtain
To boriding medium；
(2) transition metal Ni etc. or dilval are embedded to respectively in the boriding medium that step (1) obtains, transition metal with
The molar ratio of boron atom sum is 3 in boriding medium：1；
(3) product that step (2) obtains is warming up to 530 DEG C~1100 DEG C calcination processings under conditions of steam is completely cut off
0.5h~4h, so as to obtain metal and boron atom molar ratio 3：1(M3B by XRD analysis is Fe when using dilval3B, but
It is because having the presence of Ni it is considered that being the Fe of Ni doping3B metal boride water-splitting catalyst).
In the above method, the boriding medium includes but not limited to boron amorphous B, B4C、Na2B4O7、B2O3Deng or its mixing
Object；
In the above method, the activator includes but not limited to potassium fluoborate (KBF4), sodium fluoborate (NaBF4), fluorine
Sodium metasilicate (K2SiF6), sodium carbonate (Na2CO3), ammonium chloride (NH4) etc. or its mixture Cl；
In the above method, the filler includes but not limited to the alundum (Al2O3) after silicon carbide (SiC), roasting
(Al2O3), granular graphite, charcoal etc. or its mixture；
In the above method, the calcination temperature is preferably 700 DEG C~900 DEG C；
In the above method, the calcination time is preferably 1.5h~2.5h；
In the above method one, the mass ratio of the boriding medium and activator is preferably ma：mb=9：1；
In the above method two, the mass ratio of the boriding medium, activator and filler is preferably ma：mb： mc=1：
1：18；
In the above method three, the mass ratio of the boriding medium and filler is preferably ma：mc=1：1；
Metal boride catalyst described in the above method can parse in water crack in the alkaline solution (KOH) of 1M~10M
Oxygen reacts；
The present invention also provides metal boride water-splitting catalyst prepared by the above method.
Advantageous effect
Present invention comparison prior art has following innovative point：
1. synthesis material rich reserves, cheap, simple for process, convenient controllable, short preparation period is reproducible, can
Large-scale production.
2. the present invention is prepared for a series of metal borides by simple pervasive solid phase boronising, since B is electron deficient
Structure, and then promote in oxygen catalytic process is analysed the generation of high volence metal ion, it is non-noble metal intrinsic so as to improve
Activity.Increasing latent active leads to the direct increase of electrode activity, mitigates the transportation problem as caused by high load amount, equal conditions
Under, the dosage of catalyst can be reduced, saves catalyst cost.
3. catalyst of the present invention has fabulous intrinsic catalytic activity and stability under alkaline condition：Current density is
10mA cm-2When, required overpotential is 280mV~400mV；And electro-catalysis water crack parsing oxidative stability is at least
100h, performance and unattenuated, alternative noble metal promote electro-catalysis water-splitting commercial applications.
Description of the drawings
Fig. 1：The metal M and B atomic molars ratio obtained in embodiment 1 by experiment one is 1：1 X x ray diffractions (XRD)
Collection of illustrative plates；
Fig. 2：The metal M and B atomic molars ratio obtained in embodiment 1 by experiment two is 2：1 X x ray diffractions (XRD)
Collection of illustrative plates；
Fig. 3：The metal M and B atomic molars ratio obtained in embodiment 1 by experiment three is 3：1 X x ray diffractions (XRD)
Collection of illustrative plates；
Fig. 4：Using product in the embodiment of the present invention 1 as water-splitting catalyst, the water in alkaline potassium hydroxide (KOH) solution
The polarization curve of cracking analysis oxygen；
Fig. 5：Using product in the embodiment of the present invention 1 as water-splitting catalyst, the water in alkaline potassium hydroxide (KOH) solution
The stability curve of cracking analysis oxygen；
Specific embodiment
The invention will be further described by way of example and in conjunction with the accompanying drawings, but protection scope of the present invention is not limited to
Following embodiments.It it will be apparent to those skilled in the art that can be to the present invention in the case of without departing from spirit and scope of the present invention
Variation or adjustment are made, these variations or adjustment are also included in protection scope of the present invention.
Embodiment 1
Experiment one, synthesis metal and boron atom molar ratio are 1：1 (MB) metal boride water-splitting catalyst
(1) 8.1g (i.e. 0.75mol) boron amorphous (B) and 0.9g (i.e. 0.0071mol) potassium fluoborates (KBF are weighed4), fully
Ground and mixed is uniform, obtains boriding medium；
(2) boriding medium that 4 parts of steps (1) obtain is respectively put into 4 stainless steel cylinder of steels, be then respectively put into
0.75mol transition-metal Fes, Co, Mo and W are allowed to be fully embedded in boriding medium；
(3) the stainless steel cylinder of steel in step (2) is fully sealed with fire clay, it is then fully dry at 100 DEG C；
(4) by stainless steel cylinder of steel temperature programming dried in step (3) to 800 DEG C, 2h is calcined, it is former with boron to obtain metal
Sub- molar ratio is 1：1 (MB) metal boride water-splitting catalyst.
Experiment two, synthesis metal and boron atom molar ratio are 2：1(M2B) metal boride water-splitting catalyst
(1) 0.5g (i.e. 0.46mol) boron amorphous (B), 0.5g (i.e. 0.004mol) potassium fluoborates (KBF are weighed4) and 9g
(i.e. 0.225mol) silicon carbide (SiC), is fully ground uniformly mixed, obtains boriding medium；
(2) boriding medium that 3 parts of steps (1) obtain is respectively put into 3 stainless steel cylinder of steels, be then respectively put into
0.92mol transition-metal Fes, Co and Ni are allowed to be fully embedded in boriding medium；
(3) the stainless steel cylinder of steel in step (2) is fully sealed with fire clay, it is fully dry is put into 100 DEG C of baking oven；
(4) by dried stainless steel cylinder of steel temperature programming to 800 DEG C, 2h is calcined, obtains metal and boron atom molar ratio
It is 2：1(M2B) metal boride water-splitting catalyst.
Experiment three, synthesis metal and boron atom molar ratio are 3：1(M3B) metal boride water-splitting catalyst
(1) 2g (i.e. 0.185mol) boron amorphous (B) and 2g (i.e. 0.05mol) silicon carbide (SiC) are weighed, is fully ground mixing
Uniformly；
(2) boriding medium that step (1) obtains is put into quartz ampoule, is then embedded to 0.56mol transition metal Ni；
(3) by the quartz ampoule temperature programming being sealed in step (2) to 800 DEG C, 2h is calcined, obtains metal and boron atom
Molar ratio is 3：1(M3B) metal boride water-splitting catalyst.
Electro-catalysis water crack parsing oxygen (OER) property is carried out in standard three electrode electrolytic cell to material prepared by the above method
Matter is tested；Working electrode is product of the present invention in electrolytic cell, and metal foil can be directly as working electrode；Powder sample is through abundant
Perfluorinated sulfonic resin and isopropanol are scattered in after grinding, and (its volume ratio is 1:10) mixed solution, then using glass-carbon electrode as
Working electrode drops in the catalyst above glass-carbon electrode.Reference electrode is mercury oxidation mercury electrode, is platinum filament to electrode, is electrolysed
Liquid is 1M~10M KOH.It should be noted that all potentials obtained using mercury oxidation mercury as reference electrode exist in electro-catalysis test
Reversible hydrogen electrode potential is converted into property figure, external power supply is electrochemical workstation main battery.
The material prepared to the above method has carried out some structures and performance study.
Figure 1A is X-ray diffraction (XRD) collection of illustrative plates of the orthorhombic phase FeB obtained by experiment one；Figure 1B is by experiment one
X-ray diffraction (XRD) collection of illustrative plates of the orthorhombic phase CoB of acquisition；The X ray that Fig. 1 C are the tetragonal phase MoB obtained by experiment one spreads out
Penetrate (XRD) collection of illustrative plates；Fig. 1 D are X-ray diffraction (XRD) collection of illustrative plates of the tetragonal phase WB obtained by experiment one；The XRD spectra table of Fig. 1
Bright metal is 1 with boron atom molar ratio：1 (MB) metal boride is grown along [002] crystal orientation.
Fig. 2A is the tetragonal phase Fe obtained by experiment two2X-ray diffraction (XRD) collection of illustrative plates of B；Fig. 2 B is pass through experiment
The one tetragonal phase Co obtained2X-ray diffraction (XRD) collection of illustrative plates of B；Fig. 2 C are the tetragonal phase Ni obtained by experiment one2The X ray of B
Diffraction (XRD) collection of illustrative plates.
Fig. 3 is the orthorhombic phase Ni obtained by experiment three3X-ray diffraction (XRD) figure of B.
Fig. 4 A is are 1 by the metal that experiment one obtains and boron atom molar ratio：1 metal boride (MB) is in alkalinity
In potassium hydroxide (1M KOH) solution water crack parsing oxygen polarization curve, CoB, FeB, MoB, WB respectively overpotential for 360mV,
372mV, 430mV, 460mV reach current density for 10 mA/cm2.Fig. 4 B are the metal and boron atom obtained by experiment two
Molar ratio is 2：1 metal boride (M2B) polarization of water crack parsing oxygen is bent in alkaline potassium hydroxide (1M KOH) solution
Line, Ni2B、 Co2B、Fe2B is respectively 343mV, 373mV, 408mV in overpotential, reaches current density for 10 mA/cm2.Fig. 4 C
To be 3 by the metal that experiment three obtains and boron atom molar ratio：1 metal boride (M3B) in alkaline potassium hydroxide (1M
KOH) in solution water crack parsing oxygen polarization curve, Ni3B is 320mV in overpotential, reaches current density for 10mA/cm2。
Fig. 5 A is are 1 by the metal that experiment one obtains and boron atom molar ratio：1 metal boride (MB) is in alkalinity
The stability curve of water crack parsing oxygen in potassium hydroxide (1M KOH) solution.Fig. 5 B are former with boron by the metal that experiment two obtains
Sub- molar ratio is 2：1 metal boride (M2B) in alkaline potassium hydroxide (1M KOH) solution water crack parsing oxygen stability
Curve.Fig. 5 C is are 3 by the metals that experiment three obtains and boron atom molar ratio：1 metal boride (M3B) in alkaline hydrogen-oxygen
Change the stability curve of water crack parsing oxygen in potassium (1M KOH) solution.Its catalytic performance can at least stablize 100h, and unattenuated,
The catalyst is shown with fabulous catalytic stability.
Embodiment 2
It is same as Example 1, boriding medium is only changed to B4C, under the conditions of 1M KOH, the electrocatalysis of gained sample
Energy：
Metal is 1 with boron atom molar ratio：1 metal boride (MB)：CoB, FeB, MoB, WB are respectively in overpotential
361mV, 373mV, 431mV, 459mV reach current density for 10mA cm-2。
Metal is 2 with boron atom molar ratio：1 metal boride (MB)：Ni2B、Co2B、Fe2B is respectively in overpotential
345mV, 376mV, 409mV reach current density for 10mA cm-2。
Metal is 3 with boron atom molar ratio：1 metal boride (MB)：Ni3B is 313mV in overpotential, reaches electric current
Density is 10mA cm-2。
Embodiment 3
It is same as Example 1, boriding medium is only changed to NaB4O7, under the conditions of 1M KOH, the electro-catalysis of gained sample
Performance：
Metal is 1 with boron atom molar ratio：1 metal boride (MB)：CoB, FeB, MoB, WB are respectively in overpotential
364mV, 373mV, 429mV, 463mV reach current density for 10mA cm-2。
Metal is 2 with boron atom molar ratio：1 metal boride (MB)：Ni2B、Co2B、Fe2B is respectively in overpotential
348mV, 363mV, 403mV reach current density for 10mA cm-2。
Metal is 3 with boron atom molar ratio：1 metal boride (MB)：Ni3B is 312mV in overpotential, reaches electric current
Density is 10mA cm-2。
Embodiment 4
It is same as Example 1, boriding medium is only changed to B2O3, under the conditions of 1M KOH, the electrocatalysis of gained sample
Energy：
Metal is 1 with boron atom molar ratio：1 metal boride (MB)：CoB, FeB, MoB, WB are respectively in overpotential
358mV, 373mV, 436mV, 463mV reach current density for 10mA cm-2。
Metal is 2 with boron atom molar ratio：1 metal boride (MB)：Ni2B、Co2B、Fe2B is respectively in overpotential
339mV, 370mV, 411mV reach current density for 10mA cm-2。
Metal is 3 with boron atom molar ratio：1 metal boride (MB)：Ni3B is 313mV in overpotential, reaches electric current
Density is 10mA cm-2。
Embodiment 5
It is same as Example 1, the activator tested in one and experiment two is only changed to NaBF4, under the conditions of 1M KOH,
The electrocatalysis characteristic of gained sample：
Metal is 1 with boron atom molar ratio：1 metal boride (MB)：CoB, FeB, MoB, WB are respectively in overpotential
359mV, 376mV, 433mV, 462mV reach current density for 10mA cm-2。
Metal is 2 with boron atom molar ratio：1 metal boride (MB)：Ni2B、Co2B、Fe2B is respectively in overpotential
346mV, 375mV, 402mV reach current density for 10mA cm-2。
Embodiment 6
It is same as Example 1, the activator tested in one and experiment two is only changed to NaBF4, under the conditions of 1M KOH,
The electrocatalysis characteristic of gained sample：
Metal is 1 with boron atom molar ratio：1 metal boride (MB)：CoB, FeB, MoB, WB are respectively in overpotential
363mV, 374mV, 435mV, 463mV reach current density for 10mA/cm2。
Metal is 2 with boron atom molar ratio：1 metal boride (MB)：Ni2B、Co2B、Fe2B is respectively in overpotential
345mV, 374mV, 406mV reach current density for 10mA cm-2。
Embodiment 7
It is same as Example 1, the activator tested in one and experiment two is only changed to K2SiF6, under the conditions of 1M KOH,
The electrocatalysis characteristic of gained sample：
Metal is 1 with boron atom molar ratio：1 metal boride (MB)：CoB, FeB, MoB, WB are respectively in overpotential
362mV, 373mV, 435mV, 462mV reach current density for 10mA cm-2。
Metal is 2 with boron atom molar ratio：1 metal boride (MB)：Ni2B、Co2B、Fe2B is respectively in overpotential
341mV, 376mV, 411mV reach current density for 10mA cm-2。
Embodiment 8
It is same as Example 1, the activator tested in one and experiment two is only changed to NaCO3, under the conditions of 1M KOH,
The electrocatalysis characteristic of gained sample：
Metal is 1 with boron atom molar ratio：1 metal boride (MB)：CoB, FeB, MoB, WB are respectively in overpotential
357mV, 368mV, 433mV, 457mV reach current density for 10mA cm-2。
Metal is 2 with boron atom molar ratio：1 metal boride (MB)：Ni2B、Co2B、Fe2B is respectively in overpotential
346mV, 370mV, 406mV reach current density for 10mA cm-2。
Embodiment 9
It is same as Example 1, the activator tested in one and experiment two is only changed to NH4Cl, under the conditions of 1M KOH,
The electrocatalysis characteristic of gained sample：
Metal is 1 with boron atom molar ratio：1 metal boride (MB)：CoB, FeB, MoB, WB are respectively in overpotential
358mV, 373mV, 432mV, 457mV reach current density for 10mA cm-2。
Metal is 2 with boron atom molar ratio：1 metal boride (MB)：Ni2B、Co2B、Fe2B is respectively in overpotential
341mV, 370mV, 403mV reach current density for 10mA cm-2。
Embodiment 10
It is same as Example 1, the filler tested in two and experiment three is only changed to the Al after roasting2O3(by Al2O3
600℃Calcining, it is fully dry, remove moisture removal), under the conditions of 1M KOH, the electrocatalysis characteristic of gained sample：
Metal is 2 with boron atom molar ratio：1 metal boride (MB)：Ni2B、Co2B、Fe2B is respectively in overpotential
345mV, 374mV, 411mV reach current density for 10mA cm-2。
Metal is 3 with boron atom molar ratio：1 metal boride (MB)：Ni3B is 315mV in overpotential, reaches electric current
Density is 10mA cm-2。
Embodiment 11
It is same as Example 1, the filler tested in two and experiment three is only changed to granular graphite, in 1M KOH conditions
Under, the electrocatalysis characteristic of gained sample：
Metal is 2 with boron atom molar ratio：1 metal boride (MB)：Ni2B、Co2B、Fe2B is respectively in overpotential
345mV, 374mV, 405mV reach current density for 10mA cm-2。
Metal is 3 with boron atom molar ratio：1 metal boride (MB)：Ni3B is 313mV in overpotential, reaches electric current
Density is 10mA cm-2。
Embodiment 12
It is same as Example 1, the filler tested in two and experiment three is only changed to charcoal, under the conditions of 1M KOH,
The electrocatalysis characteristic of gained sample：
Metal is 2 with boron atom molar ratio：1 metal boride (MB)：Ni2B、Co2B、Fe2B is respectively in overpotential
341mV, 376mV, 412mV reach current density for 10mA cm-2。
Metal is 3 with boron atom molar ratio：1 metal boride (MB)：Ni3B is 313mV in overpotential, reaches electric current
Density is 10mA cm-2。
Embodiment 13
It is same as Example 1, calcination temperature is only changed to 530 DEG C, under the conditions of 1M KOH, the electro-catalysis of gained sample
Performance：
Metal is 1 with boron atom molar ratio：1 metal boride (MB)：CoB, FeB, MoB, WB are respectively in overpotential
362mV, 373mV, 434mV, 462mV reach current density for 10mA cm-2。
Metal is 2 with boron atom molar ratio：1 metal boride (MB)：Ni2B、Co2B、Fe2B is respectively in overpotential
348mV, 376mV, 402mV reach current density for 10mA cm-2。
Metal is 3 with boron atom molar ratio：1 metal boride (MB)：Ni3B is 318mV in overpotential, reaches electric current
Density is 10mA cm-2。
Embodiment 14
It is same as Example 1, calcination temperature is only changed to 1100 DEG C, under the conditions of 1M KOH, the electricity of gained sample is urged
Change performance：
Metal is 1 with boron atom molar ratio：1 metal boride (MB)：CoB, FeB, MoB, WB are respectively in overpotential
363mV, 374mV, 435mV, 463mV reach current density for 10mA cm-2。
Metal is 2 with boron atom molar ratio：1 metal boride (MB)：Ni2B、Co2B、Fe2B is respectively in overpotential
341mV, 370mV, 412mV reach current density for 10mA cm-2。
Metal is 3 with boron atom molar ratio：1 metal boride (MB)：Ni3B is 320mV in overpotential, reaches electric current
Density is 10mA cm-2。
Embodiment 15
It is same as Example 1, calcination time is only changed to 0.5h, under the conditions of 1M KOH, the electro-catalysis of gained sample
Performance：
Metal is 1 with boron atom molar ratio：1 metal boride (MB)：CoB, FeB, MoB, WB are respectively in overpotential
363mV, 373mV, 434mV, 465mV reach current density for 10mA cm-2。
Metal is 2 with boron atom molar ratio：1 metal boride (MB)：Ni2B、Co2B、Fe2B is respectively in overpotential
341mV, 376mV, 409mV reach current density for 10mA cm-2。
Metal is 3 with boron atom molar ratio：1 metal boride (MB)：Ni3B is 323mV in overpotential, reaches electric current
Density is 10mA cm-2。
Embodiment 16
It is same as Example 1, calcination time is only changed to 4h, under the conditions of 1M KOH, the electrocatalysis of gained sample
Energy：
Metal is 1 with boron atom molar ratio：1 metal boride (MB)：CoB, FeB, MoB, WB are respectively in overpotential
363mV, 377mV, 433mV, 466mV reach current density for 10mA cm-2。
Metal is 2 with boron atom molar ratio：1 metal boride (MB)：Ni2B、Co2B、Fe2B is respectively in overpotential
345mV, 374mV, 412mV reach current density for 10mA cm-2。
Metal is 3 with boron atom molar ratio：1 metal boride (MB)：Ni3B is 319mV in overpotential, reaches electric current
Density is 10mA cm-2。
Embodiment 17
It is same as Example 1, raw material dosage in experiment one is only changed to ma：mb=4：1st, raw material dosage in experiment two
It is changed to ma：mb：mc=9：0：0th, raw material dosage is changed to m in experiment threea：mc=1：9, under the conditions of 1M KOH, gained sample
Electrocatalysis characteristic：
Metal is 1 with boron atom molar ratio：1 metal boride (MB)：CoB, FeB, MoB, WB are respectively in overpotential
363mV, 372mV, 432mV, 465mV reach current density for 10mA cm-2。
Metal is 2 with boron atom molar ratio：1 metal boride (MB)：Ni2B、Co2B、Fe2B is respectively in overpotential
340mV, 374mV, 409mV reach current density for 10mA cm-2。
Metal is 3 with boron atom molar ratio：1 metal boride (MB)：Ni3B is 323mV in overpotential, reaches electric current
Density is 10mA cm-2。
Embodiment 18
It is same as Example 1, raw material dosage in experiment one is only changed to ma：mb=19：1st, raw material dosage in experiment two
It is changed to ma：mb：mc=5：0.5：9th, raw material dosage is changed to m in experiment threea：mc=1：5, under the conditions of 1M KOH, gained sample
The electrocatalysis characteristic of product：
Metal is 1 with boron atom molar ratio：1 metal boride (MB)：CoB, FeB, MoB, WB are respectively in overpotential
364mV, 375mV, 431mV, 463mV reach current density for 10mA cm-2。
Metal is 2 with boron atom molar ratio：1 metal boride (MB)：Ni2B、Co2B、Fe2B is respectively in overpotential
345mV, 380mV, 403mV reach current density for 10mA cm-2。
Metal is 3 with boron atom molar ratio：1 metal boride (MB)：Ni3B is 318mV in overpotential, reaches electric current
Density is 10mA cm-2。
Embodiment 19
It is same as Example 1, transition metal is only changed to dilval, under the conditions of 1M KOH, the electricity of gained sample
Catalytic performance：
Metal is 1 with boron atom molar ratio：1 metal boride (MB)：Ni-FeB is 293 mV in overpotential, reaches electricity
Current density is 10mA cm-2。
Metal is 2 with boron atom molar ratio：1 metal boride (MB)：Ni-Fe2B is 286 mV in overpotential, is reached
Current density is 10mA cm-2。
Metal is 3 with boron atom molar ratio：1 metal boride (MB)：Fe-Ni3B is 263 mV in overpotential, is reached
Current density is 10mA cm-2。
Embodiment 20
It is same as Example 1, one transition metal of experiment is only changed to stainless steel, under the conditions of 1M KOH, gained sample
Electrocatalysis characteristic：
Metal is 1 with boron atom molar ratio：1 metal boride (MB)：Boron steel is 293mV in overpotential, reaches electric current
Density is 10mA cm-2。
Embodiment 21
It is same as Example 1, only test condition is changed to test under the conditions of 5M KOH, the electrocatalysis of gained sample
Energy：
Metal is 1 with boron atom molar ratio：1 metal boride (MB)：CoB, FeB, MoB, WB are respectively in overpotential
362mV, 373mV, 435mV, 461mV reach current density for 10mA cm-2。
Metal is 2 with boron atom molar ratio：1 metal boride (MB)：Ni2B、Co2B、Fe2B is respectively in overpotential
293mV, 313mV, 328mV reach current density for 10mA cm-2。
Metal is 3 with boron atom molar ratio：1 metal boride (MB)：Ni3B is 280mV in overpotential, reaches electric current
Density is 10mA cm-2。
Embodiment 22
It is same as Example 1, only test condition is changed to test under the conditions of 10M KOH, the electrocatalysis of gained sample
Energy：
Metal is 1 with boron atom molar ratio：1 metal boride (MB)：CoB, FeB, MoB, WB are respectively in overpotential
362mV, 370mV, 431mV, 464mV reach current density for 10mA cm-2。
Metal is 2 with boron atom molar ratio：1 metal boride (MB)：Ni2B、Co2B、Fe2B is respectively in overpotential
263mV, 293mV, 308mV reach current density for 10mA cm-2。
Metal is 3 with boron atom molar ratio：1 metal boride (MB)：Ni3B is 258mV in overpotential, reaches electric current
Density is 10mA cm-2。
Claims (10)
1. a kind of preparation method of metal boride water-splitting catalyst, its step are as follows：
Method one,
(1) boriding medium and activator, mass ratio m are weigheda：mb=(4~19)：1, it is fully ground uniformly mixed, is oozed
Boron agent；
(2) in the boriding medium for obtaining transition-metal Fe, Co, Mo, W, dilval or stainless steel embedment step (1), transition gold
Belong to boriding medium in boron atom and molar ratio be 1：1；
(3) product that step (2) obtains is warming up under conditions of steam is completely cut off 530 DEG C~1100 DEG C calcination processing 0.5h~
4h, so as to obtain metal and boron atom molar ratio 1：1 metal boride water-splitting catalyst；
Or method two,
(1) boriding medium, activator and filler, mass ratio m are weigheda：mb：mc=(9~1)：(0~1)：(0~18),
It is fully ground uniformly mixed, obtains boriding medium；
(2) transition-metal Fe, Co or Ni etc. or dilval are embedded to respectively in the boriding medium that step (1) obtains, transition metal
With boron atom in boriding medium and molar ratio be 2：1；
(3) product that step (2) obtains is warming up under conditions of steam is completely cut off 530 DEG C~1100 DEG C calcination processing 0.5h~
4h, so as to obtain metal and boron atom molar ratio 2：1 metal boride water-splitting catalyst；
Or method three,
(1) boriding medium and filler, mass ratio m are weigheda：mc=1：(9~1), are fully ground uniformly mixed, are oozed
Boron agent；
(2) transition metal Ni etc. or dilval are embedded to respectively in the boriding medium that step (1) obtains, transition metal and boronising
The molar ratio of boron atom sum is 3 in medium：1；
(3) product that step (2) obtains is warming up under conditions of steam is completely cut off 530 DEG C~1100 DEG C calcination processing 0.5h~
4h, so as to obtain metal and boron atom molar ratio 3：1 metal boride water-splitting catalyst.
2. a kind of preparation method of metal boride water-splitting catalyst as described in claim 1, it is characterised in that：Boronising is situated between
Matter is boron amorphous, B4C、Na2B4O7、B2O3Or its mixture.
3. a kind of preparation method of metal boride water-splitting catalyst as described in claim 1, it is characterised in that：Activator
For potassium fluoborate KBF4, sodium fluoborate NaBF4, prodan K2SiF6, sodium carbonate Na2CO3, ammonium chloride NH4Cl or its mixture.
4. a kind of preparation method of metal boride water-splitting catalyst as described in claim 1, it is characterised in that：Filler
For the alundum (Al2O3) Al after silicon carbide SiC, roasting2O3, granular graphite, charcoal or its mixture.
5. a kind of preparation method of metal boride water-splitting catalyst as described in claim 1, it is characterised in that：Calcining temperature
It is 700 DEG C~900 DEG C to spend, and calcination time is 1.5h~2.5h.
6. a kind of preparation method of metal boride water-splitting catalyst as described in claim 1, it is characterised in that：Method one
In, the mass ratio of boriding medium and activator is ma：mb=9：1；In method two, the quality of boriding medium, activator and filler
Than being preferably ma：mb：mc=1：1：18；In method three, the mass ratio of boriding medium and filler is preferably ma：mc=1：1.
7. a kind of metal boride water-splitting catalyst, it is characterised in that：It is as the side described in claim 1~6 any one
Method is prepared.
8. application of the metal boride water-splitting catalyst in terms of electro-catalysis water-splitting described in claim 7.
9. application of the metal boride water-splitting catalyst as claimed in claim 8 in terms of electro-catalysis water-splitting, feature
It is：It is the catalysis water-splitting oxygen evolution reaction in the alkaline solution of 1M~10M.
10. application of the metal boride water-splitting catalyst as claimed in claim 9 in terms of electro-catalysis water-splitting, feature
It is：It is the catalysis water-splitting oxygen evolution reaction in KOH solution.
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