CN107376958B - NiFeP difunctional transition metal phosphide catalyst and preparation and application thereof - Google Patents
NiFeP difunctional transition metal phosphide catalyst and preparation and application thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 49
- 229910052723 transition metal Inorganic materials 0.000 title claims abstract description 30
- 150000003624 transition metals Chemical class 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims description 11
- 239000002135 nanosheet Substances 0.000 claims abstract description 43
- 239000000758 substrate Substances 0.000 claims description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 23
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 17
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- 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 description 11
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 11
- 238000001354 calcination Methods 0.000 claims description 11
- 239000004202 carbamide Substances 0.000 claims description 11
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 10
- 230000001588 bifunctional effect Effects 0.000 claims description 10
- 239000004917 carbon fiber Substances 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 239000011261 inert gas Substances 0.000 claims description 10
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 10
- 150000002815 nickel Chemical class 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 8
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 8
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 7
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 238000004321 preservation Methods 0.000 claims description 3
- 238000011144 upstream manufacturing Methods 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-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
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 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
- 229960002089 ferrous chloride Drugs 0.000 claims description 2
- 239000011790 ferrous sulphate Substances 0.000 claims description 2
- 235000003891 ferrous sulphate Nutrition 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
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 2
- 229910000359 iron(II) 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
- 239000006260 foam Substances 0.000 claims 3
- 238000000034 method Methods 0.000 claims 3
- 238000003421 catalytic decomposition reaction Methods 0.000 claims 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 9
- 230000003197 catalytic effect Effects 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
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 238000004140 cleaning Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- HTXDPTMKBJXEOW-UHFFFAOYSA-N dioxoiridium Chemical compound O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 229910052603 melanterite Inorganic materials 0.000 description 3
- 230000010287 polarization Effects 0.000 description 3
- KOUDKOMXLMXFKX-UHFFFAOYSA-N sodium oxido(oxo)phosphanium hydrate Chemical compound O.[Na+].[O-][PH+]=O KOUDKOMXLMXFKX-UHFFFAOYSA-N 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000010411 electrocatalyst Substances 0.000 description 2
- 235000019441 ethanol Nutrition 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
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 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 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 238000007789 sealing Methods 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
- 238000012360 testing method Methods 0.000 description 2
- 241000282414 Homo sapiens Species 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- 229910000457 iridium oxide Inorganic materials 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- UGKDIUIOSMUOAW-UHFFFAOYSA-N iron nickel Chemical compound [Fe].[Ni] UGKDIUIOSMUOAW-UHFFFAOYSA-N 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- YHGPYBQVSJBGHH-UHFFFAOYSA-H iron(3+);trisulfate;pentahydrate Chemical compound O.O.O.O.O.[Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O YHGPYBQVSJBGHH-UHFFFAOYSA-H 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- -1 polytetrafluoroethylene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 1
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
Images
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- 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
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- B01J35/33—Electric or magnetic properties
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
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- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
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Abstract
The invention provides a NiFeP difunctional transition metal phosphide catalyst which has a nanosheet structure, wherein the length of the nanosheet is 2-5 m, and the thickness of the nanosheet is 100-200 nm.
Description
Technical Field
The invention belongs to the field of electrochemistry, and particularly relates to a catalyst for electrocatalytic decomposition of water and preparation thereof.
Background
In recent years, resource shortage and environmental pollution have become two major global crises. Therefore, in order to realize sustainable development of human beings, the development of green and clean renewable energy is a problem to be solved urgently. Hydrogen energy is a new clean, renewable, environment-friendly and pollution-free energy source, and attracts people's attention. Hydrogen energy as an all-weather resource can be prepared by electrolyzing water, while water resources on the earth are extremely rich, and hydrogen preparation by water has incomparable great advantages and wide application prospect.
Currently, the most common hydrogen evolution catalysts are still platinum group noble metals, and the most common oxygen evolution catalysts rely on iridium oxide, ruthenium oxide. Platinum, iridium and ruthenium belong to noble metals, and the reserves on the earth are small, so that the popularization and the application of the platinum, iridium and ruthenium on the industry are not facilitated, and therefore, the development of non-noble metal catalysts with rich earth content is imperative. Heretofore, carbide and nitride of transition metal have been foundSubstances, sulfides, phosphides and the like have good catalytic action on Hydrogen Evolution Reaction (HER) and Oxygen Evolution Reaction (OER). Most of the reported transition metal hydrogen evolution catalysts have stronger catalytic activity under strong acid, while the oxygen evolution catalysts can only exist stably under alkaline condition. Therefore, how to prepare a transition metal catalyst with high catalytic performance under an alkaline environment, particularly with dual functions of hydrogen evolution and oxygen evolution, is still a problem to be solved urgently in the field of electrocatalysis. The current density of some three-element bifunctional phosphide catalysts for total hydrolysis in alkaline environment reported at present can reach 10 milliamperes/cm under the voltage of 1.6 volts2The efficiency of catalytic electrolysis of water has not yet met the economic development needs.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides the NiFeP difunctional transition metal phosphide catalyst which shows excellent catalytic performance in alkaline electrocatalytic hydrogen evolution, alkaline electrocatalytic oxygen evolution and total hydrolysis.
The second purpose of the invention is to propose the preparation of the NiFeP bifunctional transition metal phosphide catalyst.
A third object of the present invention is to propose the use of a NiFeP bifunctional transition metal phosphide catalyst.
The technical scheme for realizing the above purpose of the invention is as follows:
a NiFeP difunctional transition metal phosphide catalyst has a nanosheet structure, wherein the nanosheet is 2-5 m in length and 100-200 nm in thickness.
Wherein the chemical formula of the NiFeP difunctional transition metal phosphide is Ni(2-x)FexP, wherein x is 0.2-0.8.
A preparation method of a NiFeP difunctional transition metal phosphide catalyst comprises the following steps:
1) dissolving nickel salt, ferric salt, urea and ammonium fluoride in deionized water to obtain a mixed solution;
2) immersing a conductive substrate into the mixed solution obtained in the step 1), and preserving heat to obtain a substrate with a NiFe-L DH nano sheet growing on the surface;
3) calcining the sodium hypophosphite and the substrate obtained in the step 2) under the protection of inert gas, wherein the calcining temperature is 280-350 ℃, and obtaining the NiFeP transition metal phosphide nanosheet.
Wherein, the nickel salt, the iron salt and the sodium hypophosphite can be hydrates thereof.
The nickel salt is one or more of nickel nitrate, nickel sulfate and nickel chloride, the ferric salt is one or more of ferric sulfate, ferrous sulfate, ferric chloride, ferrous chloride, ferric nitrate and ferrous nitrate, and the molar ratio of the nickel salt to the ferric salt is (0.5-2): 1.
in the step 1), the ratio of the total mass of the nickel salt, the ferric salt, the urea and the ammonium fluoride to the volume of the deionized water is (10-50 g) to 1L, wherein the mass ratio of the urea to the ammonium fluoride is 1 (2-3).
Wherein, the conductive substrate in the step 2) is made of carbon material or transition metal and is selected from one of carbon fiber, foamed nickel, foamed copper and foamed aluminum; the heat preservation is carried out for 5-12 hours at the temperature of 95-110 ℃ under the closed condition.
And 2) placing sodium hypophosphite and the substrate obtained in the step 2) in a calcining device in the step 3), introducing inert gas into the calcining device, placing the sodium hypophosphite at the upstream of the substrate according to the airflow direction, heating to 280-400 ℃ at the speed of 2-10 ℃/min, and then preserving heat for 1-2 hours.
Preferably, the inert gas in the step 3) is one of argon, nitrogen and helium, the purity of the inert gas is more than 99.99%, and the introduced flow rate is 50-100 sccm.
The NiFeP difunctional transition metal phosphide catalyst disclosed by the invention is applied to the reaction of electrocatalytic decomposition of water.
Further, it is used for catalytically decomposing alkaline water. The alkaline water may be OH in water-The concentration of the solution is 0.1-5 mol/L.
The invention has the beneficial effects that:
compared with the prior art, the NiFeP bifunctional transition metal phosphide catalyst provided by the invention has a microstructure of a nanosheet with a large specific surface area, and has a better catalytic performance when being used as a water decomposition electrocatalyst.
The preparation method of the bifunctional phosphide catalyst provided by the invention takes a nickel-iron compound, ammonium fluoride and urea as raw materials, NiFe-L DH nanosheets grow on a substrate in a heat-preservation manner, and NiFeP transition metal phosphide nanosheets are obtained by low-temperature phosphorization, the operation is simple, the production cost is low, the prepared phosphide catalyst is applied to perhydrolysis in an alkaline environment, the perhydrolysis catalytic performance is excellent, and the current density can reach 10 milliamperes/cm under the voltage of 1.55 volts2。
Compared with noble metals such as Pt/Ir and the like, the invention takes transition metal with low price and abundant reserves as raw material, can greatly reduce the cost of the electrocatalyst, and the NiFeP bifunctional catalyst provided by the invention not only has excellent performance in the aspect of alkaline electrocatalytic hydrogen evolution, but also shows excellent catalytic performance in alkaline electrocatalytic oxygen evolution and total hydrolysis.
Drawings
FIG. 1 is a scanning electron microscope photograph of a NiFe-L DH @ NF catalyst nanosheet prepared in accordance with the present invention, wherein (a) the drawing is a partial view of a NiFe-L DH @ NF catalyst nanosheet and (b) the drawing is a partial magnified view of a NiFe-L DH @ NF catalyst nanosheet;
FIG. 2 is a scanning electron microscope photograph of a NiFe-L DH @ CF catalyst nanosheet prepared in accordance with the present invention, wherein (a) the drawing is a partial view of a NiFe-L DH @ CF catalyst nanosheet and (b) the drawing is a partial magnified view of a NiFe-L DH @ CF catalyst nanosheet;
FIG. 3 is a scanning electron microscope photograph of a NiFeP @ NF catalyst nanosheet prepared in accordance with the present invention, wherein (a) the drawing is a partial view of the NiFeP @ NF catalyst nanosheet and (b) the drawing is a partial magnified view of the NiFeP @ NF catalyst nanosheet;
FIG. 4 is a scanning electron microscope photograph of a NiFeP @ CF catalyst nanosheet prepared in accordance with the present invention, wherein (a) the drawing is a partial view of the NiFeP @ CF catalyst nanosheet and (b) the drawing is a partial magnified view of the NiFeP @ CF catalyst nanosheet;
FIG. 5 is a field emission transmission electron microscope photograph of NiFeP catalyst nanosheets prepared in accordance with the present invention;
FIG. 6 is an X-ray diffraction pattern of NiFeP catalyst nanosheets prepared in accordance with the present invention;
fig. 7 is a polarization curve diagram of NiFeP catalyst nanosheets prepared in accordance with the present invention.
Detailed Description
Ammonium fluoride, Ni (NO) used in the following examples3)2·6H2O、FeSO4·7H2O, urea and sodium hypophosphite monohydrate are used as reaction raw materials, and the reaction raw materials are all analytically pure by the national medicine group.
Example 1:
222mg ammonium fluoride, 290mg Ni (NO) are weighed out on an analytical balance3)2·6H2O、278mg FeSO4·7H2O and 600mg of urea are added to 40ml of deionized water in sequence and stirred for half an hour to uniformly mix the solution.
And sequentially adopting acetone, an alcohol solvent and deionized water to respectively ultrasonically clean the foamed Nickel (NF) for 30min, then ultrasonically cleaning the foamed Nickel (NF) for 10-20 min by using 0.1M dilute hydrochloric acid, and finally ultrasonically cleaning the foamed Nickel (NF) for 30min by using the deionized water.
And (3) putting the cleaned substrate into a polytetrafluoroethylene inner container in a 50ml reaction kettle, pouring the uniformly stirred mixed solution, sealing the reaction kettle, putting the reaction kettle into a blast oven, and keeping the temperature for 6 hours at 100 ℃, wherein NiFe-L DH nano-sheets grow on the substrate.
And (4) cooling the temperature of the reaction kettle to room temperature, taking out the substrate, and sequentially cleaning the substrate with deionized water and absolute ethyl alcohol. The drying purpose is achieved by keeping the temperature for 3h at 60 ℃ in a vacuum environment.
A sample with a substrate of foamed Nickel (NF) is observed by a scanning electron microscope (S-4800), the appearance of the sample is shown as figure 1, nano sheets uniformly distributed are grown on the substrate, and the length of the nano sheets can reach 5 mu m at most.
Placing sodium hypophosphite monohydrate and a substrate with NiFe-L DH nano sheets at two ends of a ceramic boat, placing the sodium hypophosphite monohydrate at the upstream of airflow, placing the ceramic boat in a tube furnace, sealing the tube furnace, exhausting the air in a quartz tube by using a vacuum pump and high-purity argon, and calcining under the airflow of the high-purity argon (the purity is more than or equal to 99.999%).
Heating the quartz tube from room temperature to 300 ℃ at the heating rate of 5 ℃/min, preserving the heat at 300 ℃ for 1h, and then cooling the tube furnace to the room temperature. The flow of high purity argon was maintained at 80sccm throughout the experiment.
And after the temperature is reduced to room temperature, the NiFe-L DH nano-sheets on the substrate are phosphorized, the appearance of the phosphorized NiFeP @ NF is observed by a scanning electron microscope and is shown in figure 3, the uniformly distributed nano-sheets are fully grown on the substrate, and the length can reach 5um at most.
FIG. 5 is a field emission transmission electron microscope photograph (Tecnaig2F20U-TWIN) of the transition metal NiFeP catalyst obtained in example 1. Fig. 5 shows that the transition metal NiFeP catalyst is of a nanosheet structure.
The phase of the resulting product was tested by X-ray diffraction (D/MAX-TTRIII (CBO)), as shown in FIG. 6, with standard card Ni2P PDF #89-4864 and Fe2P PDF #89-3680 is very consistent, and the obtained nano-sheet is proved to have Ni as a component1.5Fe0.5P。
Example 2
222mg ammonium fluoride, 290mg Ni (NO) are weighed out on an analytical balance3)2·6H2O、278mg FeSO4·7H2O and 600mg of urea are added to 40ml of deionized water in sequence and stirred for half an hour to uniformly mix the solution.
And sequentially adopting acetone, an alcohol solvent and deionized water to respectively ultrasonically clean the Carbon Fiber (CF) for 30min, then ultrasonically cleaning the Carbon Fiber (CF) for 10-20 min by using 0.1M dilute hydrochloric acid, and finally ultrasonically cleaning the Carbon Fiber (CF) for 30min by using the deionized water.
The other operations were the same as in example 1.
After NiFe-L DH nanometer sheets grow on the substrate, a sample with the substrate being Carbon Fiber (CF) is observed by a scanning electron microscope (S-4800), the appearance of the sample is shown as the attached figure 2, the nanometer sheets which are uniformly distributed are grown on the substrate, and the length can reach 5 mu m at most.
The appearance of the phosphated NiFeP @ CF is observed by a scanning electron microscope and is shown in figure 4, nano sheets which are uniformly distributed are fully grown on a substrate, and the length can reach 5 mu m at most. The phase of the product obtained by X-ray diffraction test is shown in FIG. 6.
Test examples
Two pieces of the catalyst prepared in example 1 were placed in a 1 mol/l aqueous solution of potassium hydroxide (pH 14) with a certain gap therebetween. One piece is connected with a working electrode of an electrochemical workstation, the other piece is connected with an auxiliary electrode and a counter electrode, and a polarization curve is drawn in a certain voltage range. The catalyst prepared in example 2 and a commercially available catalyst, Pt @ Ti-RuO, were tested in the same manner2/IrO2@ Ti, results are shown in FIG. 7.
Fig. 7 is a polarization curve of the NiFeP bifunctional transition metal nanosheet catalyst prepared in example 1 or example 2 under an alkaline environment (1 mol/l potassium hydroxide, pH 14). This figure illustrates the NiFeP nanosheet catalyst and Pt @ Ti-RuO obtained in example 12/IrO2Compared with @ Ti, the catalyst has better electrolytic water catalytic performance, and when the current density is 10 milliampere/cm2(j＝10mA·cm-2) The potential of the NiFeP nanosheet electrode relative to the standard electrode was 1.55 volts.
The applicant states that the detailed structure and composition of the present invention are described by the above embodiments, but the present invention is not limited to the above detailed structure and composition, that is, it is not meant that the present invention must be implemented by relying on the above detailed structure and composition. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (10)
1. The NiFeP difunctional transition metal phosphide catalyst is characterized by having a nanosheet structure, wherein the nanosheet is 2-5 microns long and 100-200 nm thick;
the NiFeP difunctional transition metal phosphide catalyst is prepared by adopting the following method:
1) dissolving nickel salt, ferrous salt, urea and ammonium fluoride in deionized water to obtain a mixed solution;
2) immersing a conductive substrate into the mixed solution obtained in the step 1), and preserving heat to obtain a substrate with a NiFe-L DH nano sheet growing on the surface;
3) calcining the sodium hypophosphite and the substrate obtained in the step 2) under the protection of inert gas, wherein the calcining temperature is 300 ℃, and obtaining the NiFeP transition metal phosphide nanosheet.
2. The NiFeP bifunctional transition metal phosphide catalyst of claim 1, wherein the NiFeP bifunctional transition metal phosphide has the chemical formula of Ni（2-x）FexP, wherein x = 0.2-0.8.
3. A preparation method of a NiFeP difunctional transition metal phosphide catalyst is characterized by comprising the following steps:
1) dissolving nickel salt, ferrous salt, urea and ammonium fluoride in deionized water to obtain a mixed solution;
2) immersing a conductive substrate into the mixed solution obtained in the step 1), and preserving heat to obtain a substrate with a NiFe-L DH nano sheet growing on the surface;
3) calcining the sodium hypophosphite and the substrate obtained in the step 2) under the protection of inert gas, wherein the calcining temperature is 300 ℃, and obtaining the NiFeP transition metal phosphide nanosheet.
4. The preparation method according to claim 3, wherein the nickel salt is one or more of nickel nitrate, nickel sulfate and nickel chloride, the ferrous salt is one or more of ferrous sulfate, ferrous chloride and ferrous nitrate, and the molar ratio of the nickel salt to the ferrous salt is (0.5-2): 1.
5. the preparation method according to claim 3, wherein in the step 1), the ratio of the total mass of the nickel salt, the ferrous salt, the urea and the ammonium fluoride to the volume of the deionized water is (10-50 g): 1L, wherein the mass ratio of the urea to the ammonium fluoride is 1 (2-3).
6. The method according to claim 3, wherein the conductive substrate in step 2) is made of a carbon material or a transition metal, and is selected from one of carbon fiber, nickel foam, copper foam and aluminum foam; the heat preservation is carried out for 5-12 hours at the temperature of 95-110 ℃ under the closed condition.
7. The preparation method according to claim 3, characterized in that the sodium hypophosphite obtained in the step 3) and the substrate obtained in the step 2) are placed in a calcining device, inert gas is introduced into the calcining device, the sodium hypophosphite is placed at the upstream of the substrate according to the airflow direction, the temperature is raised to 300 ℃ at the speed of 2-10 ℃/min, and then the temperature is maintained for 1-2 hours.
8. The method according to claim 3, wherein the inert gas in step 3) is one of argon, nitrogen and helium, the purity of the inert gas is more than 99.99%, and the flow rate of the inert gas is 50-100 sccm.
9. Use of a NiFeP bifunctional transition metal phosphide catalyst as defined in claim 1 or 2 in electrocatalytic water splitting reactions.
10. Use according to claim 9, for the catalytic decomposition of alkaline water.
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