CN110479328A - A kind of Fe doping hydroxyl phosphorous acid cobalt nano-chip arrays structural material and its preparation method and application - Google Patents
A kind of Fe doping hydroxyl phosphorous acid cobalt nano-chip arrays structural material and its preparation method and application Download PDFInfo
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- CN110479328A CN110479328A CN201910758746.1A CN201910758746A CN110479328A CN 110479328 A CN110479328 A CN 110479328A CN 201910758746 A CN201910758746 A CN 201910758746A CN 110479328 A CN110479328 A CN 110479328A
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- 239000000463 material Substances 0.000 title claims abstract description 72
- 238000003491 array Methods 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- -1 hydroxyl phosphorous acid cobalt Chemical compound 0.000 title abstract description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 61
- 238000006243 chemical reaction Methods 0.000 claims abstract description 45
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 31
- 239000006260 foam Substances 0.000 claims abstract description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000003054 catalyst Substances 0.000 claims abstract description 22
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 17
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000001301 oxygen Substances 0.000 claims abstract description 16
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 15
- 239000001257 hydrogen Substances 0.000 claims abstract description 15
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 150000001868 cobalt Chemical class 0.000 claims abstract description 7
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims abstract description 7
- 239000002904 solvent Substances 0.000 claims abstract description 7
- 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 3
- 239000012046 mixed solvent Substances 0.000 claims abstract description 3
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims abstract description 3
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical class O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 4
- 229910016874 Fe(NO3) Inorganic materials 0.000 claims description 2
- OQUOOEBLAKQCOP-UHFFFAOYSA-N nitric acid;hexahydrate Chemical compound O.O.O.O.O.O.O[N+]([O-])=O OQUOOEBLAKQCOP-UHFFFAOYSA-N 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 7
- 238000000354 decomposition reaction Methods 0.000 abstract description 5
- 230000010148 water-pollination Effects 0.000 abstract description 4
- 239000007772 electrode material Substances 0.000 abstract description 3
- 239000000758 substrate Substances 0.000 abstract description 3
- 238000011160 research Methods 0.000 abstract description 2
- 230000027756 respiratory electron transport chain Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 17
- 230000010287 polarization Effects 0.000 description 15
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 12
- 230000000694 effects Effects 0.000 description 11
- 238000004502 linear sweep voltammetry Methods 0.000 description 11
- 238000000034 method Methods 0.000 description 9
- 238000006555 catalytic reaction Methods 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 238000005868 electrolysis reaction Methods 0.000 description 7
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(IV) oxide Inorganic materials O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 230000005611 electricity Effects 0.000 description 6
- 239000003792 electrolyte Substances 0.000 description 6
- 229910052742 iron Inorganic materials 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- 238000000634 powder X-ray diffraction Methods 0.000 description 5
- 229910021607 Silver chloride Inorganic materials 0.000 description 4
- 239000000370 acceptor Substances 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 229960000935 dehydrated alcohol Drugs 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 239000008151 electrolyte solution Substances 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 4
- 229910002651 NO3 Inorganic materials 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 3
- 238000002083 X-ray spectrum Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229910021205 NaH2PO2 Inorganic materials 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000005518 electrochemistry Effects 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- PXFBZOLANLWPMH-UHFFFAOYSA-N 16-Epiaffinine Natural products C1C(C2=CC=CC=C2N2)=C2C(=O)CC2C(=CC)CN(C)C1C2CO PXFBZOLANLWPMH-UHFFFAOYSA-N 0.000 description 1
- 229910002554 Fe(NO3)3·9H2O Inorganic materials 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- PCWQAZUZGUIWOC-UHFFFAOYSA-N cobalt phosphorous acid Chemical compound [Co].P(O)(O)O PCWQAZUZGUIWOC-UHFFFAOYSA-N 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical compound FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- HTXDPTMKBJXEOW-UHFFFAOYSA-N iridium(IV) oxide Inorganic materials O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 1
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(III) nitrate Inorganic materials [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002060 nanoflake Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- MPNNOLHYOHFJKL-UHFFFAOYSA-N peroxyphosphoric acid Chemical group OOP(O)(O)=O MPNNOLHYOHFJKL-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 229910000319 transition metal phosphate Inorganic materials 0.000 description 1
- 230000005945 translocation Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
- B01J27/1853—Phosphorus; Compounds thereof with iron group metals or platinum group metals with iron, cobalt or nickel
-
- B01J35/23—
-
- 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
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
- C25B11/077—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound the compound being a non-noble metal oxide
-
- 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 kind of Fe doping hydroxyl phosphorous acid cobalt nano-chip arrays structural materials and its preparation method and application, molysite, cobalt salt and sodium hypophosphite are dissolved in the in the mixed solvent of water and isopropanol, solution is transferred in reaction kettle, nickel foam inclination is placed in solution, carry out solvent thermal reaction, it is cooled to room temperature after reaction, product is washed, dry, can be prepared by Fe doping Co11(HPO3)8(OH)6Nano-chip arrays structural material, the present invention designs in foam nickel substrate has synthesized Fe doping Co11(HPO3)8(OH)6Nano-chip arrays structure can effectively adjust Co using Fe doping11(HPO3)8(OH)6Electronic structure, reduce resistance, increase active sites, improve hydrophily, accelerate electron transfer rate, the Fe adulterates Co11(HPO3)8(OH)6The elctro-catalyst that nano-chip arrays structural material is reacted as oxygen evolution reaction, evolving hydrogen reaction and total moisture solution, active advantage high, durability is good and preparation process is simple, low in cost has value to the practical application of research water decomposition electro catalytic electrode material very much.
Description
Technical field
The invention belongs to preparation method of nano material and electro-catalysis application fields, and in particular to a kind of Fe doping hydroxyl phosphorous
Sour cobalt nano-chip arrays structural material and its preparation method and application.
Background technique
Electrolysis water generates hydrogen and oxygen and provides a kind of very promising method for renewable energy storage.The technology
Key is to develop with high activity, durable and economic traits elctro-catalyst, realizes analysis oxygen (OER) and liberation of hydrogen (HER) two
The efficient progress of half-reaction.It is well known that IrO2And RuO2It is considered as advanced OER catalyst, and Pt sill is advanced
HER catalyst.But these noble metal catalysts are at high cost and durability is poor seriously hinders its large-scale application.Therefore, very
It is necessary to the elctro-catalyst with low overpotential, high-durability is found from earth resource material abundant.
In recent years, 3d transition metal (such as Ni, Co, Fe and Mn) phosphate becomes a kind of effective in neutral and alkaline medium
The elctro-catalyst of difunctional especially OER reaction.The different coordination configuration of transition metal phosphate and structure type can be stablized
The intermediate state of metal center, it is often more important that, phosphate radical can be used as proton carrier accelerating proton (H+) movement, and keep stable
Local pH environment, to greatly improve OER catalytic activity.The more activity of oxygen element offer water absorption abundant in phosphate radical
Site is also beneficial to oxygen precipitation.In addition, transition metal metaphosphate and hydrophosphate are respectively provided with PO3 -Or HPO4 2-Proton acceptor
It may be alternatively used for OER electro-catalysis, and hydroxyl is another kind of proton acceptor, there is hydroxyl phosphate different proton acceptors to be expected to mention
The catalytic activity of high-moisture solution.
Transition metal hydroxyl phosphorous acid cobalt Co11(HPO3)8(OH)6Pass through MO6The shared side of octahedron and angle have three-dimensional octahedral
Volume array structure has triangle and hexagonal channels along C axis direction.Its unique micro channel can be effectively by active site
It is exposed in electrolyte, realizes quick interface electric charge transfer, have become multiduty energy stores electrode material.
Although hydroxyl phosphorous acid cobalt Co11(HPO3)8(OH)6It has a good application prospect, still, hydroxyl in the prior art
Base phosphorous acid cobalt Co11(HPO3)8(OH)6Preparation method it is complicated, and catalytic activity is lower.
Summary of the invention
In order to solve the above technical problems, the present invention provides a kind of Fe to adulterate hydroxyl phosphorous acid cobalt nano-chip arrays structural wood
Material and its preparation method and application.The Fe doping being carried in foam nickel base has been prepared by a step liquid phase solvent thermal response
Co11(HPO3)8(OH)6Nano-chip arrays structural material can be applied to OER, HER and total moisture solution application.In Co11(HPO3)8
(OH)6In nanometer sheet, hydroxyl and two proton receptor of orthophosphite accelerate proton translocation and electronic movement velocity, outside introducing
Carry out metal cation Fe3+Co can effectively be adjusted11(HPO3)8(OH)6Electronic structure, improve hydrophily, accelerate electronics turn
Rate is moved, electric conductivity is enhanced, increases active sites, realizes electro-catalysis water decomposition activity and stability outstanding.
A kind of Fe provided by the invention adulterates Co11(HPO3)8(OH)6The preparation method of nano-chip arrays structural material, including
Following steps:
Molysite, cobalt salt and hypophosphites are dissolved in the in the mixed solvent of water and isopropanol, solution is transferred to reaction kettle
In, nickel foam inclination is placed in solution, solvent thermal reaction is carried out, is cooled to room temperature after reaction, product is washed, dry
It is dry, it can be prepared by Fe doping Co11(HPO3)8(OH)6Nano-chip arrays structural material.
Further, the molysite is Fe(NO3)39H2O；The cobalt salt is cabaltous nitrate hexahydrate；The hypophosphites is
Sodium hypophosphite.
The ratio between amount of substance of the molysite, cobalt salt, hypophosphites is 0.2~0.8:1~2:1, preferably 0.6:1:1.
Concentration of the hypophosphites in water and isopropanol is 0.025M.
The aqueous solvent and the volume ratio of isopropanol are 1~2:3~2, preferably 1:3.
The condition of the solvent thermal reaction is to react 4-8h, preferably 160 DEG C reaction 6h at 160 DEG C.
It needs to be cleaned before nickel foam (NF) use, specific cleaning step are as follows: first removed with 6M salt acid soak 15min
Then the oxidation film of outer layer is respectively cleaned 3-5 times with deionized water and dehydrated alcohol；In use, to be cut into 2 × 3cm big for nickel foam
It is small.
The washing is respectively to be cleaned 3-5 times with deionized water and dehydrated alcohol.
The drying is the naturally dry in air atmosphere.
The present invention also provides a kind of Fe being prepared such as above-mentioned preparation method to adulterate Co11(HPO3)8(OH)6Nanometer sheet
Array structure materials, the Fe adulterate Co11(HPO3)8(OH)6The pattern of nano-chip arrays structural material is 300 by average-size
The nanometer sheet of~500nm forms, Fe3+In Co11(HPO3)8(OH)6It is uniformly distributed in nanometer sheet.
The present invention also provides the Fe to adulterate Co11(HPO3)8(OH)6Nano-chip arrays structural material is as oxygen evolution reaction
Or the application of evolving hydrogen reaction or total moisture solution reaction elctro-catalyst.
The Fe adulterates Co11(HPO3)8(OH)6Nano-chip arrays structural material is as oxygen evolution reaction (OER) elctro-catalyst
In application, method particularly includes: the Fe prepared in nickel foam is adulterated into Co11(HPO3)8(OH)6Nano-chip arrays structural material is cut
At 0.5 × 0.5cm size as working electrode, using 1M KOH solution as electrolyte, carried out with CHI 760E electrochemical workstation
Test.With platinum filament and Ag/AgCl electrode respectively as to electrode and reference electrode.Using linear sweep voltammetry (LSV) In
2.0mV·s-1Sweep speed and ohm compensation for 90% lower obtain polarization curve；It is close by measuring electric current under constant voltage
It spends time graph and obtains stability.Electrochemical surface area (ECSA) passes through under without obvious faraday region different scanning rates
(10,12,14,16,18,20 and 22mVs-1) cyclic voltammetric (CV) measure electric double layer capacitance (Cdl) assessed；Electrochemistry
Impedance (EIS) open-circuit voltage in the frequency range of 100kHz to 0.1Hz is tested.And respectively with business RuO2And Co11
(HPO3)8(OH)6Nanometer sheet, which is supported in nickel foam, is used as working electrode, and the performance for measuring their OER respectively, which is used as, to be compared.
The Fe adulterates Co11(HPO3)8(OH)6Nano-chip arrays structural material is as evolving hydrogen reaction (HER) elctro-catalyst
In application, method particularly includes: the Fe prepared in nickel foam is adulterated into Co11(HPO3)8(OH)6Nano-chip arrays structural material is cut
At 0.5 × 0.5cm size as working electrode, using 1M KOH solution as electrolyte, carried out with CHI 760E electrochemical workstation
Test.With carbon-point and Ag/AgCl electrode respectively as to electrode and reference electrode.Using linear sweep voltammetry (LSV) In
2.0mV·s-1Sweep speed and ohm compensation for 90% lower obtain polarization curve；It is close by measuring electric current under constant voltage
It spends time graph and obtains stability.Electrochemical surface area (ECSA) passes through under without obvious faraday region different scanning rates
(10,12,14,16,18,20 and 22mVs-1) cyclic voltammetric (CV) measure electric double layer capacitance (Cdl) assessed；Electrochemistry
Impedance (EIS) open-circuit voltage in the frequency range of 100kHz to 0.1Hz is tested.And respectively with business Pt/C and Co11
(HPO3)8(OH)6Nanometer sheet is supported in nickel foam as working electrode, and the performance of measurement OER, which is used as, respectively compares.
The Fe adulterates Co11(HPO3)8(OH)6The elctro-catalyst that nano-chip arrays structural material is reacted as total moisture solution
In application, method particularly includes: by the Fe prepared in nickel foam adulterate Co11(HPO3)8(OH)6Nano-chip arrays structural material
2 0.5 × 0.5cm sizes are cut into respectively as cathode and anode assembling in dual-electrode electrolysis slot, pass through 90%iR compensation
LSV polarization curve and the current density time graph test total moisture solution performance under constant voltage.As a comparison, double electricity are had studied
The noble metal RuO being supported in the electrolytic cell of pole in nickel foam2LSV polarization curve as anode and Pt/C as cathode.
In the present invention, Fe adulterates the electronic structure for having adjusted catalyst, reduces resistance, increases electro-chemical activity face
Product.Fe adulterates Co11(HPO3)8(OH)6Existing defect sturcture effectively exposes active sites in electrolyte solution.Hydroxyl and
Orthophosphite proton acceptor can form hydrogen bond with hydrone, lead to the wettability that surface is high, be conducive to proton-electron and quickly turn
It moves.Fe doping causes the distortion of Local C o environment that water is promoted to be adsorbed onto active sites, increases the compatible and affine of catalyst surface water
Power.High hydrophily promotes electrolyte permeability, further promotes the electric charge transfer rate between electrolyte and catalyst, and raising is urged
Change activity.Fe adulterates Co11(HPO3)8(OH)6Defect present on nanometer sheet and twisted straps are used to inhale come the coordination site more opened
Reaction enclosure intermediate accelerates interfacial charge transfer rate.Therefore the material is anti-to oxygen evolution reaction, liberation of hydrogen in the alkaline electrolyte
It should be reacted with total moisture solution and show activity outstanding and brilliant durability, to research water decomposition electro catalytic electrode material
Practical application has value very much.
Compared with prior art, the present invention uses simple chemical liquid phase reaction, H2PO2 -Ionic portions hydrolysis generates OH-From
Son, OH-Ion then with unhydrolysed H2PO2 -Ion generates PH by disproportionated reaction3Molecule and HPO3 2-Ion.HPO3 2-Ion
Further with Co2+Ion and OH-Ionic reaction generates Co11(HPO3)8(OH)6Crystal seed, while Fe3+It mixes in lattice.Absorption
In Co11(HPO3)8(OH)6Isopropanol molecule on crystal seed is passivated surface atom, makes Co11(HPO3)8(OH)6Crystal seed is grown into
2D nanometer sheet.Fe adulterates Co11(HPO3)8(OH)6Nano-chip arrays structural material is to oxygen evolution reaction, evolving hydrogen reaction and total moisture solution
Reaction shows brilliant catalytic activity and stability, and preparation process is environmental-friendly, simple, at low cost.
Detailed description of the invention
Fig. 1 is that Fe prepared by embodiment 1 adulterates Co11(HPO3)8(OH)6The X-ray powder of nano-chip arrays structural material
Diffraction (XRD) figure；
Fig. 2 is that Fe prepared by embodiment 1 adulterates Co11(HPO3)8(OH)6The energy dispersion X of nano-chip arrays structural material is penetrated
Line spectrum (EDX) figure；
Fig. 3 is that Fe prepared by embodiment 1 adulterates Co11(HPO3)8(OH)6The scanning electron of nano-chip arrays structural material is aobvious
Micro mirror (SEM) figure；
Fig. 4 is that Fe prepared by embodiment 1 adulterates Co11(HPO3)8(OH)6The transmitted electron of nano-chip arrays structural material is aobvious
Micro mirror (TEM) figure；
Fig. 5 is that Fe prepared by embodiment 1 adulterates Co11(HPO3)8(OH)6The high-resolution lattice of nano-chip arrays structural material
Striped (HRTEM) image；
Fig. 6 is that Fe prepared by embodiment 1 adulterates Co11(HPO3)8(OH)6The scanning electron of nano-chip arrays structural material is aobvious
Micro mirror picture (SEM) and corresponding distribution diagram of element；
Fig. 7 is that Fe prepared by embodiment 1 adulterates Co11(HPO3)8(OH)6The infrared spectrogram of nano-chip arrays structural material；
Fig. 8 is that Fe adulterates Co in embodiment 111(HPO3)8(OH)6Nano-chip arrays structural material Contact-angle measurement result figure；
Fig. 9 is the Fe doping Co that Fe doping prepared by embodiment 2 is 8.1% and 15.1%11(HPO3)8(OH)6Nanometer sheet
X-ray powder diffraction (XRD) figure of array structure materials；
Figure 10 is the Fe doping Co that Fe doping prepared by embodiment 2 is 8.1% and 15.1%11(HPO3)8(OH)6Nanometer
Energy dispersion X-ray spectrum (EDX) figure of chip arrays structural material；
Figure 11 is the Fe doping Co that Fe doping prepared by embodiment 2 is 8.1%11(HPO3)8(OH)6Nano-chip arrays knot
Scanning electron microscope (SEM) figure of structure material；
Figure 12 is the Fe doping Co that Fe doping prepared by embodiment 2 is 15.1%11(HPO3)8(OH)6Nano-chip arrays knot
Scanning electron microscope (SEM) figure of structure material；
Figure 13 is different Fe contents (8.1%, 11.7% and Fe doping 15.1%) prepared by embodiment 1 and embodiment 2
Co11(HPO3)8(OH)6The LSV curve graph of the oxygen evolution reaction (OER) of nano-chip arrays structural material；
Figure 14 is different Fe contents (8.1%, 11.7% and Fe doping 15.1%) prepared by embodiment 1 and embodiment 2
Co11(HPO3)8(OH)6The LSV curve graph of the evolving hydrogen reaction (HER) of nano-chip arrays structural material；
Figure 15 is that Fe adulterates Co in embodiment 311(HPO3)8(OH)6Nano-chip arrays structural material oxygen evolution reaction (OER)
LSV curve graph (illustration is the polarization curve under high current density)；
Figure 16 is that Fe adulterates Co in embodiment 311(HPO3)8(OH)6Nano-chip arrays structural material oxygen evolution reaction (OER)
Current density time plot；
Figure 17 is that Fe adulterates Co in embodiment 311(HPO3)8(OH)6Nano-chip arrays structural material sweeps the electricity under speed in difference
Capacitance current figure；
Figure 18 is that Fe adulterates Co in embodiment 311(HPO3)8(OH)6The impedance diagram of nano-chip arrays structural material；
Figure 19 is that Fe adulterates Co in embodiment 411(HPO3)8(OH)6Nano-chip arrays structural material evolving hydrogen reaction (HER)
LSV curve graph (illustration is the polarization curve under high current density)；
Figure 20 is that Fe adulterates Co in embodiment 511(HPO3)8(OH)6Nano-chip arrays structural material evolving hydrogen reaction (HER)
Current density time plot；
Figure 21 is that Fe adulterates Co in embodiment 611(HPO3)8(OH)6Nano-chip arrays structural material is complete in two electrode systems
The polarization curve of water decomposition (illustration is the polarization curve under high current density)；
Figure 22 is that Fe adulterates Co in embodiment 611(HPO3)8(OH)6Nano-chip arrays structural material is complete in two electrode systems
The current density time plot of water decomposition.
Specific embodiment
Below with reference to embodiment and Figure of description, the present invention is described in detail.
Embodiment 1
A kind of Fe doping Co11(HPO3)8(OH)6The preparation method of nano-chip arrays structural material, comprising the following steps:
The nickel foam of 2 × 3cm size is immersed in 6M hydrochloric acid solution, after 15min, with deionized water and dehydrated alcohol point
Qing Xi not be nickel foam 3 times, it is dry, obtain the nickel foam of surface cleaning.Accurate measurement 10mL deionized water and 30mL isopropanol add
Enter in clean small beaker, then weighs 0.6mmol Fe (NO respectively3)3·9H2O, 1mmol Co (NO3)2·6H2O and
1mmol NaH2PO2·6H2Small beaker is added in O, and stirring and dissolving 30min obtains homogeneous solution.Solution is transferred to 50mL poly- four
Vinyl fluoride is that the nickel foam oblique cutting pre-processed is entered in solution in the stainless steel cauldron of liner, seals and dries at 160 DEG C
6h is reacted in case, to cooled to room temperature after reaction, will cover the nickel foam deionized water and dehydrated alcohol of sample
Nickel foam, is then placed in air atmosphere and spontaneously dries by each cleaning 3 times, and Fe doping Co can be obtained11(HPO3)8(OH)6Nanometer sheet
Array structure materials.
It carries out object to 1 products therefrom of embodiment with X-ray powder diffraction instrument mutually to characterize, as a result as shown in Figure 1, all spread out
Penetrate peak with the hexagonal phase Co in JCPDS no.44-1326 card11(HPO3)8(OH)6It coincide.Compared to standard card number, spread out
Penetrating peak, there is no offsets.
Product is analyzed using energy dispersion X-ray spectrum (EDX), as shown in Fig. 2, Fe, Co and P element atom hundred
Dividing ratio is 0.29:1:1.08, shows that Fe element is successfully coupled in sample, and calculating Fe doping accordingly is 11.7%, wherein
The appearance at nickel peak is derived from nickel foam substrate.
Morphology analysis is carried out to sample prepared by embodiment 1 using scanning electron microscope (SEM), as shown in figure 3, showing
Sample is made of nano-chip arrays, and nanometer sheet average-size is 300~500nm.
The pattern that sample is further looked at using transmission electron microscope (TEM), as a result as shown in figure 4, further demonstrating that
Sample is made of flexible nano flake.
High resolution transmission electron microscopy (HRTEM) image of nanometer sheet is as shown in Figure 5, it is shown that its crystallographic property, but
There is also some defects and distortion, show that nanometer sheet has defect sturcture abundant.The wherein interplanar of 0.37nm and 0.42nm
Away from corresponding respectively to Co11(HPO3)8(OH)6(201) and (210) crystal face.
The scanning electron microscope distribution diagram of element of Fig. 6 illustrates that Fe adulterates Co11(HPO3)8(OH)6Nano-chip arrays structural wood
Co, P, O and Fe element are uniformly distributed in material.
The infrared spectroscopy of product further demonstrates Fe doping Co in Fig. 711(HPO3)8(OH)6Successful preparation.With
3442cm-1Centered on broad absorption band be O-H stretching vibration, in 2414cm-1The absorption peak at place is P-H stretching vibration, 1639cm-1The peak at place is P-O-H bending vibration, 1107,1057,1016cm-1The absorption peak at place is P-O stretching vibration, 573cm-1The suction at place
Receive the bending vibration that peak is orthophosphite.
Determine Fe doping Co respectively using contact angle method11(HPO3)8(OH)6The surface wettability of nanometer chip architecture.Fig. 8
Indicate that water droplet drips to Fe doping Co11(HPO3)8(OH)6The typical water droplet profile diagram of moment after film surface.Fe adulterates Co11
(HPO3)8(OH)6The contact angle of film is about 9o, shows the hydrophily of product.
Embodiment 2
Fe adulterates Co11(HPO3)8(OH)6The preparation method of nano-chip arrays structural material, comprising the following steps:
In the accurate small beaker for measuring 10mL deionized water and the addition cleaning of 30mL isopropanol, then weigh respectively
0.4mmol or 0.8mmol Fe (NO3)3·9H2O, 1mmol Co (NO3)2·6H2O and 1mmol NaH2PO2·6H2O is added
Small beaker stirs evenly.Nickel foam oblique cutting after drying is entered in the stainless steel cauldron that 50mL polytetrafluoroethylene (PTFE) is liner, to
Solution is transferred in reaction kettle after completely dissolution, after sealing in an oven 160 DEG C react 6 hours.To fully reacting, natural cooling
To room temperature, by cover sample nickel foam deionized water and washes of absolute alcohol several times, then will cover the nickel foam of sample
It is placed in air atmosphere and spontaneously dries, Fe (NO3)3·9H2The additional amount of O be 0.4mmol when, obtain be Fe doping be 8.1%
Nanometer sheet composition Fe adulterate Co11(HPO3)8(OH)6Nano-chip arrays structural material；Fe(NO3)3·9H2The additional amount of O is
When 0.8mmol, that obtain is the Fe doping Co for the nanometer sheet composition that Fe doping is 15.1%11(HPO3)8(OH)6Nanometer sheet battle array
Array structure material.
It carries out object to 2 products therefrom of embodiment with X-ray powder diffraction instrument mutually to characterize, as a result as shown in figure 9, all spread out
Penetrate peak with the hexagonal phase Co in JCPDS no.44-1326 card11(HPO3)8(OH)6It coincide.
Synthesized nanometer sheet is analyzed using energy dispersion X-ray spectrum (EDX), as shown in Figure 10, Fe, Co and
P element atomic percent is respectively 0.18:1:1.08 and 0.40:1:1.25, and calculating Fe doping accordingly is 8.1% He
15.1%, wherein nickel peak derives from nickel foam substrate.
It is analyzed using the sample topography that scanning electron microscope (SEM) prepares embodiment 2, Figure 11 and Figure 12 difference
It is that the Fe that Fe doping is 8.1% and 15.1% adulterates Co11(HPO3)8(OH)6SEM figure, show sample be nanometer sheet composition
Array structure.
Embodiment 3
A kind of Fe doping Co11(HPO3)8(OH)6Application of the nanometer sheet structural material as oxygen evolution reaction (OER) catalyst.
Concrete application method are as follows: the Fe of 0.5 × 0.5cm of area is adulterated into Co11(HPO3)8(OH)6Nanometer sheet structural material is made
For working electrode, with platinum filament and Ag/AgCl electrode respectively as to electrode and reference electrode in 1.0M KOH electrolyte solution
It is tested using CHI760E electrochemical workstation.Respectively with business RuO2And Co11(HPO3)8(OH)6Nanometer sheet is supported on bubble
It is used as working electrode on foam nickel, measures the performance of their OER respectively as a comparison, Co11(HPO3)8(OH)6Preparation be to implement
Fe (the NO in raw material is eliminated on the basis of example 13)3·9H2What O was prepared.Using linear sweep voltammetry (LSV) In
2.0mV·s-1Sweep speed and ohm compensation for 90% lower obtain polarization curve.
Figure 13 is that the Fe with 8.1%, 11.7% and 15.1% difference Fe content adulterates Co11(HPO3)8(OH)6Nanometer sheet
Oxygen evolution reaction (OER) polarization curve.Showing Fe doping significantly influences OER activity, and the sample of Fe doping 11.7% is excellent
In 8.1% and 15.1% sample.
Figure 15 is that Fe adulterates Co11(HPO3)8(OH)6Nano-chip arrays structural material, Co11(HPO3)8(OH)6Nanometer sheet,
RuO2With oxygen evolution reaction (OER) polarization curve of nickel foam, it can be seen from the figure that Fe adulterate Co11(HPO3)8(OH)6Nanometer sheet
The overpotential that structural material only needs 206mV low can realize 20mAcm-2Current density, compare Co respectively11(HPO3)8
(OH)6With business RuO2Small 105mV and 131mV.
In addition, Fe adulterates Co11(HPO3)8(OH)6Nanometer sheet structural material can be in the lesser overpotential of 252mV and 268mV
Under reach 200mAcm-2And 500mAcm-2High current density, Figure 16 be under overpotential 206,252,268mV using electricity
Current density time graph assesses OER electro-catalysis stability, it can be seen from the figure that the continuous electrolysis by 12 hours reacts, electricity
Current density remains initial 98.5% or more, shows excellent electro-catalysis stability.
Figure 17 is the different capacitance current figures swept under speed, with the electrochemical surface area of electric double layer capacitance assessment material, Fe
Adulterate Co11(HPO3)8(OH)6Electric double layer capacitance is 4.95mFcm-2, it is greater than Co11(HPO3)8(OH)62.45mFcm-2, table
Bright Fe doping increases the electrochemical surface area of sample.
The bright Fe of electrochemical impedance (EIS) chart of Figure 18 adulterates Co11(HPO3)8(OH)6The half of nano-chip arrays structural material
Circular diameter is small, illustrates that its resistance is small, has faster catalytic kinetics；And straight line portion slope is big, illustrates its better matter
Measure transport behavior.
Embodiment 4
A kind of Fe doping Co11(HPO3)8(OH)6Application of the nanometer sheet structural material as evolving hydrogen reaction (HER) catalyst.
Concrete application method are as follows: the Fe of 0.5 × 0.5cm of area is adulterated into Co11(HPO3)8(OH)6Nanometer sheet structural material is made
For working electrode, with carbon-point and Ag/AgCl electrode respectively as to electrode and reference electrode, in 1.0M KOH electrolyte solution
It is tested using CHI760E electrochemical workstation.Respectively with business Pt/C and Co11(HPO3)8(OH)6Nanometer sheet is supported on bubble
It is used as working electrode on foam nickel, measures the performance of their HER respectively as a comparison, Co11(HPO3)8(OH)6Preparation be to implement
Fe (the NO in raw material is eliminated on the basis of example 13)3·9H2What O was prepared.Using linear sweep voltammetry (LSV) In
2.0mV·s-2Sweep speed and ohm compensation for 90% lower obtain polarization curve.
Figure 14 is that the Fe with 8.1%, 11.7% and 15.1% difference Fe content adulterates Co11(HPO3)8(OH)6Nanometer sheet
Evolving hydrogen reaction (HER) polarization curve.Show that Fe doping also significantly affects the HER activity of catalyst, Fe doping 11.7%
Sample reach best.
Figure 19 is that Fe adulterates Co11(HPO3)8(OH)6Nano-chip arrays structural material, Co11(HPO3)8(OH)6Nanometer sheet,
Evolving hydrogen reaction (HER) polarization curve of Pt/C and nickel foam, it can be seen from the figure that Fe adulterates Co11(HPO3)8(OH)6Nanometer sheet
Structure can reach 10mAcm under 102mV overpotential-2Current density is much smaller than Co11(HPO3)8(OH)6Catalyst
189mV.Although Pt/C electrode shows HER activity outstanding under low current density, at higher current densities, material is easily
It falls off and influences activity.
In addition, Fe adulterates Co11(HPO3)8(OH)6Nanometer chip architecture can be assigned in the lesser overpotential of 228mV and 263mV
To 200mAcm-2And 500mAcm-2High current density.Using under constant overpotential 138,228,263mV when current density
Half interval contour assesses the stability of HER electro-catalysis, as shown in figure 20, reacts by 12 hours continuous electrolysis, current density is protected
Holding is initial 96.4% or more, shows good HER electro-catalysis stability.
Embodiment 6
A kind of Fe doping Co11(HPO3)8(OH)6Application of the nanometer sheet structural material as total moisture solution catalysts.
Concrete application method are as follows: the Fe that 2 areas are 0.5 × 0.5cm is adulterated into Co11(HPO3)8(OH)6Nanometer chip architecture
It is assembled in dual-electrode electrolysis slot respectively as anode and cathode, total moisture solution is tested in 1.0M KOH electrolyte solution
Energy.And with RuO2The electricity formed with Pt/C respectively as anode and cathode is to as comparing.
Figure 21,22 are respectively current density time graph under the LSV polarization curve and constant voltage that 90%iR is compensated.From figure
21 as can be seen that Fe adulterates Co11(HPO3)8(OH)6Nano-chip arrays structural material can reach under the voltage of 1.494V
10mA·cm-2Current density, it is only necessary to which the voltage of 1.772V can drive 500mAcm-2High current density.Although business
RuO2With the electricity of Pt/C composition under low current density activity it is slightly higher, but be unable to reach 500mA because material easily falls off
cm-2High current density.
As can be seen from Figure 22, Fe adulterates Co11(HPO3)8(OH)6Nano-chip arrays structural material in constant voltage 1.530,
There is no apparent decaying occurs, current density remains initial 97.1% to continuous electrolysis within 12 hours under 1.690,1.772V
More than, illustrate that there is excellent durability in dual-electrode electrolysis slot.
It is above-mentioned that hydroxyl phosphorous acid cobalt nano-chip arrays structural material and preparation method thereof is adulterated to a kind of Fe referring to embodiment
The detailed description carried out with application, is illustrative without being restrictive, can enumerate several realities according to limited range
Example, therefore the change and modification in the case where not departing from present general inventive concept are applied, should be belonged within protection scope of the present invention.
Claims (10)
1. a kind of Fe adulterates Co11(HPO3)8(OH)6The preparation method of nano-chip arrays structural material, which is characterized in that the system
Preparation Method the following steps are included:
Molysite, cobalt salt and hypophosphites are dissolved in the in the mixed solvent of water and isopropanol, solution is transferred in reaction kettle, it will
Nickel foam inclination is placed in solution, is carried out solvent thermal reaction, is cooled to room temperature after reaction, and product is washed, dry
Fe is made and adulterates Co11(HPO3)8(OH)6Nano-chip arrays structural material.
2. preparation method according to claim 1, which is characterized in that the molysite is Fe(NO3)39H2O；The cobalt salt
For cabaltous nitrate hexahydrate；The hypophosphites is sodium hypophosphite.
3. preparation method according to claim 1 or 2, which is characterized in that the substance of the molysite, cobalt salt and hypophosphites
The ratio between amount be 0.2~0.8:1~2:1.
4. preparation method according to claim 1 or 2, which is characterized in that the hypophosphites is in the mixed of water and isopropanol
Concentration in bonding solvent is 0.025M.
5. preparation method according to claim 1 or 2, which is characterized in that the volume ratio of the water and isopropanol is 1~2:
3~2.
6. preparation method according to claim 1 or 2, which is characterized in that the condition of the solvent thermal reaction is at 160 DEG C
React 4-8h.
7. Fe doping Co is prepared in a kind of preparation method as claimed in any one of claims 1 to 611(HPO3)8(OH)6Nanometer
Chip arrays structural material.
8. Fe according to claim 7 adulterates Co11(HPO3)8(OH)6Nano-chip arrays structural material is as oxygen evolution reaction
(OER) application of elctro-catalyst.
9. Fe according to claim 7 adulterates Co11(HPO3)8(OH)6Nano-chip arrays structural material is as evolving hydrogen reaction
(HER) application of elctro-catalyst.
10. Fe according to claim 7 adulterates Co11(HPO3)8(OH)6Nano-chip arrays structural material is as total moisture solution
React the application of elctro-catalyst.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111686764A (en) * | 2020-05-06 | 2020-09-22 | 东莞理工学院 | Fe-Ni (OH)2/Ni3S2@ NF heterostructure and preparation method and application thereof |
| CN111889119A (en) * | 2020-06-11 | 2020-11-06 | 安徽师范大学 | Three-dimensional net-shaped nano-structure material assembled by Sn-doped nickel hydroxyphosphite nanowires and preparation method and application thereof |
| CN113174608A (en) * | 2021-03-02 | 2021-07-27 | 江苏大学 | Preparation method of double-doped porous cobalt phosphide nanosheet electrocatalytic material |
| CN113481534A (en) * | 2021-06-11 | 2021-10-08 | 江苏大学 | Preparation method of zirconium-doped cobalt-iron layered double hydroxide with low crystallinity and application of zirconium-doped cobalt-iron layered double hydroxide in hydrogen production by water electrolysis |
| CN114807968A (en) * | 2022-05-13 | 2022-07-29 | 西安交通大学 | Preparation method of metaphosphate-loaded ruthenium phosphide catalytic material and application of metaphosphate-loaded ruthenium phosphide catalytic material in electrocatalytic total decomposition water |
| CN115072674A (en) * | 2022-06-22 | 2022-09-20 | 安徽师范大学 | Sulfur ion doped cuprous selenide honeycomb-shaped flexible nanosheet array structure material, preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100133111A1 (en) * | 2008-10-08 | 2010-06-03 | Massachusetts Institute Of Technology | Catalytic materials, photoanodes, and photoelectrochemical cells for water electrolysis and other electrochemical techniques |
| US20160289849A1 (en) * | 2015-03-31 | 2016-10-06 | Yujie Sun | Bifunctional water splitting catalysts and associated methods |
| CN107670667A (en) * | 2017-10-17 | 2018-02-09 | 华南理工大学 | It is a kind of to be used to analyse nanoporous Ni Fe bimetallic layered hydroxide electrocatalysis materials of oxygen and its preparation method and application |
| CN108946692A (en) * | 2018-07-26 | 2018-12-07 | 江南大学 | A kind of cobalt phosphate nano material and its preparation method and application |
-
2019
- 2019-08-16 CN CN201910758746.1A patent/CN110479328B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100133111A1 (en) * | 2008-10-08 | 2010-06-03 | Massachusetts Institute Of Technology | Catalytic materials, photoanodes, and photoelectrochemical cells for water electrolysis and other electrochemical techniques |
| US20160289849A1 (en) * | 2015-03-31 | 2016-10-06 | Yujie Sun | Bifunctional water splitting catalysts and associated methods |
| CN107670667A (en) * | 2017-10-17 | 2018-02-09 | 华南理工大学 | It is a kind of to be used to analyse nanoporous Ni Fe bimetallic layered hydroxide electrocatalysis materials of oxygen and its preparation method and application |
| CN108946692A (en) * | 2018-07-26 | 2018-12-07 | 江南大学 | A kind of cobalt phosphate nano material and its preparation method and application |
Non-Patent Citations (4)
| Title |
|---|
| HUAMEI DAN ET AL: "Ni-Doped Cobalt Phosphite, Co11(HPO3)8(OH)6, with Different Morphologies Grown on Ni Foam Hydro(solvo)thermally for High-Performance Supercapacitor", 《ACS APPLIED MATERIALS & INTERFACES》 * |
| JIAN WU ET AL: "Novel nickel–cobalt phosphite with face-sharing octahedra derived electrocatalyst for efficient water splitting", 《INORGANIC CHEMISTRY FRONTIERS》 * |
| LEI ZHOU ET AL: "Two-dimensional ultrathin arrays of CoP: Electronic modulation toward high performance overall water splitting", 《NANO ENERGY》 * |
| 郑春满等: "《高等合成化学-方法与实践》", 30 September 2018, 国防工业出版社 * |
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|---|---|---|---|---|
| CN111686764A (en) * | 2020-05-06 | 2020-09-22 | 东莞理工学院 | Fe-Ni (OH)2/Ni3S2@ NF heterostructure and preparation method and application thereof |
| CN111686764B (en) * | 2020-05-06 | 2022-09-30 | 东莞理工学院 | Fe-Ni (OH) 2 /Ni 3 S 2 @ NF heterostructure and preparation method and application thereof |
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| CN113481534B (en) * | 2021-06-11 | 2022-05-20 | 江苏大学 | Preparation method of zirconium-doped cobalt-iron layered double hydroxide with low crystallinity and application of zirconium-doped cobalt-iron layered double hydroxide in hydrogen production by water electrolysis |
| CN114807968A (en) * | 2022-05-13 | 2022-07-29 | 西安交通大学 | Preparation method of metaphosphate-loaded ruthenium phosphide catalytic material and application of metaphosphate-loaded ruthenium phosphide catalytic material in electrocatalytic total decomposition water |
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