CN106694005A - Preparation method of electric catalyst for acidic fully-decomposed water - Google Patents
Preparation method of electric catalyst for acidic fully-decomposed water Download PDFInfo
- Publication number
- CN106694005A CN106694005A CN201611081350.0A CN201611081350A CN106694005A CN 106694005 A CN106694005 A CN 106694005A CN 201611081350 A CN201611081350 A CN 201611081350A CN 106694005 A CN106694005 A CN 106694005A
- Authority
- CN
- China
- Prior art keywords
- manganese
- cobalt
- mol
- soluble
- conductive substrates
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 239000003054 catalyst Substances 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 230000002378 acidificating effect Effects 0.000 title abstract 4
- 239000000758 substrate Substances 0.000 claims abstract description 38
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 27
- 239000010941 cobalt Substances 0.000 claims abstract description 27
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 27
- MZZUATUOLXMCEY-UHFFFAOYSA-N cobalt manganese Chemical compound [Mn].[Co] MZZUATUOLXMCEY-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000002070 nanowire Substances 0.000 claims abstract description 16
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000004202 carbamide Substances 0.000 claims abstract description 12
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 11
- 150000002696 manganese Chemical class 0.000 claims abstract description 10
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 9
- 239000011574 phosphorus Substances 0.000 claims abstract description 9
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 8
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 8
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims abstract description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims abstract description 5
- 150000001868 cobalt Chemical class 0.000 claims abstract description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 3
- 239000001488 sodium phosphate Substances 0.000 claims abstract description 3
- 229910000162 sodium phosphate Inorganic materials 0.000 claims abstract description 3
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims abstract description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 28
- 238000000354 decomposition reaction Methods 0.000 claims description 20
- 239000002253 acid Substances 0.000 claims description 17
- 239000006260 foam Substances 0.000 claims description 14
- 229910052759 nickel Inorganic materials 0.000 claims description 14
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 13
- 239000002131 composite material Substances 0.000 claims description 13
- 239000011572 manganese Substances 0.000 claims description 13
- 239000000243 solution Substances 0.000 claims description 11
- 229910052748 manganese Inorganic materials 0.000 claims description 10
- 239000003708 ampul Substances 0.000 claims description 9
- 229910052573 porcelain Inorganic materials 0.000 claims description 9
- 239000010453 quartz Substances 0.000 claims description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 230000035484 reaction time Effects 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 238000013019 agitation Methods 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 238000010792 warming Methods 0.000 claims description 6
- 238000006555 catalytic reaction Methods 0.000 claims description 5
- 239000004744 fabric Substances 0.000 claims description 5
- 239000010936 titanium Substances 0.000 claims description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 4
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-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
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
- 239000001509 sodium citrate Substances 0.000 claims description 4
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- 238000003682 fluorination reaction Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-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
- 239000011668 ascorbic acid Substances 0.000 claims description 2
- 229960005070 ascorbic acid Drugs 0.000 claims description 2
- 235000010323 ascorbic acid Nutrition 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 claims description 2
- 229910001437 manganese ion Inorganic materials 0.000 claims description 2
- 238000003491 array Methods 0.000 claims 1
- 230000034655 secondary growth Effects 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 24
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 abstract description 5
- 239000003513 alkali Substances 0.000 abstract description 5
- 238000000034 method Methods 0.000 abstract description 5
- 238000005516 engineering process Methods 0.000 abstract description 3
- 238000001354 calcination Methods 0.000 abstract description 2
- 230000000694 effects Effects 0.000 abstract description 2
- 239000012299 nitrogen atmosphere Substances 0.000 abstract description 2
- 239000002135 nanosheet Substances 0.000 abstract 3
- 239000012300 argon atmosphere Substances 0.000 abstract 1
- 238000005406 washing Methods 0.000 abstract 1
- 239000000463 material Substances 0.000 description 46
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 30
- 239000001257 hydrogen Substances 0.000 description 30
- 229910052739 hydrogen Inorganic materials 0.000 description 30
- 238000010586 diagram Methods 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 15
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 13
- 239000001301 oxygen Substances 0.000 description 13
- 229910052760 oxygen Inorganic materials 0.000 description 13
- 230000010287 polarization Effects 0.000 description 12
- 238000004458 analytical method Methods 0.000 description 10
- 238000001228 spectrum Methods 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 6
- 230000002441 reversible effect Effects 0.000 description 6
- HTXDPTMKBJXEOW-UHFFFAOYSA-N iridium(IV) oxide Inorganic materials O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 4
- 229910052723 transition metal Inorganic materials 0.000 description 4
- 150000003624 transition metals Chemical class 0.000 description 4
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 3
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 238000003487 electrochemical reaction Methods 0.000 description 3
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 230000036632 reaction speed Effects 0.000 description 3
- 230000001052 transient effect Effects 0.000 description 3
- 241000209094 Oryza Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000005518 electrochemistry Effects 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 235000012149 noodles Nutrition 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000002134 carbon nanofiber Substances 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 229910001429 cobalt ion Inorganic materials 0.000 description 1
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(IV) oxide Inorganic materials O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 1
- 238000003786 synthesis reaction 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
- B01J27/187—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with manganese, technetium or rhenium
-
- 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—
-
- B01J35/33—
-
- B01J35/61—
-
- 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
-
- 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
The invention discloses a preparation method of an electric catalyst for acidic fully-decomposed water. The preparation method comprises the following steps: carrying out ultrasonic washing on a conductive substrate; preparing a first water solution containing soluble cobalt salt, soluble manganese salt, ammonium fluoride and urea; vertically forming a manganese-cobalt alkali type carbonate nanowire array on the surface of the substrate in a reaction kettle; preparing a second water solution containing the soluble cobalt salt, the soluble manganese salt, a reducing agent, the ammonium fluoride and the urea; growing for a second time to form a manganese-cobalt alkali type carbonate nano-sheet, so as to form a manganese-cobalt alkali type carbonate nano-sheet compounded nanowire multi-grade structure; taking sodium hypophosphite or sodium phosphate as a phosphorus source in a tubular furnace; calcining in a nitrogen or argon atmosphere at 200 DEG C to 1000 DEG C to prepare the electric catalyst for the acidic fully-decomposed water, which has a manganese-doped cobalt phosphide ultrathin nano-sheet compounded nanowire multi-grade structure. According to the preparation method disclosed by the invention, a simple hydrothermal synthesis and low-temperature phosphating treatment process is carried out, and a technology is simple and easy to regulate and control; the catalyst is a dual-purpose electric catalyst which has an extremely good application prospect and has an extremely good effect in the acidic fully-decomposed water.
Description
Technical field
The present invention is that, on elctro-catalyst, more particularly to a kind of transient metal doped being combined with ultrathin nanometer piece is received
Full decomposition water elctro-catalyst of acidity of rice noodles multilevel hierarchy array and preparation method thereof.
Background technology
Full electrolysis aquatic products hydrogen and product oxygen in same electrolyte are to tackle energy shortage and one kind of environmental pollution to have
Effect solution route, but huge challenge is also faced with simultaneously.In this area, design and obtain high performance evolving hydrogen reaction
And the difunctional electro catalytic electrode material of oxygen evolution reaction (OER) is always the target of researcher (HER).At present, noble metal (Pt,
IrO2And RuO2Deng) catalyst surface active is high, there is fabulous catalytic performance to HER and OER, but its high cost, reserves are less simultaneously
Actual demand can not be met.Therefore, carbide, chloride, sulfide and the phosphorus constituted with transition metal are developed in recent years
Compound etc. as high-efficiency environment friendly HER catalyst, the oxide and phosphate etc. of transition metal composition are used as efficient OER electricity
Catalyst turns into current study hotspot.But, it is difunctional that these catalyst are used as OER and HER simultaneously in same electrolyte
Catalyst, then have active low, stability, so as to limit their scale application.Based on this, design is closed
Into new, high-performance, can realize that the difunctional electricity of the non-noble metallic materials of efficient liberation of hydrogen and analysis oxygen is urged in same electrolyte
Agent, the study hotspot as current material science Yu new energy field.
The content of the invention
The purpose of the present invention, is to be used as double work(in same electrolyte to solve existing analysis oxygen and evolving hydrogen reaction catalyst
Can catalyst when, the catalytic current density for existing is low, and overpotential is higher, stability difference the problems such as, there is provided a kind of transition metal is mixed
The miscellaneous full decomposition water elctro-catalyst with ultrathin nanometer piece composite nano-line multilevel hierarchy array, significantly reduces analysis oxygen anti-
Should be the functional direction design and performance optimization of full decomposition water System Catalyst with the overpotential of evolving hydrogen reaction and a spike potential
There is provided new thinking and strategy.
The present invention is achieved by following technical solution.
A kind of preparation method of acid full decomposition water elctro-catalyst, comprises the following steps that：
(1) conductive substrates are cleaned by ultrasonic 5~20 minutes in the hydrochloric acid of 1 mol/L~5 mol/L, are then transferred to
It is cleaned by ultrasonic 5~20 minutes in acetone soln, transfers in ethanol solution and be cleaned by ultrasonic 5~20 minutes, finally uses deionization
Water rinses conductive substrates surfaces, then is put into 25~80 DEG C of baking oven and dries 60~180 minutes.
(2) first aqueous solution with soluble cobalt, soluble manganese salt, ammonium fluoride and urea, the solubility are prepared
Cobalt salt concentration is 0.001-0.01 mol/Ls, and soluble manganese salinity is 0.0005-0.01 mol/Ls, and fluorination ammonium concentration is
0.01-0.1 mol/Ls, urea concentration is 0.0125-0.1 mol/Ls, and the soluble cobalt and manganese salt are nitrate, sulfuric acid
Any one of salt or acetate；
Above-mentioned first solution magnetic agitation is transferred in reactor after 5~30 minutes, then by step (1) treatment after lead
Electric substrate tilt is put into the first reactor, then the closed reactor, is warming up to 80 DEG C~200 DEG C, is entered at autogenous pressures
Row first time hydro-thermal reaction, the reaction time is 5~20 hours, with the vertical-growth manganese cobalt basic carbonate on the conductive substrates surface
Salt nano-wire array；
(3) conductive substrates of step (2) are taken out, with deionized water rinsing conductive substrates surface, 25~80 DEG C is subsequently placed into
Baking oven in dry 60~180 minutes；
(4) second aqueous solution of the configuration with soluble cobalt, soluble manganese salt, reducing agent, ammonium fluoride and urea, described
Soluble cobalt concentration be 0.001-0.01 mol/Ls, soluble manganese salinity be 0.0005-0.01 mol/Ls, manganese ion and
The total ion concentration of cobalt ions maintains 0.0015 mol/L, and reductant concentration is 0.0005-0.01 mol/Ls, and ammonium fluoride is dense
It is 0.01-0.1 mol/Ls to spend, and urea concentration is 0.0125-0.1 mol/Ls, the soluble cobalt and manganese salt be nitrate,
Any one of sulfate or acetate, reducing agent are sodium citrate or ascorbic acid；
Above-mentioned second solution magnetic agitation is transferred in the second reactor after 5~30 minutes, then by after step (3) treatment
Conductive substrates it is tilting be put into the second reactor, seal the reactor, be warming up to 80 DEG C~200 DEG C, enter at autogenous pressures
Second hydro-thermal reaction of row, the reaction time is 5~20 hours, with enterprising in each described manganese cobalt subcarbonate nanowire surface
Row diauxic growth manganese cobalt subcarbonate nanometer sheet, forms manganese cobalt subcarbonate nanometer sheet composite nano-line multilevel hierarchy；
(5) step (4) conductive substrates are taken out again, with the deionized water rinsing conductive substrates surface, are then put into 25
Dried 60~180 minutes in~80 DEG C of baking oven；
(6) two porcelain boats are placed in the quartz ampoule of tube furnace, the conductive substrates after step (5) treatment is put into quartz ampoule
In the porcelain boat of lower section, while phosphorus source is put into the porcelain boat of air inlet in quartz ampoule upper end, in nitrogen or argon gas atmosphere,
Calcined 0.5~8 hour at 200~1000 DEG C, be subsequently cooled to room temperature so that manganese cobalt subcarbonate ultrathin nanometer piece is compound to be received
The full water power that decomposes of acidity that rice noodles multilevel hierarchy is changed into the phosphatization cobalt ultrathin nanometer piece composite nano-line multilevel hierarchy for mixing manganese is urged
Agent, is named as 1D/2D Mn-CoP.
The conductive substrates of the step (1) are nickel foam both any one of NF, titanium sheet or carbon cloth.
The phosphorus source of the step (6) is sodium hypophosphite, sodium phosphate.
Beneficial effects of the present invention are as follows：
The preparation method is made up of simple hydro-thermal reaction and low temperature phosphor treatment, and step is simple, the reaction time is short, operation
It is convenient, it is very friendly to environment, repeatable strong；Material of the invention is fabulous difunctional electro-catalysis in acid full decomposition water
Agent, when current density is 10mA/cm2When, overpotential is 0.35V, while be also fabulous elctro-catalyst in acid evolving hydrogen reaction,
When current density is 10mA/cm2When, overpotential is 0.042V, close to business Pt/C catalyst, and excellent stability.This hair
Bright material, by introducing external transition metal, not only contributes to OH due to doping effect-Absorption so that hydrogen is easy
Desorption, reduces the reaction barrier of evolving hydrogen reaction, super thin vapor interface is formed between solid-liquid two-phase, additionally, due to ultrathin nanometer piece
The presence of composite nano-line multilevel hierarchy greatly increases the specific surface area of electrode active material, there is provided more avtive spots,
The collaboration of these factors enhances electro-catalysis ability of the material in acid full decomposition water reaction.
Brief description of the drawings
Fig. 1 is the transient metal doped with the complete of ultrathin nanometer piece composite nano-line multilevel hierarchy array of embodiment 1
The structural representation of decomposition water elctro-catalyst；
Fig. 2 is that the phosphatization cobalt material of the additive Mn after a hydrothermal growth phosphorating treatment of comparative example (is named as
Scanning electron microscope (SEM) photograph (SEM) 1DMn-CoP)；
Fig. 3 is the stereoscan photograph figure (SEM) of the material shown in embodiment 1；
Fig. 4 is the scanning electron microscope (SEM) photograph (SEM) of the high power of the material shown in embodiment 1；
Fig. 5 is that the low power of the material shown in embodiment 1 projects electron microscope (TEM)；
Fig. 6 is that the high-resolution of the material shown in embodiment 1 projects electron microscope (HRTEM)；
Fig. 7 a are the low power scanning electron microscope (SEM) photographs of the phosphatization cobalt multilevel hierarchy for being grown in the additive Mn on carbon cloth of embodiment 2
(SEM)；Fig. 7 b are the high power scanning electron microscope (SEM) photographs of the phosphatization cobalt multilevel hierarchy for being grown in the additive Mn on carbon cloth of embodiment 2
(SEM)；
Fig. 8 is polarization curve (LSV) figure of material shown in embodiment 2 evolving hydrogen reaction in acid condition, reference electricity
Extremely reversible hydrogen electrode；
Fig. 9 is the X-ray diffractogram (XRD) of the material shown in embodiment 1；
Figure 10 is the x-ray photoelectron energy spectrum diagram (XPS) of the cobalt element of the material shown in embodiment 1；
Figure 11 is the x-ray photoelectron energy spectrum diagram (XPS) of the manganese element of the material shown in embodiment 1；
Figure 12 is the x-ray photoelectron energy spectrum diagram (XPS) of the P elements of the material shown in embodiment 1；
Figure 13 is X-ray microcell energy spectrum diagram (EDS) of the material shown in embodiment 1；
Figure 14 is foam nickel base, the material shown in comparative example, the material shown in embodiment 1 and Pt/C in acid
Polarization curve (LSV) comparison diagram of evolving hydrogen reaction under the conditions of property, reference electrode is reversible hydrogen electrode；
Figure 15 is foam nickel base, the material shown in comparative example, the material shown in embodiment 1 and Pt/C in acid
Tafel curve slope (Tafel) under the conditions of property compares figure；
Figure 16 is foam nickel base, the material shown in comparative example, the material shown in embodiment 1 and Pt/C in acid
Electrochemistry specific surface comparison diagram under the conditions of property；
Figure 17 is the material shown in comparative example, the material and IrO shown in embodiment 12Analyse in acid condition
Polarization curve (LSV) comparison diagram of oxygen reaction, reference electrode is reversible hydrogen electrode；
Figure 18 is corresponding material and IrO in material, embodiment 1 shown in comparative example2Analyse in acid condition
The Tafel curve slope (Tafel) of oxygen reaction compares figure；
Figure 19 is Pt/C as negative electrode IrO2As the material shown in anode and embodiment 1 simultaneously as anode and negative electrode
The full decomposition water reaction of acidity polarization curve (LSV) comparison diagram；
Figure 20 is that the material shown in embodiment 1 is tested as the constant-pressure stable that anode and negative electrode carry out full decomposition water
Figure；
Figure 21 is polarization curve (LSV) figure of material shown in embodiment 3 evolving hydrogen reaction in acid condition.
Specific embodiment
Below by specific embodiment, the invention will be further described, what embodiment was merely exemplary, and unrestricted
Property.
Embodiment 1
Conductive substrates are nickel foam, and phosphorus source is sodium hypophosphite, and reducing agent is sodium citrate.
(1) nickel foam conductive substrates are cleaned, to remove the dirt on surface and impurity.First surpass in the hydrochloric acid of 3 mol/Ls
Sound is cleaned 10 minutes, is then transferred to be cleaned by ultrasonic 10 minutes in acetone soln, to be transferred to and be cleaned by ultrasonic 10 in ethanol solution
Minute, finally repeatedly rinse conductive substrates surface with deionized water, then be put into 60 DEG C of baking oven and dry 60 minutes；
(2) prepare comprising the cobalt nitrate of 0.001 mol/L, the manganese nitrate of 0.0005 mol/L, 0.0125 mol/L
First aqueous solution of the urea of ammonium fluoride and 0.01 mol/L, magnetic agitation is transferred in reactor after 15 minutes, then will be passed through
The nickel foam of step (1) treatment is inclined and is put into reactor, and then the closed reactor, is warming up to 100 DEG C, at autogenous pressures
First time hydro-thermal reaction is carried out, the reaction time is 12 hours, with vertical substrate grown manganese cobalt alkali formula on the foam nickel surface
Carbonate nano-wire array；
(3) the nickel foam conductive substrates are taken out, with deionized water rinsing nickel foam conductive substrates surface, 60 DEG C is subsequently placed into
Baking oven in dry 60 minutes；
(4) configuration rubs comprising the cobalt nitrate comprising 0.001 mol/L, the sodium citrate of 0.0005 mol/L, 0.0005
You/liter manganese nitrate, the ammonium fluoride of 0.0125 mol/L and 0.01 mol/L the aqueous solution of urea second, 15 points of magnetic agitation
Be transferred to after clock in the second reactor, then by step (3) treatment after nickel foam conductive substrates it is tilting be put into the second reactor,
Seal the reactor, be warming up to 100 DEG C, carry out second hydro-thermal reaction at autogenous pressures, the reaction time is 10 hours, with
Diauxic growth manganese cobalt subcarbonate nanometer sheet is carried out in each described manganese cobalt subcarbonate nanowire surface, manganese cobalt alkali is formed
Formula carbonate nanometer sheet composite nano-line multilevel hierarchy；
(5) the nickel foam conductive substrates are taken out again, is repeatedly rinsed with deionized water and is changed conductive substrates surface, be then put into
Dried 60 minutes in 60 DEG C of baking oven；
(6) two porcelain boats are placed in the quartz ampoule of tube furnace, the conductive substrates after step (5) treatment is put into quartz ampoule
In the porcelain boat of middle lower section, while be put into sodium hypophosphite in the porcelain boat of air inlet in quartz ampoule upper end, in argon gas atmosphere,
Calcined 3 hours in 300 DEG C of tube furnace, be subsequently cooled to room temperature so that manganese cobalt subcarbonate ultrathin nanometer piece composite Nano
Line multilevel hierarchy is changed into the full decomposition water electro-catalysis of acidity of the phosphatization cobalt ultrathin nanometer piece composite nano-line multilevel hierarchy for mixing manganese
Agent, is named as 1D/2D Mn-CoP.
Analysis oxygen of the material in the sulfuric acid solution of 0.5 mol/L, liberation of hydrogen and full decomposition water are tested using three-electrode system
Performance, wherein, it is platinized platinum to electrode, reference electrode is reversible hydrogen electrode, and sweep speed is 5mV/s.
Fig. 1 is the structural representation of the 1D/2D Mn-CoP of embodiment 1, it can be seen that nanometer sheet homoepitaxial is in nano wire
Surface, such multilevel hierarchy in an array manner vertical-growth on conductive substrates surface.
Fig. 3 is the low power scanning electron microscope (SEM) photograph (SEM) of the 1D/2D Mn-CoP of embodiment 1, wherein clearly show, it is ultra-thin
Nanometer sheet composite nano-line multilevel hierarchy array is perpendicular to foam nickel surface homoepitaxial.
Fig. 4 is the high power scanning electron microscope (SEM) photograph (SEM) of the 1D/2D Mn-CoP of embodiment 1, it can be seen that nanowire surface is equal
It is even to grow nanometer sheet, interlaced between nanometer sheet, formation network structure；Nanowire diameter is in 100-150nm, length
10-20μm。
Fig. 5 is the low power transmission electron microscope picture (TEM) of the 1D/2D Mn-CoP of embodiment 1, it is known that observed with scanning electron microscope (SEM) photograph
Result is consistent, is still kept by multilevel hierarchy after low temperature phosphor treatment.
Fig. 6 is that the high-resolution of the 1D/2D Mn-CoP of embodiment 1 projects electron microscope (HRTEM), by measuring spacing of lattice,
The material for proving synthesis is phosphatization cobalt, and the doping of manganese is without the crystal structure for changing phosphatization cobalt.
Fig. 9 is the X-ray diffractogram (XRD) of the 1D/2D Mn-CoP of embodiment 1, and this can be identified with standard spectrogram contrast
The material composition of invention is phosphatization cobalt, corresponding with high-resolution projection electron microscope.
Figure 10 is the x-ray photoelectron energy spectrum diagram (XPS) of the cobalt element of the 1D/2D Mn-CoP of embodiment 1, it is known that cobalt
Valence state has+3 and+2.
Figure 11 is the x-ray photoelectron energy spectrum diagram (XPS) of the manganese element of the 1D/2D Mn-CoP of embodiment 1, it was demonstrated that material
In contain manganese element, manganese valence has+3 and+2.
Figure 12 is the x-ray photoelectron energy spectrum diagram (XPS) of the P elements of the 1D/2D Mn-CoP of embodiment 1, Co 2p3/2With
P 2p3/2Corresponding position is the P-Co keys in typical phosphatization cobalt.
Figure 13 is X-ray microcell energy spectrum diagram (EDS) of the 1D/2D Mn-CoP of embodiment 1, it was demonstrated that in material containing manganese,
Cobalt, three kinds of elements of phosphorus, the doping of manganese is 1.49%, the content ratio about 1 to 1 of cobalt and phosphorus.
Figure 14 is the liberation of hydrogen of the 1D/2D Mn-CoP of embodiment 1,1D Mn-CoP, NF of comparative example and business Pt/C
Polarization curve comparison diagram, it is known that 1D/2D Mn-CoP are in -10mA/cm2Corresponding overpotential is 42mV, close to business Pt/C catalysis
Agent.
Figure 15 is the liberation of hydrogen of the 1D/2D Mn-CoP of embodiment 1,1D Mn-CoP, NF of comparative example and business Pt/C
The Tafel slope comparison diagram of reaction, it is known that 1D/2D Mn-CoP have smaller Tafel slope, further relate to 1D/2D Mn-
CoP has faster electrochemical reaction speed.
Figure 16 is the 1D/2D Mn-CoP of embodiment 1,1D Mn-CoP, NF of comparative example and business Pt/C in liberation of hydrogen
Electrochemical surface area during reaction compares figure, it is known that the electrochemistry of 1D/2D Mn-CoP compares face highest, and electro catalytic activity is also most
It is high.
Figure 17 is the 1D Mn-CoP and business IrO of the 1D/2D Mn-CoP of embodiment 1, comparative example2Oxygen evolution reaction
When polarization curve comparison diagram, it is known that 1D/2D Mn-CoP analysis oxygen performances in acid condition be better than 1D Mn-CoP and business
IrO2。
Figure 18 is the analysis oxygen of the 1D/2D Mn-CoP of embodiment 1,1D Mn-CoP, NF of comparative example and business Pt/C
The Tafel slope comparison diagram of reaction, it is known that 1D/2D Mn-CoP have smaller Tafel slope, further relate to 1D/2D Mn-
CoP has faster electrochemical reaction speed.
Figure 19 is Pt/C as negative electrode IrO2As the 1D/2D Mn-CoP of anode and embodiment 1 simultaneously as anode and the moon
Polarization curve (LSV) comparison diagram of the full decomposition water reaction of acidity of pole.Understand 1D/2D Mn-CoP simultaneously as anode and negative electrode
Full decomposition water is carried out, when electric current reaches 10mA/cm2When overpotential be 0.35V.
Figure 20 is that the 1D/2D Mn-CoP of embodiment 1 are tested as the constant-pressure stable that anode and negative electrode carry out full decomposition water
Figure.Understand under the voltage of 1.4V, tested by the constant pressures of 20000 seconds, the electric current that the material is produced remains unchanged.
Embodiment 2
A kind of transient metal doped full decomposition water of the acidity with ultrathin nanometer piece composite nano-line multilevel hierarchy array
The method of elctro-catalyst, the conductive substrates are carbon cloths.
The preparation method of the electrocatalysis material is substantially the same manner as Example 1, and difference is：By leading in step (1)
Electric substrate is changed to carbon cloth.The electrocatalysis material is named as 1D/2D Mn-CoP/CC.
Fig. 7 a are the low power scanning electron microscope (SEM) photographs of the 1D/2D Mn-CoP/CC of embodiment 2, it can be seen that the material is uniformly given birth to
It is long to can be seen that nanometer sheet is equably grown in nanowire surface in the surface of carbon nano-fiber, Fig. 7 b, form nanometer sheet and answer
Close nano wire multilevel hierarchy.
Fig. 8 is polarization curve (LSV) figure of the 1D/2D Mn-CoP/CC evolving hydrogen reactions in acid condition of embodiment 2, from
It can be seen that when electric current reaches -10mA/cm in figure2When, evolving hydrogen reaction is 52mV with respect to the overpotential of reversible hydrogen electrode, is indicated
The fabulous catalytic hydrogen evolution reactivity worth of the material.
Embodiment 3
The preparation method of the electrocatalysis material is substantially the same manner as Example 1, and difference is：By leading in step (1)
Electric substrate is changed to titanium sheet.The material designation is 1D/2D Mn-CoP/Ti.
Figure 21 is the polarization curve of 1D/2D Mn-CoP/Ti evolving hydrogen reactions under sour environment, as can be seen from the figure
When electric current reaches -10mA/cm2When, evolving hydrogen reaction is 63mV with respect to the overpotential of reversible hydrogen electrode, indicates the material fabulous
Catalytic hydrogen evolution reactivity worth.
Embodiment 4
The preparation method of the electrocatalysis material is substantially the same manner as Example 1, and difference is：By step (2) and step
(4) concentration of the cobalt nitrate in is changed to 0.01 mol/L.
Embodiment 5
The preparation method of the electrocatalysis material is substantially the same manner as Example 1, and difference is：By step (2) and step
(4) concentration of the manganese nitrate in is changed to 0.01 mol/L.
Embodiment 6
The preparation method of the electrocatalysis material is substantially the same manner as Example 1, and difference is：By argon gas in step (6)
Atmosphere is changed to nitrogen atmosphere, and calcination time was changed to 0.5 hour by 3 hours.
Comparative example
The preparation method of the electrocatalysis material is substantially the same manner as Example 1, and difference is：By step (3) once
Phosphorating treatment is directly carried out after hydrothermal growth, the material designation is 1D Mn-CoP.
Fig. 2 is the scanning electron microscope (SEM) photograph of 1D Mn-CoP, it may be clearly seen that one-dimensional nano wire is uniform in an array manner
Be grown in conductive substrates surface, and nanowire surface is very smooth.
Figure 14 is the liberation of hydrogen polarization curve of the 1D Mn-CoP of comparative example, it is known that 1D Mn-CoP are in -10mA/cm2
Corresponding overpotential is 88mV, and overpotential of hydrogen evolution will differ from 46mV compared with 1D/2D Mn-CoP.
Figure 15 is the Tafel slope figure of the 1D Mn-CoP evolving hydrogen reactions of comparative example, it is known that 1D Mn-CoP Ta Feier
Slope position 98mV/dec, illustrates that 1DMn-CoP electrochemical reaction speeds are slower than 1D/2D Mn-CoP.
Figure 17 is the analysis oxygen polarization curve of the 1D Mn-CoP of comparative example, it is known that 1D Mn-CoP are in 100mA/cm2
Corresponding voltage is 1.68V, analyses oxygen performance close to noble metal IrO2。
The preferred embodiment of the present invention described in detail above, but, the present invention is not limited in above-mentioned implementation method
Detail, in range of the technology design of the invention, various simple variants can be carried out to technical scheme, this
A little simple variants belong to protection scope of the present invention.
It is further to note that each particular technique feature described in above-mentioned specific embodiment, in not lance
In the case of shield, can be combined by any suitable means, in order to avoid unnecessary repetition, the present invention to it is various can
The combination of energy is no longer separately illustrated.
Additionally, can also be combined between a variety of implementation methods of the invention, as long as it is without prejudice to originally
The thought of invention, it should equally be considered as content disclosed in this invention.
Claims (3)
1. a kind of preparation method of acid full decomposition water elctro-catalyst, comprises the following steps that：
(1) conductive substrates are cleaned by ultrasonic 5~20 minutes in the hydrochloric acid of 1 mol/L~5 mol/L, are then transferred to acetone
It is cleaned by ultrasonic 5~20 minutes in solution, transfers in ethanol solution and be cleaned by ultrasonic 5~20 minutes, is finally rushed with deionized water
Wash conductive substrates surface, then be put into 25~80 DEG C of baking oven and dry 60~180 minutes.
(2) first aqueous solution with soluble cobalt, soluble manganese salt, ammonium fluoride and urea, the soluble cobalt are prepared
Concentration is 0.001-0.01 mol/Ls, and soluble manganese salinity is 0.0005-0.01 mol/Ls, and fluorination ammonium concentration is 0.01-
0.1 mol/L, urea concentration is 0.0125-0.1 mol/Ls, the soluble cobalt and manganese salt be nitrate, sulfate or
Any one of acetate；
Above-mentioned first solution magnetic agitation is transferred in reactor after 5~30 minutes, then by the conductive base after step (1) treatment
Slanted floor is put into the first reactor, then the closed reactor, is warming up to 80 DEG C~200 DEG C, and is carried out at autogenous pressures
Hydro-thermal reaction, the reaction time is 5~20 hours, is received with the vertical-growth manganese cobalt subcarbonate on the conductive substrates surface
Nanowire arrays；
(3) conductive substrates of step (2) are taken out, with deionized water rinsing conductive substrates surface, 25~80 DEG C of baking is subsequently placed into
Dried 60~180 minutes in case；
(4) second aqueous solution of the configuration with soluble cobalt, soluble manganese salt, reducing agent, ammonium fluoride and urea, described solvable
Property cobalt salt concentration be 0.001-0.01 mol/Ls, soluble manganese salinity is 0.0005-0.01 mol/Ls, manganese ion and cobalt from
The total ion concentration of son maintains 0.0015 mol/L, and reductant concentration is 0.0005-0.01 mol/Ls, and fluorination ammonium concentration is
0.01-0.1 mol/Ls, urea concentration is 0.0125-0.1 mol/Ls, and the soluble cobalt and manganese salt are nitrate, sulfuric acid
Any one of salt or acetate, reducing agent are sodium citrate or ascorbic acid；
Above-mentioned second solution magnetic agitation is transferred in the second reactor after 5~30 minutes, then by step (3) treatment after lead
Electric substrate is tilting to be put into the second reactor, seals the reactor, is warming up to 80 DEG C~200 DEG C, and is carried out at autogenous pressures
Secondary hydro-thermal reaction, the reaction time is 5~20 hours, and two are carried out with each described manganese cobalt subcarbonate nanowire surface
Secondary growth manganese cobalt subcarbonate nanometer sheet, forms manganese cobalt subcarbonate nanometer sheet composite nano-line multilevel hierarchy；
(5) step (4) conductive substrates are taken out again, with the deionized water rinsing conductive substrates surface, are then put into 25~80
DEG C baking oven in dry 60~180 minutes；
(6) two porcelain boats are placed in the quartz ampoule of tube furnace, the conductive substrates after step (5) treatment is put into quartz ampoule lower section
Porcelain boat in, while be put into phosphorus source in the porcelain boat of air inlet in quartz ampoule upper end, in nitrogen or argon gas atmosphere,
200~1000 DEG C are calcined 0.5~8 hour, are subsequently cooled to room temperature so that manganese cobalt subcarbonate ultrathin nanometer piece composite Nano
Line multilevel hierarchy is changed into the full decomposition water electro-catalysis of acidity of the phosphatization cobalt ultrathin nanometer piece composite nano-line multilevel hierarchy for mixing manganese
Agent, is named as 1D/2D Mn-CoP.
2. a kind of preparation method of acid full decomposition water elctro-catalyst according to claim 1, it is characterised in that the step
Suddenly the conductive substrates of (1) are nickel foam both any one of NF, titanium sheet or carbon cloth.
3. a kind of preparation method of acid full decomposition water elctro-catalyst according to claim 1, it is characterised in that the step
Suddenly the phosphorus source of (6) is sodium hypophosphite, sodium phosphate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611081350.0A CN106694005A (en) | 2016-11-30 | 2016-11-30 | Preparation method of electric catalyst for acidic fully-decomposed water |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611081350.0A CN106694005A (en) | 2016-11-30 | 2016-11-30 | Preparation method of electric catalyst for acidic fully-decomposed water |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106694005A true CN106694005A (en) | 2017-05-24 |
Family
ID=58934219
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201611081350.0A Pending CN106694005A (en) | 2016-11-30 | 2016-11-30 | Preparation method of electric catalyst for acidic fully-decomposed water |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106694005A (en) |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107376961A (en) * | 2017-07-25 | 2017-11-24 | 江苏大学 | Preparation and application of the integrated CoP nano-chip arrays as monoblock type class peroxidase |
| CN108315762A (en) * | 2018-02-08 | 2018-07-24 | 华南师范大学 | The synthetic method of the Ni-Mo-Co liberation of hydrogen catalyst of high activity under a kind of acidic environment |
| CN108511202A (en) * | 2018-02-06 | 2018-09-07 | 四川大学 | A kind of preparation method of Mn doping CoP nano wires modification nano-chip arrays hierarchical structure electrode material for super capacitor |
| CN109174162A (en) * | 2018-10-26 | 2019-01-11 | 江苏大学 | A kind of Fe2O3 doping double-metal phosphide elctro-catalyst and its preparation method and application |
| CN109746007A (en) * | 2018-12-25 | 2019-05-14 | 中山大学 | A kind of functionalization transition metal phosphide-oxide composite nano materials and the preparation method and application thereof |
| CN111250119A (en) * | 2020-01-22 | 2020-06-09 | 北京大学 | CoP grown on surface of conductive substratexOyNano array composite material and preparation and application thereof |
| CN111501061A (en) * | 2020-04-24 | 2020-08-07 | 唐友莲 | Nano Ni2P-MoS2Electrocatalytic hydrogen production material modified with graphene and preparation method thereof |
| CN111690945A (en) * | 2019-03-15 | 2020-09-22 | 国家纳米科学中心 | Method for producing hydrogen by electrolyzing waste lignocellulose |
| CN111701607A (en) * | 2020-06-15 | 2020-09-25 | 西北大学 | MnCo2O4@Ni2P/NF difunctional full-hydrolysis catalyst and preparation method and application thereof |
| CN112121829A (en) * | 2020-09-25 | 2020-12-25 | 合肥工业大学 | Manganese-doped transition metal atom metal phosphide catalyst, preparation method thereof and application thereof in hydrogen production by water electrolysis |
| CN113053674A (en) * | 2021-03-15 | 2021-06-29 | 中国科学技术大学 | Binderless electrode material, and preparation method and application thereof |
| CN113955728A (en) * | 2021-09-15 | 2022-01-21 | 浙江大学 | Preparation of hollow-grade-structure cobalt phosphide/cobalt manganese phosphide and application of hollow-grade-structure cobalt phosphide/cobalt manganese phosphide in electrolytic water |
| CN114243030A (en) * | 2021-12-21 | 2022-03-25 | 广西师范大学 | Preparation method and application of doping type tubular cobalt-based material based on template-free method |
| CN114574898A (en) * | 2022-03-28 | 2022-06-03 | 广东工业大学 | Mn doped Co2P core-shell nanosphere and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105332003A (en) * | 2015-11-30 | 2016-02-17 | 天津理工大学 | Ultrathin nanosheet array electro-catalytic material with nano-porous structure and oxygen vacancies |
| CN106025302A (en) * | 2016-07-18 | 2016-10-12 | 天津理工大学 | Single-cell-thickness nano porous cobalt oxide nanosheet array electrocatalytic material |
-
2016
- 2016-11-30 CN CN201611081350.0A patent/CN106694005A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105332003A (en) * | 2015-11-30 | 2016-02-17 | 天津理工大学 | Ultrathin nanosheet array electro-catalytic material with nano-porous structure and oxygen vacancies |
| CN106025302A (en) * | 2016-07-18 | 2016-10-12 | 天津理工大学 | Single-cell-thickness nano porous cobalt oxide nanosheet array electrocatalytic material |
Non-Patent Citations (2)
| Title |
|---|
| JILIN HUANG, ET AL.: ""MoS2 nanosheet-coated CoS2 nanowire arrays on carbon cloth as three-dimensional electrodes for efficient electrocatalytic hydrogen evolution"", 《J. MATER. CHEM. A》 * |
| TINGTING LIU, ET AL.: ""Mn Doping of CoP Nanosheets Array: An Efficient Electrocatalyst for Hydrogen Evolution Reaction with Enhanced Activity at All pH Values"", 《ACS CATAL.》 * |
Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107376961A (en) * | 2017-07-25 | 2017-11-24 | 江苏大学 | Preparation and application of the integrated CoP nano-chip arrays as monoblock type class peroxidase |
| CN108511202A (en) * | 2018-02-06 | 2018-09-07 | 四川大学 | A kind of preparation method of Mn doping CoP nano wires modification nano-chip arrays hierarchical structure electrode material for super capacitor |
| CN108315762A (en) * | 2018-02-08 | 2018-07-24 | 华南师范大学 | The synthetic method of the Ni-Mo-Co liberation of hydrogen catalyst of high activity under a kind of acidic environment |
| CN108315762B (en) * | 2018-02-08 | 2020-06-09 | 华南师范大学 | Synthesis method of Ni-Mo-Co hydrogen evolution catalyst with high activity in acidic environment |
| CN109174162A (en) * | 2018-10-26 | 2019-01-11 | 江苏大学 | A kind of Fe2O3 doping double-metal phosphide elctro-catalyst and its preparation method and application |
| CN109746007A (en) * | 2018-12-25 | 2019-05-14 | 中山大学 | A kind of functionalization transition metal phosphide-oxide composite nano materials and the preparation method and application thereof |
| CN111690945A (en) * | 2019-03-15 | 2020-09-22 | 国家纳米科学中心 | Method for producing hydrogen by electrolyzing waste lignocellulose |
| CN111690945B (en) * | 2019-03-15 | 2021-05-28 | 国家纳米科学中心 | Method for producing hydrogen by electrolyzing waste lignocellulose |
| CN111250119A (en) * | 2020-01-22 | 2020-06-09 | 北京大学 | CoP grown on surface of conductive substratexOyNano array composite material and preparation and application thereof |
| CN111501061A (en) * | 2020-04-24 | 2020-08-07 | 唐友莲 | Nano Ni2P-MoS2Electrocatalytic hydrogen production material modified with graphene and preparation method thereof |
| CN111701607A (en) * | 2020-06-15 | 2020-09-25 | 西北大学 | MnCo2O4@Ni2P/NF difunctional full-hydrolysis catalyst and preparation method and application thereof |
| CN112121829A (en) * | 2020-09-25 | 2020-12-25 | 合肥工业大学 | Manganese-doped transition metal atom metal phosphide catalyst, preparation method thereof and application thereof in hydrogen production by water electrolysis |
| CN113053674A (en) * | 2021-03-15 | 2021-06-29 | 中国科学技术大学 | Binderless electrode material, and preparation method and application thereof |
| CN113955728A (en) * | 2021-09-15 | 2022-01-21 | 浙江大学 | Preparation of hollow-grade-structure cobalt phosphide/cobalt manganese phosphide and application of hollow-grade-structure cobalt phosphide/cobalt manganese phosphide in electrolytic water |
| CN113955728B (en) * | 2021-09-15 | 2023-08-11 | 浙江大学 | Preparation of cobalt phosphide/cobalt manganese phosphide with hollow grade structure and application of electrolytic water |
| CN114243030A (en) * | 2021-12-21 | 2022-03-25 | 广西师范大学 | Preparation method and application of doping type tubular cobalt-based material based on template-free method |
| CN114574898A (en) * | 2022-03-28 | 2022-06-03 | 广东工业大学 | Mn doped Co2P core-shell nanosphere and preparation method and application thereof |
| CN114574898B (en) * | 2022-03-28 | 2023-05-26 | 广东工业大学 | Mn doped Co 2 P core-shell nanosphere and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106694005A (en) | Preparation method of electric catalyst for acidic fully-decomposed water | |
| Wu et al. | Integrating the active OER and HER components as the heterostructures for the efficient overall water splitting | |
| Cao et al. | Aqueous electrocatalytic N 2 reduction under ambient conditions | |
| Shang et al. | In situ growth of NixSy controlled by surface treatment of nickel foam as efficient electrocatalyst for oxygen evolution reaction | |
| CN106025302A (en) | Single-cell-thickness nano porous cobalt oxide nanosheet array electrocatalytic material | |
| CN106732649A (en) | A kind of preparation method of alkaline oxygen evolution reaction elctro-catalyst | |
| CN110201697A (en) | A kind of three-dimensional N doping transition metal oxide/vulcanization nickel composite catalyst and preparation method and application | |
| Wang et al. | Preparation of nanostructured Cu (OH) 2 and CuO electrocatalysts for water oxidation by electrophoresis deposition | |
| Chen et al. | Tuning octahedron sites in MnFe2O4 spinel by boron doping for highly efficient seawater splitting | |
| CN103952720B (en) | Metal base/containing cobalt acrylic/hydrotalcite-like nano membrane electrode and preparation method thereof | |
| CN111663152B (en) | Preparation method and application of foam nickel-loaded amorphous phosphorus-doped nickel molybdate bifunctional electrocatalytic electrode | |
| CN106757143A (en) | A kind of water decomposition reaction catalysis electrode and preparation method thereof | |
| Zhang et al. | Photo-deposition of ZnO/Co 3 O 4 core-shell nanorods with pn junction for efficient oxygen evolution reaction | |
| Lam et al. | H2O2 treated La0. 8Sr0. 2CoO3-δ as an efficient catalyst for oxygen evolution reaction | |
| CN113445072B (en) | Foamed nickel composite electrode and preparation method and application thereof | |
| Wang et al. | A highly efficient electrochemical oxygen evolution reaction catalyst constructed from a S-treated two-dimensional Prussian blue analogue | |
| CN108823591B (en) | Nickel-iron-selenium compound and preparation method and application thereof | |
| CN111701607A (en) | MnCo2O4@Ni2P/NF difunctional full-hydrolysis catalyst and preparation method and application thereof | |
| JP2020059917A (en) | Tricobalt tetroxide array/titanium mesh electrode for water decomposition oxygen evolution and manufacturing method thereof | |
| Zhang et al. | In-situ integration of nickel-iron Prussian blue analog heterostructure on Ni foam by chemical corrosion and partial conversion for oxygen evolution reaction | |
| Yang et al. | Electrochemical deposition of CeO2 nanocrystals on Co3O4 nanoneedle arrays for efficient oxygen evolution | |
| Baibars et al. | Boosted electrolytic hydrogen production at tailor-tuned nano-dendritic Ni-doped Co foam-like catalyst | |
| CN111604061A (en) | Caterpillar nickel-cobalt sulfide nano array and its synthesis and application | |
| CN114875442A (en) | Ruthenium-modified molybdenum-nickel nanorod composite catalyst and preparation method and application thereof | |
| Wu et al. | Molybdenum carbide MXene embedded with nickel sulfide clusters as an efficient electrocatalyst for hydrogen evolution reaction |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20170524 |