CN107376958A - The difunctional transition metal phosphide catalysts of NiFeP and its preparation and use - Google Patents
The difunctional transition metal phosphide catalysts of NiFeP and its preparation and use Download PDFInfo
- Publication number
- CN107376958A CN107376958A CN201710414816.2A CN201710414816A CN107376958A CN 107376958 A CN107376958 A CN 107376958A CN 201710414816 A CN201710414816 A CN 201710414816A CN 107376958 A CN107376958 A CN 107376958A
- Authority
- CN
- China
- Prior art keywords
- nifep
- transition metal
- difunctional
- metal phosphide
- preparation
- 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.)
- Granted
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 54
- 229910052723 transition metal Inorganic materials 0.000 title claims abstract description 33
- 150000003624 transition metals Chemical class 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000000758 substrate Substances 0.000 claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 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
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000004202 carbamide Substances 0.000 claims abstract description 9
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 15
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 13
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 10
- 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 description 9
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 9
- 150000002815 nickel Chemical class 0.000 claims description 9
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 9
- 239000011261 inert gas Substances 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 7
- 239000004917 carbon fiber Substances 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 239000006260 foam Substances 0.000 claims description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 5
- 238000009413 insulation Methods 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 3
- 238000011144 upstream manufacturing Methods 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 239000004411 aluminium Substances 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims description 2
- 239000003575 carbonaceous material Substances 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims description 2
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 238000010792 warming Methods 0.000 claims description 2
- 235000003891 ferrous sulphate Nutrition 0.000 claims 1
- 239000011790 ferrous sulphate Substances 0.000 claims 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims 1
- 229910052751 metal Inorganic materials 0.000 claims 1
- 239000002184 metal Substances 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 11
- 239000002994 raw material Substances 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 2
- UGKDIUIOSMUOAW-UHFFFAOYSA-N iron nickel Chemical compound [Fe].[Ni] UGKDIUIOSMUOAW-UHFFFAOYSA-N 0.000 abstract description 2
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 abstract 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 9
- 239000001257 hydrogen Substances 0.000 description 9
- 229910052739 hydrogen Inorganic materials 0.000 description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000010276 construction Methods 0.000 description 3
- 238000005868 electrolysis reaction Methods 0.000 description 3
- 230000036571 hydration Effects 0.000 description 3
- 238000006703 hydration reaction Methods 0.000 description 3
- 229910052603 melanterite Inorganic materials 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 230000010287 polarization Effects 0.000 description 3
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 241000209094 Oryza Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical class [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 description 2
- 238000003556 assay Methods 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 229910052741 iridium Inorganic materials 0.000 description 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 2
- HTXDPTMKBJXEOW-UHFFFAOYSA-N iridium(IV) oxide Inorganic materials O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000002604 ultrasonography Methods 0.000 description 2
- 210000002700 urine Anatomy 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003708 ampul Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229940126678 chinese medicines Drugs 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000003756 stirring 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- 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
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Metallurgy (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
The present invention provides a kind of difunctional transition metal phosphide catalysts of NiFeP, and the difunctional transition metal phosphide catalysts of NiFeP have nanometer chip architecture, and the length of nanometer sheet is 2~5m, and thickness is 100~200nm.The present invention also proposes the preparation method and purposes of the difunctional transition metal phosphide catalysts of the NiFeP.NiFeP bi-functionals transition metal phosphide catalyst provided by the invention, its microstructure are the nanometer sheets for having large specific surface area, and as water decomposition elctro-catalyst, it has more preferable catalytic performance.Preparation method proposed by the present invention, using nickel iron compound, ammonium fluoride and urea as raw material, growth NiFe LDH nanometer sheets are incubated in substrate, by low temperature phosphor, obtain NiFeP transition metal phosphide nanometer sheets.Aforesaid operations are simple, low production cost, and prepared phosphide catalyst is applied in all-hydrolytic under alkaline environment, have excellent all-hydrolytic catalytic performance.
Description
Technical field
The invention belongs to electrochemical field, and in particular to a kind of catalyst and its preparation for electrocatalytic decomposition water.
Background technology
In recent years, shortage of resources and environmental pollution turn into the two big crises that the whole world faces.Therefore, can in order to realize the mankind
Sustainable development, developing the regenerative resource of green cleaning turns into people's problem in the urgent need to address.A kind of cleaning of Hydrogen Energy conduct,
Renewable, environment-friendly, free of contamination new energy, attracts people's attention.Hydrogen Energy can pass through as a kind of round-the-clock resource
Electrolysis water is produced, and tellurian water resource is extremely abundant, with water hydrogen manufacturing have unrivaled huge advantage and it is wide should
Use prospect.
At present, the most frequently used liberation of hydrogen catalyst is still platinum group noble metal, and most common oxygen-separating catalyst then depends on oxygen
Change iridium, ruthenium-oxide.Platinum, iridium, ruthenium belong to noble metal and reserves on earth are small, and being unfavorable for its popularization industrially should
With therefore, the non-precious metal catalyst for developing earth rich content is imperative.Before this, it has been found that transition metal carbide,
Nitride, sulfide, phosphide etc. all have good catalytic action to evolving hydrogen reaction (HER) and oxygen evolution reaction (OER).At present
The transition metal liberation of hydrogen catalyst of most of reports is all just to have stronger catalytic activity under strong acid, and oxygen-separating catalyst is only
It can be stabilized in the basic conditions.Therefore, how to prepare has high catalytic performance under alkaline environment, particularly has analysis concurrently
Hydrogen and the transition-metal catalyst of analysis oxygen bi-functional are still a problem urgently to be resolved hurrily in electro-catalysis field now.At present
Some of report are used for the fully hydrolyzed ternary bi-functional phosphide catalyst of alkaline environment, and its current density is mostly at 1.6 volts
Could be up to 10 milliamperes/centimetre under voltage2, the efficiency of catalytic electrolysis water can not still meet the needs of economic development.
The content of the invention
Part in view of the shortcomings of the prior art of the invention, there is provided a kind of difunctional transition metal phosphides of NiFeP are urged
Agent, excellent catalytic performance is shown in alkaline electrocatalytic hydrogen evolution, alkaline electro-catalysis analysis oxygen and all-hydrolytic.
Second object of the present invention is to propose the preparation of the difunctional transition metal phosphide catalysts of NiFeP.
Third object of the present invention is to propose the purposes of the difunctional transition metal phosphide catalysts of NiFeP.
The technical scheme for realizing above-mentioned purpose of the present invention is：
A kind of difunctional transition metal phosphide catalysts of NiFeP, the difunctional transition metal phosphide catalysis of NiFeP
Agent has nanometer chip architecture, and the length of the nanometer sheet is 2~5m, and thickness is 100~200nm.
Wherein, the chemical formula of the difunctional transition metal phosphides of the NiFeP is Ni(2-x)FexP, wherein x=0.2~
0.8。
A kind of preparation method of the difunctional transition metal phosphide catalysts of NiFeP, including step:
1) nickel salt and molysite, urea and ammonium fluoride are dissolved in deionized water, obtain mixed solution；
2) conductive substrates are immersed in into insulation in mixed solution obtained by step 1) obtaining superficial growth has NiFe-LDH nanometers
The substrate of piece；
3) substrate that sodium hypophosphite and step 2) obtain is calcined under inert gas shielding, the temperature of calcining is 280
~350 DEG C, obtain NiFeP transition metal phosphide nanometer sheets.
Wherein, described nickel salt and molysite, sodium hypophosphite may each be its hydrate.
Wherein, the nickel salt is the one or more in nickel nitrate, nickel sulfate, nickel chloride, and the molysite is ferric sulfate, sulphur
The molar ratio of sour ferrous iron, iron chloride, frerrous chloride, ferric nitrate, the one or more of ferrous nitrate, nickel salt and molysite is (0.5
~2)：1.
Wherein, in step 1), nickel salt, molysite, urea and the ratio of ammonium fluoride gross mass and deionized water volume for (10~
50g):1L；Wherein urea and ammonium fluoride mass ratio are 1：(2~3).
Wherein, conductive substrates are made up of carbon material or transition metal described in step 2), selected from carbon fiber, nickel foam, bubble
One kind in foam copper, foamed aluminium；It is described insulation be 95~110 DEG C, under confined conditions be incubated 5~12 hours.
Wherein, the substrate that sodium hypophosphite and step 2) obtain is placed in calciner in step 3), to calciner
In be passed through inert gas, according to airflow direction, sodium hypophosphite is placed in the upstream of the substrate, with 2~10 DEG C/min speed
280~400 DEG C are warming up to, is then incubated 1~2 hour.
Preferably, inert gas described in step 3) is one kind in argon gas, nitrogen, helium, and the purity of inert gas exists
More than 99.99%, the flow being passed through is 50~100sccm.
Use of the difunctional transition metal phosphide catalysts of NiFeP of the present invention in the reaction of electrocatalytic decomposition water
On the way.
Further, it is to be used to alkaline water be catalytically decomposed.The alkaline water, can be OH in water-Concentration be 0.1~
5mol/L solution.
The beneficial effects of the present invention are：
Compared to prior art, NiFeP bi-functionals transition metal phosphide catalyst provided by the invention, its microcosmic knot
Structure is the nanometer sheet for having large specific surface area, and as water decomposition elctro-catalyst, it has more preferable catalytic performance.
The preparation method of the bi-functional phosphide catalyst proposed by the present invention, with nickel iron compound, ammonium fluoride and
Urea is raw material, is incubated growth NiFe-LDH nanometer sheets in substrate, by low temperature phosphor, obtains NiFeP transition metal phosphides
Nanometer sheet.Aforesaid operations are simple, low production cost, and prepared phosphide catalyst applies the all-hydrolytic under alkaline environment
In, there is excellent all-hydrolytic catalytic performance, in the case where voltage is 1.55 volts, current density is i.e. up to 10 milliamperes/centimetre2。
Relative to noble metals such as Pt/Ir, the present invention is using cheap and rich reserves transition metal as raw material, Neng Gou great
Width reduces the cost of elctro-catalyst, and NiFeP bi-functionals catalyst provided by the invention is not only in alkaline electrocatalytic hydrogen evolution side
Face has excellent performance, and excellent catalytic performance is also shown in oxygen and all-hydrolytic are analysed in alkaline electro-catalysis.
Brief description of the drawings
Fig. 1 is the scanning electron microscope diagram piece of NiFe-LDH@NF catalyst nano pieces prepared by the present invention, wherein (a)
Figure is the Local map of NiFe-LDH@NF catalyst nano pieces, and (b) figure is the partial enlargement of NiFe-LDH@NF catalyst nano pieces
Figure；
Fig. 2 is the scanning electron microscope diagram piece of NiFe-LDH@CF catalyst nano pieces prepared by the present invention, wherein (a)
Figure is the Local map of NiFe-LDH@CF catalyst nano pieces, and (b) figure is the partial enlargement of NiFe-LDH@CF catalyst nano pieces
Figure；
Fig. 3 is the scanning electron microscope diagram piece of NiFeP@NF catalyst nano pieces prepared by the present invention, wherein (a) figure is
The Local map of NiFeP@NF catalyst nano pieces, (b) figure are the partial enlarged drawing of NiFeP@NF catalyst nano pieces；
Fig. 4 is the scanning electron microscope diagram piece of NiFeP@CF catalyst nano pieces prepared by the present invention, wherein (a) figure is
The Local map of NiFeP@CF catalyst nano pieces, (b) figure are the partial enlarged drawing of NiFeP@CF catalyst nano pieces；
Fig. 5 is the Flied emission transmission electron micrograph of NiFeP catalyst nano pieces prepared by the present invention；
Fig. 6 is the X-ray diffractogram of NiFeP catalyst nano pieces prepared by the present invention；
Fig. 7 is the polarization curve of NiFeP catalyst nano pieces prepared by the present invention.
Embodiment
Ammonium fluoride, the Ni (NO of following examples use3)2·6H2O、FeSO4·7H2O, urea and a hydration ortho phosphorous acid
For sodium as reaction raw materials, it is that Chinese medicines group analysis is pure.
Embodiment 1：
Claim 222mg ammonium fluorides, 290mg Ni (NO with assay balance3)2·6H2O、278mg FeSO4·7H2O and 600mg urine
Element is added sequentially in 40ml deionized water, is stirred half an hour, is well mixed solution.
Nickel foam (NF) 30min is cleaned by ultrasonic using acetone, alcohols solvent, deionized water respectively successively, then, uses 0.1M
Watery hydrochloric acid 10~20min of ultrasound, finally with deionized water be cleaned by ultrasonic 30min.
Above-mentioned cleaned substrate is placed in the polytetrafluoroethylliner liner in 50ml reactors, pours into above-mentioned stir
Mixed solution, seal reactor, then place it in and be incubated 6h in convection oven at 100 DEG C, NiFe- is grown with substrate
LDH nanometer sheets.
After temperature of reaction kettle drops to room temperature, substrate is taken out, successively with deionized water, washes of absolute alcohol.In vacuum environment
Lower 60 DEG C of insulations 3h reaches the purpose of drying.
With SEM (S-4800) observation substrate be nickel foam (NF) sample, its pattern as shown in Figure 1,
Equally distributed nanometer sheet is overgrowed with substrate, length is most long up to 5 μm.
The substrate that one hydration sodium hypophosphite and growth there are NiFe-LDH nanometer sheets is placed in the both ends of ceramic boat, a hydration
Ceramic boat is placed in tube furnace, good seal tube furnace in air-flow upstream by sodium hypophosphite, with vavuum pump and high-purity argon quartz
Air total number discharge in pipe, is calcined under the air-flow of high-purity argon (purity >=99.999%).
Quartz ampoule is heated to 300 DEG C from room temperature with 5 DEG C/min heating rate, 1h is incubated at 300 DEG C, then allows tubular type
Stove cools to room temperature.It is 80sccm that whole experiment, which keeps the air-flow size of high-purity argon,.
After dropping to room temperature, the NiFe-LDH nanometer sheets in substrate are by phosphatization.After scanning electron microscopic observation phosphatization
NiFeP@NF patterns overgrow with equally distributed nanometer sheet, the most long reachable 5um of length as shown in Figure 3, in substrate.
Fig. 5 is that embodiment 1 obtains the Flied emission transmission electron micrograph (Tecnai of transition metal NiFeP catalyst
G2F20U-TWIN).Fig. 5 shows that transition metal NiFeP catalyst is nanometer chip architecture.
With X-ray diffraction (D/MAX-TTRIII (CBO)) test products therefrom thing phase, as shown in Figure 6 with standard card
Piece Ni2P PDF#89-4864 and Fe2P PDF#89-3680 coincide very much, it was demonstrated that the composition of gained nanometer sheet is
Ni1.5Fe0.5P。
Embodiment 2
Claim 222mg ammonium fluorides, 290mg Ni (NO with assay balance3)2·6H2O、278mg FeSO4·7H2O and 600mg urine
Element is added sequentially in 40ml deionized water, is stirred half an hour, is well mixed solution.
Carbon fiber (CF) 30min is cleaned by ultrasonic using acetone, alcohols solvent, deionized water respectively successively, then, uses 0.1M
Watery hydrochloric acid 10~20min of ultrasound, finally with deionized water be cleaned by ultrasonic 30min.
Other operations are the same as embodiment 1.
After growing NiFe-LDH nanometer sheets in substrate, it is carbon fiber to observe substrate with SEM (S-4800)
(CF) sample, its pattern overgrow with equally distributed nanometer sheet as shown in Figure 2, in substrate, and length is most long up to 5 μm.
With the NiFeP@CF patterns after scanning electron microscopic observation phosphatization as shown in figure 4, overgrowing with equally distributed receive in substrate
Rice piece, length are most long up to 5 μm.The thing of X-ray diffraction test products therefrom is met each other Fig. 6.
Test example
The catalyst for taking two panels embodiment 1 to be prepared is placed in 1 mol/L potassium hydroxide aqueous solution (pH=14), is protected
Hold certain spacing.It is connected a piece of with the working electrode of electrochemical workstation, another is connected with auxiliary electrode and to electrode,
Polarization curve is drawn in certain voltage range.The catalyst that is prepared with same method testing example 2 and commercially available
Catalyst, Pt@Ti-RuO2/IrO2@Ti, as a result such as Fig. 7.
The NiFeP bi-functional transition metal nanometer sheet catalyst that Fig. 7 is embodiment 1, embodiment 2 is prepared is in alkalescence
The polarization curve of (1 mol/L potassium hydroxide, pH=14) under environment.The figure illustrates the NiFeP nanometer sheets obtained by embodiment 1
Catalyst and Pt@Ti-RuO2/IrO2@Ti are compared, and possess more preferable electrolysis water catalytic performance, when current density is 10 milliamperes/li
Rice2(j=10mAcm-2) when, NiFeP nanometers plate electrode is 1.55 volts relative to current potential during normal electrode.
Applicant states that the present invention illustrates the detailed construction of the present invention and composition, but the present invention by above-described embodiment
Above-mentioned detailed construction and composition are not limited to, that is, does not mean that the present invention has to rely on above-mentioned detailed construction and composition could be real
Apply.Person of ordinary skill in the field is it will be clearly understood that any improvement in the present invention, to the equivalent of each raw material of product of the present invention
Replacement and the addition of auxiliary element, the selection of concrete mode etc., within the scope of all falling within protection scope of the present invention and disclosing.
Claims (10)
- A kind of 1. difunctional transition metal phosphide catalysts of NiFeP, it is characterised in that the difunctional transition metal of NiFeP Phosphide catalyst has nanometer chip architecture, and the length of the nanometer sheet is 2~5m, and thickness is 100~200nm.
- 2. the difunctional transition metal phosphide catalysts of NiFeP according to claim 1, it is characterised in that the NiFeP The chemical formula of difunctional transition metal phosphide is Ni(2-x)FexP, wherein x=0.2~0.8.
- 3. a kind of preparation method of the difunctional transition metal phosphide catalysts of NiFeP, it is characterised in that including step:1) nickel salt and molysite, urea and ammonium fluoride are dissolved in deionized water, obtain mixed solution；2) conductive substrates are immersed in into insulation in mixed solution obtained by step 1) obtaining superficial growth has NiFe-LDH nanometer sheets Substrate；3) substrate that sodium hypophosphite and step 2) obtain is calcined under inert gas shielding, the temperature of calcining is 280~350 DEG C, obtain NiFeP transition metal phosphide nanometer sheets.
- 4. preparation method according to claim 3, it is characterised in that the nickel salt is in nickel nitrate, nickel sulfate, nickel chloride One or more, the molysite be ferric sulfate, ferrous sulfate, iron chloride, frerrous chloride, ferric nitrate, one kind of ferrous nitrate Or it is a variety of, the molar ratio of nickel salt and molysite is (0.5~2)：1.
- 5. preparation method according to claim 3, it is characterised in that in step 1), nickel salt, molysite, urea and ammonium fluoride The ratio of gross mass and deionized water volume is (10~50g):1L；Wherein urea and ammonium fluoride mass ratio are 1：(2~3).
- 6. preparation method according to claim 3, it is characterised in that conductive substrates described in step 2) are carbon material or mistake Cross metal to be made, one kind in carbon fiber, nickel foam, foam copper, foamed aluminium；It is described insulation be 95~110 DEG C, it is closed Under the conditions of be incubated 5~12 hours.
- 7. preparation method according to claim 3, it is characterised in that obtain sodium hypophosphite and step 2) in step 3) Substrate be placed in calciner, inert gas is passed through into calciner, according to airflow direction, sodium hypophosphite is placed in institute The upstream of substrate is stated, 280~400 DEG C are warming up to 2~10 DEG C/min speed, is then incubated 1~2 hour.
- 8. preparation method according to claim 3, it is characterised in that inert gas described in step 3) be argon gas, nitrogen, One kind in helium, for the purity of inert gas more than 99.99%, the flow being passed through is 50~100sccm.
- 9. the difunctional transition metal phosphide catalysts of the NiFeP of claim 1 or 2 are in the reaction of electrocatalytic decomposition water Purposes.
- 10. purposes according to claim 9, it is characterised in that for alkaline water to be catalytically decomposed.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710414816.2A CN107376958B (en) | 2017-06-05 | 2017-06-05 | NiFeP difunctional transition metal phosphide catalyst and preparation and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710414816.2A CN107376958B (en) | 2017-06-05 | 2017-06-05 | NiFeP difunctional transition metal phosphide catalyst and preparation and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107376958A true CN107376958A (en) | 2017-11-24 |
| CN107376958B CN107376958B (en) | 2020-07-10 |
Family
ID=60332943
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710414816.2A Active CN107376958B (en) | 2017-06-05 | 2017-06-05 | NiFeP difunctional transition metal phosphide catalyst and preparation and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107376958B (en) |
Cited By (28)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108118362A (en) * | 2018-01-09 | 2018-06-05 | 国家纳米科学中心 | A kind of molybdenum disulfide electro-catalysis production hydrogen electrode and its preparation method and application |
| CN108511767A (en) * | 2018-04-24 | 2018-09-07 | 深圳大学 | A kind of elctro-catalyst and preparation method thereof |
| CN108554413A (en) * | 2018-04-11 | 2018-09-21 | 北京化工大学 | A kind of three-dimensional multistage structure high-dispersed nickel electrocatalysis material and preparation method thereof |
| CN108828039A (en) * | 2018-08-16 | 2018-11-16 | 广州钰芯传感科技有限公司 | A kind of double modifying foam nickel electrodes and preparation method thereof and electrochemistry formaldehyde sensor using the electrode |
| CN108940329A (en) * | 2018-07-25 | 2018-12-07 | 南京大学 | A kind of preparation method of high activity NiFe-LDHs catalyst |
| CN109012187A (en) * | 2018-08-29 | 2018-12-18 | 北京工业大学 | A kind of method of growth in situ layered bi-metal oxide nanofiltration membrane |
| CN109133259A (en) * | 2018-09-26 | 2019-01-04 | 上海电力学院 | A method of utilizing light anode activation sulfuric acid salt treatment waste water and by-product hydrogen |
| CN109395752A (en) * | 2018-06-20 | 2019-03-01 | 长沙理工大学 | A kind of self-supporting double-metal phosphide Ni2P-Cu3P composite material and preparation method |
| CN109847760A (en) * | 2019-01-09 | 2019-06-07 | 济南大学 | It is a kind of based on the three-dimensional elctro-catalyst of stainless steel nanostructure and its application |
| CN110344078A (en) * | 2019-07-03 | 2019-10-18 | 湖北大学 | A kind of nickel foam@cobalt molybdenum phosphide/ferronickel double-hydroxide electrode and the preparation method and application thereof |
| CN110586148A (en) * | 2019-10-10 | 2019-12-20 | 哈尔滨师范大学 | Preparation method of self-supporting flower-shaped nickel phosphide/ferrous phosphate heterostructure full-electrolysis hydro-electric catalyst |
| CN110813334A (en) * | 2019-10-16 | 2020-02-21 | 武汉工程大学 | Preparation method and application of foam nickel-loaded iron-nickel-based composite material |
| CN111068695A (en) * | 2019-11-25 | 2020-04-28 | 浙江大学 | Preparation method of multi-metal phosphorus-doped electrocatalyst derived based on ternary LDH |
| CN111068726A (en) * | 2019-11-26 | 2020-04-28 | 浙江大学 | Preparation method of iron-doped nickel phosphide composite nitrogen-doped reduced graphene oxide electrocatalytic material |
| CN111111718A (en) * | 2019-11-25 | 2020-05-08 | 浙江大学 | Preparation method of multi-metal phosphorus-doped electrocatalyst derived based on binary LDH |
| CN111389429A (en) * | 2020-04-13 | 2020-07-10 | 苏州大学 | Preparation method of catalyst for catalyzing ammonia borane hydrolysis |
| CN111424285A (en) * | 2020-04-29 | 2020-07-17 | 郑州大学 | Preparation method for constructing catalytic electrode by taking foamed cobalt as substrate under low-temperature condition |
| CN111468150A (en) * | 2020-05-26 | 2020-07-31 | 陕西科技大学 | Fullerene nanorod/transition metal phosphide electrocatalyst and preparation method thereof |
| CN111747388A (en) * | 2020-06-24 | 2020-10-09 | 三峡大学 | Preparation method of self-supporting nickel phosphide-iron composite nanosheet |
| CN111790416A (en) * | 2020-08-07 | 2020-10-20 | 中南林业科技大学 | High-efficiency oxygen evolution electrocatalyst and preparation method thereof |
| CN112458482A (en) * | 2020-11-18 | 2021-03-09 | 华中科技大学 | Amorphous NiFeP transition metal catalyst, preparation method and application |
| CN112591724A (en) * | 2020-12-16 | 2021-04-02 | 陕西科技大学 | Preparation method of nickel iron phosphide catalyst |
| CN113061929A (en) * | 2021-03-19 | 2021-07-02 | 齐齐哈尔大学 | Nickel phosphide-doped iron-based three-dimensional ultrathin nanosheet material and preparation method and application thereof |
| CN113104824A (en) * | 2021-03-01 | 2021-07-13 | 三峡大学 | Se doped Fe2Preparation method of P self-supporting sodium ion battery cathode material |
| CN113136603A (en) * | 2021-04-26 | 2021-07-20 | 云南大学 | Foam nickel-based erbium-doped nickel-cobalt bimetallic phosphide nano-array and preparation method and application thereof |
| CN114093678A (en) * | 2021-11-24 | 2022-02-25 | 滨州学院 | Preparation method of transition metal phosphide nanosheet electrode material |
| CN114438616A (en) * | 2022-03-07 | 2022-05-06 | 巢湖学院 | Preparation method of transition metal phosphorus sulfide nano-fiber, prepared product and application thereof |
| CN117604569A (en) * | 2024-01-17 | 2024-02-27 | 海南深远海新能源科技有限公司 | Preparation method and application of heterostructure catalyst for hydrogen production by water electrolysis |
-
2017
- 2017-06-05 CN CN201710414816.2A patent/CN107376958B/en active Active
Non-Patent Citations (1)
| Title |
|---|
| JIAHAO YU等: "Hierarchical NiFeP microflowers directly grown on Ni foam for efficient electrocatalytic oxygen evolution", 《J. MATER. CHEM.》 * |
Cited By (37)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108118362A (en) * | 2018-01-09 | 2018-06-05 | 国家纳米科学中心 | A kind of molybdenum disulfide electro-catalysis production hydrogen electrode and its preparation method and application |
| CN108554413B (en) * | 2018-04-11 | 2020-10-02 | 北京化工大学 | Three-dimensional multi-stage structure high-dispersion nickel-based electro-catalytic material and preparation method thereof |
| CN108554413A (en) * | 2018-04-11 | 2018-09-21 | 北京化工大学 | A kind of three-dimensional multistage structure high-dispersed nickel electrocatalysis material and preparation method thereof |
| CN108511767A (en) * | 2018-04-24 | 2018-09-07 | 深圳大学 | A kind of elctro-catalyst and preparation method thereof |
| CN109395752A (en) * | 2018-06-20 | 2019-03-01 | 长沙理工大学 | A kind of self-supporting double-metal phosphide Ni2P-Cu3P composite material and preparation method |
| CN108940329A (en) * | 2018-07-25 | 2018-12-07 | 南京大学 | A kind of preparation method of high activity NiFe-LDHs catalyst |
| CN108828039A (en) * | 2018-08-16 | 2018-11-16 | 广州钰芯传感科技有限公司 | A kind of double modifying foam nickel electrodes and preparation method thereof and electrochemistry formaldehyde sensor using the electrode |
| CN109012187A (en) * | 2018-08-29 | 2018-12-18 | 北京工业大学 | A kind of method of growth in situ layered bi-metal oxide nanofiltration membrane |
| CN109133259A (en) * | 2018-09-26 | 2019-01-04 | 上海电力学院 | A method of utilizing light anode activation sulfuric acid salt treatment waste water and by-product hydrogen |
| CN109847760A (en) * | 2019-01-09 | 2019-06-07 | 济南大学 | It is a kind of based on the three-dimensional elctro-catalyst of stainless steel nanostructure and its application |
| CN109847760B (en) * | 2019-01-09 | 2022-06-03 | 济南大学 | Three-dimensional electrocatalyst based on stainless steel nanostructure and application thereof |
| CN110344078A (en) * | 2019-07-03 | 2019-10-18 | 湖北大学 | A kind of nickel foam@cobalt molybdenum phosphide/ferronickel double-hydroxide electrode and the preparation method and application thereof |
| CN110344078B (en) * | 2019-07-03 | 2021-04-13 | 湖北大学 | Foamed nickel @ cobalt molybdenum phosphide/nickel iron double hydroxide electrode and preparation method and application thereof |
| CN110586148A (en) * | 2019-10-10 | 2019-12-20 | 哈尔滨师范大学 | Preparation method of self-supporting flower-shaped nickel phosphide/ferrous phosphate heterostructure full-electrolysis hydro-electric catalyst |
| CN110813334B (en) * | 2019-10-16 | 2023-01-10 | 武汉工程大学 | Preparation method and application of foam nickel loaded iron-nickel based composite material |
| CN110813334A (en) * | 2019-10-16 | 2020-02-21 | 武汉工程大学 | Preparation method and application of foam nickel-loaded iron-nickel-based composite material |
| CN111111718A (en) * | 2019-11-25 | 2020-05-08 | 浙江大学 | Preparation method of multi-metal phosphorus-doped electrocatalyst derived based on binary LDH |
| CN111068695A (en) * | 2019-11-25 | 2020-04-28 | 浙江大学 | Preparation method of multi-metal phosphorus-doped electrocatalyst derived based on ternary LDH |
| CN111068726A (en) * | 2019-11-26 | 2020-04-28 | 浙江大学 | Preparation method of iron-doped nickel phosphide composite nitrogen-doped reduced graphene oxide electrocatalytic material |
| CN111389429A (en) * | 2020-04-13 | 2020-07-10 | 苏州大学 | Preparation method of catalyst for catalyzing ammonia borane hydrolysis |
| CN111389429B (en) * | 2020-04-13 | 2023-04-11 | 苏州大学 | Preparation method of catalyst for catalyzing ammonia borane hydrolysis |
| CN111424285B (en) * | 2020-04-29 | 2022-03-18 | 郑州大学 | Preparation method for constructing catalytic electrode by taking foamed cobalt as substrate under low-temperature condition |
| CN111424285A (en) * | 2020-04-29 | 2020-07-17 | 郑州大学 | Preparation method for constructing catalytic electrode by taking foamed cobalt as substrate under low-temperature condition |
| CN111468150A (en) * | 2020-05-26 | 2020-07-31 | 陕西科技大学 | Fullerene nanorod/transition metal phosphide electrocatalyst and preparation method thereof |
| CN111747388A (en) * | 2020-06-24 | 2020-10-09 | 三峡大学 | Preparation method of self-supporting nickel phosphide-iron composite nanosheet |
| CN111790416A (en) * | 2020-08-07 | 2020-10-20 | 中南林业科技大学 | High-efficiency oxygen evolution electrocatalyst and preparation method thereof |
| CN112458482A (en) * | 2020-11-18 | 2021-03-09 | 华中科技大学 | Amorphous NiFeP transition metal catalyst, preparation method and application |
| CN112458482B (en) * | 2020-11-18 | 2021-11-19 | 华中科技大学 | Amorphous NiFeP transition metal catalyst, preparation method and application |
| CN112591724A (en) * | 2020-12-16 | 2021-04-02 | 陕西科技大学 | Preparation method of nickel iron phosphide catalyst |
| CN113104824A (en) * | 2021-03-01 | 2021-07-13 | 三峡大学 | Se doped Fe2Preparation method of P self-supporting sodium ion battery cathode material |
| CN113061929B (en) * | 2021-03-19 | 2021-12-07 | 齐齐哈尔大学 | Nickel phosphide-doped iron-based three-dimensional ultrathin nanosheet material and preparation method and application thereof |
| CN113061929A (en) * | 2021-03-19 | 2021-07-02 | 齐齐哈尔大学 | Nickel phosphide-doped iron-based three-dimensional ultrathin nanosheet material and preparation method and application thereof |
| CN113136603A (en) * | 2021-04-26 | 2021-07-20 | 云南大学 | Foam nickel-based erbium-doped nickel-cobalt bimetallic phosphide nano-array and preparation method and application thereof |
| CN114093678A (en) * | 2021-11-24 | 2022-02-25 | 滨州学院 | Preparation method of transition metal phosphide nanosheet electrode material |
| CN114438616A (en) * | 2022-03-07 | 2022-05-06 | 巢湖学院 | Preparation method of transition metal phosphorus sulfide nano-fiber, prepared product and application thereof |
| CN114438616B (en) * | 2022-03-07 | 2023-10-31 | 巢湖学院 | Preparation method of transition metal phosphorus sulfide nanofiber, prepared product and application thereof |
| CN117604569A (en) * | 2024-01-17 | 2024-02-27 | 海南深远海新能源科技有限公司 | Preparation method and application of heterostructure catalyst for hydrogen production by water electrolysis |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107376958B (en) | 2020-07-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107376958A (en) | The difunctional transition metal phosphide catalysts of NiFeP and its preparation and use | |
| CN109174162B (en) | Iron-doped bimetallic phosphide electrocatalyst and preparation method and application thereof | |
| Yang et al. | An efficient bifunctional electrocatalyst for water splitting based on cobalt phosphide | |
| CN105951123A (en) | Preparation method for NiCoP nanowire electro-catalytic electrode | |
| CN107051550A (en) | A kind of electro-catalysis water decomposition MoSe2/Co0.85Se composites and preparation method and application | |
| CN110743603B (en) | Cobalt-iron bimetal nitride composite electrocatalyst and preparation method and application thereof | |
| CN108554413A (en) | A kind of three-dimensional multistage structure high-dispersed nickel electrocatalysis material and preparation method thereof | |
| CN106694005A (en) | Preparation method of electric catalyst for acidic fully-decomposed water | |
| CN108439549A (en) | A kind of preparation of array structure transition metal selenides electrode and its application in electrolysis water | |
| WO2020252820A1 (en) | Ferronickel catalytic material, preparation method therefor, and application thereof in preparing hydrogen from electrolyzed water and preparing liquid solar fuel | |
| CN111270263B (en) | Cobaltosic oxide electrode with foam nickel loaded with rich boron and oxygen vacancies and preparation method thereof | |
| CN110538662A (en) | Preparation method of cobalt-doped rhenium disulfide nanosheet array for electrocatalytic hydrogen evolution | |
| CN111036247B (en) | Cobalt-iron oxide-cobalt phosphate electrocatalytic oxygen evolution composite material and preparation method and application thereof | |
| CN109847760A (en) | It is a kind of based on the three-dimensional elctro-catalyst of stainless steel nanostructure and its application | |
| CN111206271B (en) | Preparation method, product and application of self-supporting metal doped iron nitride electrode | |
| CN109621981A (en) | A kind of compound analysis oxygen elctro-catalyst of metal oxide-sulfide and its preparation method and application | |
| CN107519905A (en) | Vanadium carbide nanometer sieve electrocatalysis material that can be used under wide pH scopes and preparation method thereof | |
| CN112354549A (en) | Preparation method of metal composite porous nanosheet | |
| CN109201083A (en) | A kind of nano flower-like vanadium disulfide/difunctional composite electrocatalyst of hydroxyl vanadium oxide and preparation method thereof | |
| CN114411198B (en) | Transition metal sulfide Cu x S/Co 9 S 8 Heterojunction electrolytic water catalyst and preparation method and application thereof | |
| CN110219013A (en) | A kind of electrode material of self-supporting nitrogen modification nickel iron hydroxide | |
| CN110699701B (en) | Foam nickel loaded with metal nickel and vanadium trioxide compound and preparation method and application thereof | |
| CN110841658A (en) | Preparation method of cobalt-based sulfide nanorod array | |
| CN113201752B (en) | Preparation method and application of CoNiP-P nano catalyst with rich heterojunction | |
| CN110449170A (en) | A kind of amorphous state MoS2Modify CoS/Co0.85The preparation method of the heterogeneous nano-tube array elctro-catalyst of Se |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |