CN111871426B - Pd nanoparticle-supported nickel-iron double hydroxide nanosheet array structure material, preparation method and application thereof - Google Patents
Pd nanoparticle-supported nickel-iron double hydroxide nanosheet array structure material, preparation method and application thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 87
- 239000002135 nanosheet Substances 0.000 title claims abstract description 76
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 title claims abstract description 20
- UGKDIUIOSMUOAW-UHFFFAOYSA-N iron nickel Chemical compound [Fe].[Ni] UGKDIUIOSMUOAW-UHFFFAOYSA-N 0.000 title claims abstract description 16
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 158
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 84
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 claims abstract description 70
- 239000002105 nanoparticle Substances 0.000 claims abstract description 62
- 238000006243 chemical reaction Methods 0.000 claims abstract description 61
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 27
- 239000001257 hydrogen Substances 0.000 claims abstract description 25
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 25
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 24
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000001301 oxygen Substances 0.000 claims abstract description 23
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 22
- 239000000243 solution Substances 0.000 claims abstract description 18
- 239000006260 foam Substances 0.000 claims abstract description 16
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000004202 carbamide Substances 0.000 claims abstract description 10
- 150000002815 nickel Chemical class 0.000 claims abstract description 10
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims abstract description 9
- 150000003839 salts Chemical class 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 7
- 238000004729 solvothermal method Methods 0.000 claims abstract description 6
- 238000005406 washing Methods 0.000 claims abstract description 6
- 238000001816 cooling Methods 0.000 claims abstract description 5
- 238000004090 dissolution Methods 0.000 claims abstract description 3
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 239000002064 nanoplatelet Substances 0.000 claims description 31
- 238000000034 method Methods 0.000 claims description 11
- 239000010411 electrocatalyst Substances 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 6
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical group [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 5
- 238000009826 distribution Methods 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 2
- SZQUEWJRBJDHSM-UHFFFAOYSA-N iron(3+);trinitrate;nonahydrate Chemical group O.O.O.O.O.O.O.O.O.[Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SZQUEWJRBJDHSM-UHFFFAOYSA-N 0.000 claims description 2
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical group O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 20
- 238000000354 decomposition reaction Methods 0.000 abstract description 16
- 230000000694 effects Effects 0.000 abstract description 14
- 239000011259 mixed solution Substances 0.000 abstract description 8
- 239000003792 electrolyte Substances 0.000 abstract description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 48
- 230000010287 polarization Effects 0.000 description 18
- 238000011068 loading method Methods 0.000 description 14
- 238000004502 linear sweep voltammetry Methods 0.000 description 13
- 239000000047 product Substances 0.000 description 12
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 10
- 230000005540 biological transmission Effects 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 7
- 238000010586 diagram Methods 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 101150003085 Pdcl gene Proteins 0.000 description 6
- 229910052742 iron Inorganic materials 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 229910021607 Silver chloride Inorganic materials 0.000 description 4
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- 229910003297 Ni(NO3)3·6H2O Inorganic materials 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 239000008151 electrolyte solution Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 238000000634 powder X-ray diffraction Methods 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 150000003624 transition metals Chemical class 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910002554 Fe(NO3)3·9H2O Inorganic materials 0.000 description 2
- 238000001069 Raman spectroscopy Methods 0.000 description 2
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- -1 polytetrafluoroethylene Polymers 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
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- 230000001105 regulatory effect Effects 0.000 description 2
- 230000027756 respiratory electron transport chain Effects 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 229910002588 FeOOH Inorganic materials 0.000 description 1
- 229910017135 Fe—O Inorganic materials 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 229910003271 Ni-Fe Inorganic materials 0.000 description 1
- 239000011865 Pt-based catalyst Substances 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
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- 238000011161 development Methods 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
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- 238000006460 hydrolysis reaction Methods 0.000 description 1
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- 150000004679 hydroxides Chemical class 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
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Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/892—Nickel and noble metals
-
- B01J35/33—
-
- B01J35/40—
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The invention discloses a Pd nanoparticle-supported nickel-iron double hydroxide nanosheet array structure material, a preparation method and application thereof; adding nickel salt, ferric salt, urea and quaternary ammonium salt into anhydrous methanol, adding palladium source solution after ultrasonic dissolution, uniformly mixing, transferring the mixed solution into a reaction kettle, obliquely placing foam nickel into the mixed solution, performing solvothermal reaction, naturally cooling to room temperature, washing and drying to obtain Pd nano-particle loaded NiFe LDH nano-sheet array structure material; the catalyst has the advantages of high activity, good durability, simple preparation process and low cost in alkaline electrolyte, has excellent activity and stability for oxygen evolution reaction, hydrogen evolution reaction and full water decomposition reaction, and is very valuable in practical application of electrocatalytic water decomposition materials.
Description
Technical Field
The invention belongs to the field of nano material preparation methods and electrocatalytic cross application, and particularly relates to a Pd nanoparticle-supported nickel-iron double hydroxide nano sheet array structure material, a preparation method and application thereof.
Background
The electrolysis of water to produce hydrogen and oxygen provides an environmentally friendly and sustainable method for energy storage and conversion. The water splitting reaction consists of two half reactions: anodic Oxygen Evolution (OER) and cathodic Hydrogen Evolution (HER). Advances in this technology require the preparation of highly active and stable electrocatalysts to accelerate the catalytic kinetics of OER and HER. Pt-based catalysts are well known as advanced HER catalyst materials, ruO 2 And IrO 2 Is an advanced OER catalyst, and the characteristics of high cost, poor stability and the like of the noble metal catalysts limit the application of full hydrolysis. Thus, inexpensive OER and HER electrocatalysts are produced which have both high activity and stability under alkaline conditionsThe challenge.
Among transition metal catalysts, transition metal Layered Double Hydroxides (LDHs) are widely used in OER reactions, where NiFe LDHs have proved to have the highest OER catalytic activity. Although Ni in NiFe LDH 2+ Center to water molecules and OH - The intermediate has excellent adsorption capacity, but the hydrogen intermediate is in Fe 3+ Adsorption on the center is weak and HER kinetics in alkaline solutions are slow. In addition, poor conductivity of NiFe LDH limits the electron transfer rate during catalysis. Pd is considered to be the precious metal with electrocatalytic HER activity closest to Pt and has some OER activity, while Pd is cheaper than precious metals such as Pt, ru and Ir. Therefore, the Pd nano-particles are loaded on the nickel-iron double hydroxide to form a heterostructure, so that the consumption of noble metals can be reduced, and the catalytic activity and stability of the catalyst for water decomposition can be improved.
However, in the prior art, the preparation method for forming the heterostructure catalyst by combining Pd and the transition metal layered double hydroxide is complex, and uniform loading of Pd nano particles on the surface of the double hydroxide is difficult to realize in the preparation process. Therefore, the problems of high preparation cost, poor activity and stability and the like of the catalyst in the prior art still limit the development and application of electrocatalytic water decomposition.
Disclosure of Invention
The invention aims to provide a Pd nanoparticle-supported nickel-iron double hydroxide (NiFe LDH) nanosheet array structure material, a preparation method and application thereof. Preparing a Pd nano particle loaded NiFe LDH nano sheet array structure material with foamed nickel as a conductive substrate through one-step liquid phase reaction, wherein the average particle size of the Pd nano particles is 1.5-3.0 nm; and to OER, HER and full water splitting applications. NiFe LDH nanosheets can adsorb H through hydrogen bonds 2 O molecules and are cleaved into adsorbed H by taking electrons + And OH (OH) - Ions help to accelerate adsorption and dissociation of water molecules. After Pd nano particles are introduced on the surface of the NiFe LDH nano sheet, the electronic structure of Pd, ni and Fe atoms can be effectively regulated, the energy barrier of the intermediate is optimized to accelerate the catalytic dynamics, and the conductivity of the catalyst is improved to accelerate the electron transfer speedThe rate of the catalyst is increased, the exposure of the active site is increased, and the activity and stability of the catalyst for water decomposition are improved.
The invention provides a preparation method of a Pd nanoparticle-loaded NiFe LDH nanosheet array structure material, which comprises the following steps: adding nickel salt, ferric salt, urea and quaternary ammonium salt into absolute methanol, adding palladium source solution after ultrasonic dissolution, transferring the mixed solution into a reaction kettle after uniform mixing, obliquely placing foam nickel into the mixed solution, carrying out solvothermal reaction, naturally cooling to room temperature, washing and drying to obtain the Pd nano-particle loaded NiFe LDH nano-sheet array structure material.
Further, the ratio of the amounts of the substances of the nickel salt, the ferric salt, the urea, the quaternary ammonium salt and the palladium source is as follows: 1.0:0.11-0.67:0.8-1.2:0.062-0.31:0.0075-0.0125;
the ratio of the amounts of the substances of the nickel salt, the ferric salt, the urea, the quaternary ammonium salt and the palladium source is preferably 1.0:0.25:1.0:0.186:0.0075-0.0125; more preferably 1.0:0.25:1.0:0.186:0.01.
The nickel salt is nickel nitrate hexahydrate (Ni (NO 3 ) 3 ·6H 2 O); the ferric salt is ferric nitrate nonahydrate (Fe (NO) 3 ) 3 ·9H 2 O); the quaternary ammonium salt is tetra-n-butyl ammonium bromide (C) 16 H 36 BrN); the palladium source solution is an aqueous solution of chloropalladite.
The concentration of the nickel salt in anhydrous methanol was 0.033M.
The concentration of the iron salt in the absolute methanol is 0.0036 to 0.0223M, preferably 0.0083M.
The concentration of the quaternary ammonium salt in the anhydrous methanol is 2.07-10.34M, preferably 6.2M.
The concentration of urea in anhydrous methanol was 0.033M.
The concentration of the palladium source solution is 2.256 multiplied by 10 -2 M, the amount of the substance added to the anhydrous methanol is 7.5 to 12.5. Mu. Mol, preferably 10. Mu. Mol.
The solvothermal reaction conditions are from 4 to 8 hours at 120 ℃, preferably for 6 hours at 120 ℃.
The foam nickel is required to be cleaned before being used, and the specific cleaning method comprises the following steps: the outer oxide film is removed by soaking in 6M hydrochloric acid for 15min, and then washed by deionized water and absolute ethyl alcohol, and cut into 2X 3cm size when in use.
The solvothermal reaction is performed in a polytetrafluoroethylene-lined stainless steel reaction kettle.
The washing is as follows: washing with deionized water for 3-5 times, and washing with absolute ethanol for 3-5 times.
The drying is as follows: drying in a vacuum drying oven at 60 ℃ for 12 hours.
The invention also provides the Pd nano-particle loaded NiFe LDH nano-sheet array structure material prepared by the preparation method, the morphology of the Pd nano-particle loaded NiFe LDH nano-sheet array structure material is a nano-sheet array with the transverse dimension of 75-150nm, and Pd nano-particles with the average dimension of 2nm are uniformly loaded on the surface of the NiFe LDH nano-sheet array.
The invention also provides application of the Pd nanoparticle-loaded NiFe LDH nanosheet array structure material as an electrocatalyst for Oxygen Evolution Reaction (OER), hydrogen Evolution Reaction (HER) or full water decomposition reaction.
When the Pd nanoparticle-supported NiFe LDH nanosheet array structure material is used as an electrocatalyst for Oxygen Evolution Reaction (OER), the specific method comprises the following steps: and cutting the Pd nanoparticle-loaded NiFe LDH nanosheet array structure material into 0.5X0.5 cm size to serve as a working electrode, respectively using a platinum wire and an Ag/AgCl electrode as a counter electrode and a reference electrode, using an electrolyte of 1.0M KOH solution, and performing electrochemical test by using a CHI 760E electrochemical workstation. Linear scanning polarization curve (LSV) at 5.0 mV.s -1 Is performed at a scan rate of 90%. Stability was obtained by measuring the current density time curve at constant voltage. Electrochemically active areas (ECSA) are obtained by measuring the surface area of the substrate (40, 60, 80, 100, 120, 140 and 160 mV.s) -1 ) Electrochemical double layer capacitance (C) measurement using cyclic voltammetry dl ) Evaluating the voltage range of the test to be 0.523-0.623V (vs. RHE); electrochemical Impedance (EIS) was tested at a frequency range of 100kHz to 0.1Hz and at 1.45V (vs. rhe). In the form of commercial RuO 2 The OER performance was tested as an electrode on nickel foam as a comparison.
When the Pd nanoparticle-loaded NiFe LDH nanosheet array structure material is used as a Hydrogen Evolution Reaction (HER) electrocatalyst, the specific method comprises the following steps: and cutting the Pd nanoparticle-loaded NiFe LDH nanosheet array structure material into 0.5X0.5 cm size to serve as a working electrode, respectively using a carbon rod and an Ag/AgCl electrode as a counter electrode and a reference electrode, using an electrolyte of 1.0M KOH solution, and performing electrochemical test by using a CHI 760E electrochemical workstation. Linear scanning polarization curve (LSV) at 5.0 mV.s -1 Is performed at a scan rate of 90%. Stability was obtained by measuring the current density time curve at constant voltage. Electrochemically active areas (ECSA) are obtained by scanning at different scanning rates (40, 60, 80, 100, 120, 140 and 160 mV.s -1 ) Electrochemical double-layer capacitor (C) dl ) Evaluating the test voltage range to be-0.107 to-0.007V (vs. RHE); electrochemical Impedance (EIS) was tested at-0.1V (vs. RHE) at a frequency range of 100kHz to 0.1 Hz. HER performance was tested as a comparison with commercial Pt/C loading on nickel foam as the working electrode.
When the Pd nanoparticle-loaded NiFe LDH nanosheet array structure material is used as a full-water decomposition reaction electrocatalyst, the specific method comprises the following steps: and shearing the Pd nanoparticle-loaded NiFe LDH nanosheet array structure material into 2 pieces of 0.5X0.5 cm, respectively serving as an anode and a cathode, assembling the pieces in a double-electrode electrolytic tank, and testing the full-water decomposition performance through an LSV polarization curve compensated by 90% iR and a current density time curve under constant voltage. In contrast, noble metal RuO supported on nickel foam in a double electrode cell was studied 2 LSV polarization curves as anode and Pt/C as cathode.
In the invention, the Pd nano particles load the NiFe LDH nano sheets and optimize the electronic structure of the catalyst, and through the electron migration among Pd, ni and Fe atoms, the electron interaction among Pd, ni and Fe atoms can be effectively regulated, the electron density of the Pd atom surface is improved, and H in the HER process is accelerated + To H 2 Is transformed by the above method. And reduces the occupation of the inverse bond state orbitals of Ni and Fe atoms, improves the adsorption of surface oxidation substances (such as: OH and OOH), and enhances the OER activity.Meanwhile, the Pd nano particles are loaded, so that the electrochemical active area of a sample can be increased, and more catalytic active sites are exposed. In addition, the increased conductivity significantly enhances the transfer rate of interface charges. Therefore, the material has excellent activity and stability for oxygen evolution reaction, hydrogen evolution reaction and full water decomposition reaction in alkaline electrolyte, and is very valuable in practical application of electrocatalytic water decomposition material.
Compared with the prior art, the invention provides alkaline environment by urea through simple one-step chemical liquid phase synthesis, ni 2+ And Fe (Fe) 3+ Hydrolyzing under alkaline condition, growing nickel-iron double hydroxide nano-sheet array on the surface of foam nickel, and Br under the action of tetra-n-butyl ammonium bromide - The catalyst can be selectively adsorbed on the surface of Pd nano particles, the surface energy is reduced, the agglomeration of the Pd nano particles is inhibited, pd nano particles with the average size of 2nm are formed under the reduction action of methanol, and the Pd nano particles are uniformly loaded with the NiFe LDH nano sheet array structure material in situ. The Pd nanoparticle uniformly loaded NiFe LDH nanosheet array structure material provided by the invention is used as Oxygen Evolution Reaction (OER), hydrogen Evolution Reaction (HER) and full-water decomposition electrocatalyst material, and has the characteristics of low overpotential under high current density, good stability, environment-friendly preparation process and low cost.
Drawings
FIG. 1 is an X-ray powder diffraction (XRD) pattern of a Pd nanoparticle-supported NiFe LDH nanosheet array structure material prepared in example 1;
FIG. 2 is a Scanning Electron Microscope (SEM) image of a Pd nanoparticle-supported NiFe LDH nanosheet array structure material prepared in example 1;
FIG. 3 is an energy dispersive X-ray (EDX) spectrum of a Pd nanoparticle-supported NiFe LDH nanosheet array structure material prepared in example 1;
FIG. 4 is a Transmission Electron Microscope (TEM) image of the Pd nanoparticle-supported NiFe LDH nanosheet array structure material prepared in example 1;
FIG. 5 is a Scanning Transmission Electron Microscope (STEM) diagram and corresponding elemental distribution diagram of a Pd nanoparticle-supported NiFe LDH nanosheet array structure material prepared in example 1;
FIG. 6 is a high resolution lattice fringe (HRTEM) image of the Pd nanoparticle supported NiFe LDH nanosheet array structure material prepared in example 1;
FIG. 7 is a Raman spectrum (Raman) diagram of the Pd nanoparticle-supported NiFe LDH nanosheet array structure material prepared in example 1;
FIG. 8 is an energy dispersive X-ray spectroscopy (EDX) plot of the NiFe LDH nanoplatelet array structure material prepared in example 2 having mass percentages of 0.69% and 1.14%;
FIG. 9 is a Scanning Electron Microscope (SEM) image of a NiFe LDH nanosheet array structure material with a mass percent of 0.69% of the Pd nanoparticles prepared in example 2;
FIG. 10 is a Scanning Electron Microscope (SEM) image of a NiFe LDH nanosheet array structure material having a mass percent of Pd nanoparticles of 1.14% prepared in example 2;
FIG. 11 is a Transmission Electron Microscope (TEM) image of a NiFe LDH nanoplatelet array structure material having a Pd mass percent of 0.69% prepared in example 2;
FIG. 12 is a Transmission Electron Microscope (TEM) image of a NiFe LDH nanoplatelet array structure material having a Pd mass percent of 1.14% prepared in example 2;
FIG. 13 is a LSV polarization curve of Oxygen Evolution Reaction (OER) for Pd nanoparticle-supported NiFe LDH nanoplatelet array structures of different Pd contents (0.69%, 0.92% and 1.14%) prepared in example 1 and example 2;
FIG. 14 is a LSV graph (inset shows polarization curve at high current density) of Oxygen Evolution Reaction (OER) of Pd nanoparticle supported NiFe LDH nanoplatelet array structure material of example 3;
FIG. 15 is a graph of current density versus time for Oxygen Evolution Reaction (OER) of Pd nanoparticle supported NiFe LDH nanoplatelet array structure material of example 3;
FIG. 16 is a capacitance current diagram of Oxygen Evolution Reaction (OER) of Pd nanoparticle supported NiFe LDH nanosheet array structure material at different sweep rates in example 3;
FIG. 17 is a graph showing the impedance of Oxygen Evolution Reaction (OER) for Pd nanoparticle supported NiFe LDH nanoplatelet array structure material of example 3;
FIG. 18 is a LSV polarization curve of Hydrogen Evolution Reactions (HERs) of Pd nanoparticle-supported NiFe LDH nanoplatelet array structures of different Pd contents (0.69%, 0.92% and 1.14%) prepared in example 1 and example 2;
FIG. 19 is a LSV graph (inset shows polarization curve at high current density) of Hydrogen Evolution Reaction (HER) of Pd nanoparticle supported NiFe LDH nanoplatelet array structure material of example 4;
FIG. 20 is a graph of current density versus time for a Hydrogen Evolution Reaction (HER) of the Pd nanoparticle supported NiFe LDH nanoplatelet array structure of example 4;
FIG. 21 is a capacitance current plot of Hydrogen Evolution Reactions (HERs) at different sweep rates for Pd nanoparticle supported NiFe LDH nanoplatelet array structure materials of example 4;
FIG. 22 is a graph of the resistance of Hydrogen Evolution Reaction (HER) of Pd nanoparticle supported NiFe LDH nanoplatelet array structure material of example 4;
FIG. 23 is a graph showing the polarization curve of Pd nanoparticle-supported NiFe LDH nanoplatelet array structure material in example 5 for total water decomposition in a two-electrode system (the inset shows the polarization curve at high current density);
FIG. 24 is a graph of current density versus time for full water decomposition of Pd nanoparticle supported NiFe LDH nanoplatelet array structure material in a two electrode system in example 5.
Detailed Description
The invention will now be described in detail with reference to the examples and the accompanying drawings.
Example 1
The preparation method of the Pd nanoparticle-loaded NiFe LDH nanosheet array structure material comprises the following steps of:
a piece of Nickel Foam (NF) having an area of 2X 3cm was immersed in 6M hydrochloric acid for 15 minutes, and then washed 3 times with deionized water and absolute ethanol, respectively. Accurately weighing 30mL of anhydrous methanol, adding into a clean small beaker, accurately weighing 1mmol of Ni (NO 3 ) 3 ·6H 2 O，0.25mmol Fe(NO 3 ) 3 ·9H 2 O,1mmol urea, 60mg tetra-n-butyl ammonium bromide are added into the small beaker to form a mixed solution, and the mixed solution is stirred for 30min by ultrasonic444. Mu.L of 2.256X 10 concentration was added -2 H of M 2 PdCl 4 The solution is continuously stirred to obtain a uniform tan solution, the tan solution is transferred into a stainless steel reaction kettle with 50mL polytetrafluoroethylene as a lining, the pretreated foam nickel is obliquely put into the stainless steel reaction kettle, and the reaction is carried out for 6 hours in a baking oven at 120 ℃. And naturally cooling to room temperature after the reaction is finished, cleaning foam nickel covered by a tan sample with deionized water and absolute ethyl alcohol for 3 times, and drying the obtained sample in a vacuum drying oven at 60 ℃ for 12 hours to obtain the Pd nanoparticle-loaded NiFe double hydroxide nano sheet array structure material.
Characterization of structure and morphology of the product:
the final product obtained in example 1 was phase identified by X-ray powder diffractometer (XRD). As shown in FIG. 1, all diffraction peaks are associated with alpha-Ni (OH) 2 (JCPDS No. 38-0715) are identical.
The product obtained in example 1 was subjected to morphological analysis by means of a Scanning Electron Microscope (SEM). As shown in fig. 2, the sample has a uniformly distributed nano-sheet array structure, and the transverse dimension of the nano-sheet is 75-150nm.
The final product composition of example 1 was analyzed using energy dispersive X-ray (EDX) spectroscopy. As shown in FIG. 3, the atomic percentages of Ni, fe and Pd elements are 1:0.24:0.0099. Thus, the mass percentage of Pd element was calculated to be 0.92%, and the product was defined as Pd 0.92％ /Ni x Fe 1-x (OH) 2 . Ni-Fe was calculated to be 0.8:0.2 based on the atomic percentages of Ni and Fe, whereby the product of example 1 was written as Pd 0.92％ /Ni 0.8 Fe 0.2 (OH) 2 。
The product of example 1 was subjected to morphological analysis using a Transmission Electron Microscope (TEM). As shown in fig. 4, the nanosheet array structure of the product consisted of Pd nanoparticle-loaded NiFe LDH nanosheets with an average size of 2nm of Pd nanoparticles on the nanosheets.
The product of example 1 was analyzed for surface element distribution using scanning transmission electron microscopy element profile. As shown in FIG. 5, ni, fe, O and Pd elements are in Pd 0.92％ /Ni 0.8 Fe 0.2 (OH) 2 The Pd element is uniformly distributed in the nano-sheet array, wherein the distribution density of the Pd element is obviously lower than that of Ni, fe and O elements.
The crystal planes of the product of example 1 were characterized using a High Resolution Transmission Electron Microscope (HRTEM) to confirm the presence of Pd nanoparticles and NiFe LDH. As shown in fig. 6, the lattice fringes with a interplanar spacing of 0.26nm correspond to the (012) planes of the NiFe LDH and the lattice fringes with a interplanar spacing of 0.22nm correspond to the (111) planes of the Pd nanoparticles.
Characterization of the lattice vibration mode of the product obtained in example 1 using raman spectroscopy further confirmed the presence of NiFe LDH, as shown in fig. 7. Raman spectra showed three bands, located at 455.0cm -1 Corresponds to M in LDH phase 2+ -O-M 3 + Or Ni in NiFe LDH 2+ O vibration of 537.3cm -1 And 704.7cm -1 The bands of (2) can be attributed to defective or disordered Ni (OH), respectively 2 And Fe-O vibration in disordered FeOOH.
Example 2
Accurately weighing 30mL of anhydrous methanol, adding into a clean small beaker, accurately weighing 1mmol of Ni (NO 3 ) 3 ·6H 2 O，0.25mmol Fe(NO 3 ) 3 ·9H 2 O,1mmol urea, 60mg tetra-n-butyl ammonium bromide are added into the small beaker to form a mixed solution, and after ultrasonic stirring is carried out for 30min, 333 mu L or 555 mu L of the mixed solution with the concentration of 2.256 multiplied by 10 is added -2 H of M 2 PdCl 4 The solution is continuously stirred to obtain a uniform tan solution, the tan solution is transferred into a 50mL stainless steel reaction kettle with polytetrafluoroethylene as a lining, the pretreated foam nickel is obliquely put into the solution, and the reaction is carried out for 6 hours in a baking oven at 120 ℃. And naturally cooling to room temperature after the reaction is finished, cleaning foam nickel covered by a tan sample with deionized water and absolute ethyl alcohol for 3 times, and drying the obtained sample in a vacuum drying oven at 60 ℃ for 12 hours.
H 2 PdCl 4 When the addition amount of the catalyst is 333 mu L, pd nano-particle loaded NiFe LDH nano-sheet array structural material with Pd loading amount of 0.69% is obtained; h 2 PdCl 4 When the addition amount of (2) is 555 mu L, pd nano-particle load with Pd load amount of 1.14% is obtainedNiFe LDH nanoplatelet array structure material.
The product composition of example 2 was analyzed using energy dispersive X-ray spectroscopy (EDX). As shown in fig. 8, wherein the atomic percentages of Ni, fe and Pd elements are respectively 1:0.25:0.0075 and 1:0.25:0.0124, and calculated Pd mass percent is 0.69% and 1.14% respectively. Ni to Fe was calculated to be 0.8:0.2 based on atomic percentages of Ni and Fe, from which the product was written as Pd 0.69％ /Ni 0.8 Fe 0.2 (OH) 2 And Pd (Pd) 1.14％ /Ni 0.8 Fe 0.2 (OH) 2 。
The morphology of the example 2 samples was analyzed using a Scanning Electron Microscope (SEM). FIGS. 9 and 10 are Pd, respectively 069％ /Ni 0.8 Fe 0.2 (OH) 2 Nanosheet array and Pd 1.14％ /Ni 0.8 Fe 0.2 (OH) 2 SEM images of the nanoplatelet arrays show that the samples are uniformly distributed nanoplatelet array structures.
The morphology of the example 2 samples was further analyzed using a Transmission Electron Microscope (TEM). FIGS. 11 and 12 are Pd, respectively 069％ /Ni 0.8 Fe 0.2 (OH) 2 Nanosheet array and Pd 1.14％ /Ni 0.8 Fe 0.2 (OH) 2 TEM images of the nanoplatelet arrays show that the samples are composed of nanoplatelets loaded with Pd nanoparticles. Wherein the average size of Pd nanoparticles on the nanoplatelets was 1.7nm at a Pd loading of 0.69% (fig. 11). At a Pd loading of 1.14%, the average size of Pd nanoparticles on the nanoplatelets was 3nm, and part of the nanoparticles were agglomerated (fig. 12).
Example 3
An application of Pd nanoparticle-loaded NiFe LDH nanosheet array structure material as an Oxygen Evolution Reaction (OER) catalyst.
The specific application method comprises the following steps: pd nano particles with the area of 0.5 multiplied by 0.5cm are used for loading NiFe LDH nano sheet array structural materials to be used as working electrodes, and a platinum wire and an Ag/AgCl electrode are used as a counter electrode and a reference electrode respectively. Electrochemical testing was performed in a 1.0M KOH electrolyte solution at room temperature (25 ℃) using a CHI 760E electrochemical workstation. In the form of commercial RuO 2 Load(s)The electrode is used as a benchmark to compare OER performance. The preparation of the NiFe LDH nano-sheet is based on the embodiment 1, the H in the raw material is omitted 2 PdCl 4 Prepared, which is defined as Ni 0.8 Fe 0.2 (OH) 2 . At 5.0 mV.s by Linear Sweep Voltammetry (LSV) -1 The polarization curve is obtained at a scan rate of 90% and with an ohmic compensation.
FIG. 13 is an Oxygen Evolution Reaction (OER) polarization curve for Pd nanoparticle supported NiFe double hydroxide nanoplatelet array structure materials with different Pd loadings of 0.69%,0.92% and 1.14%. The mass percent of Pd loading is shown to significantly affect Oxygen Evolution Reaction (OER) activity, with 0.92% of Pd loading being better than 0.69% and 1.14% of Pd loading.
FIG. 14 is Pd 0.92％ /Ni 0.8 Fe 0.2 (OH) 2 Nanosheet array structural material and Ni 0.8 Fe 0.2 (OH) 2 Nanosheets, ruO 2 And Oxygen Evolution Reaction (OER) polarization curve of nickel foam. From the figure, pd 0.92％ /Ni 0.8 Fe 0.2 (OH) 2 The nano-sheet array structural material can reach 100mA cm only by 243mV low overpotential -2 Current density of (C) is respectively higher than Ni 0.8 Fe 0.2 (OH) 2 Nanoplatelets and commercial RuO 2 Less than 25mV and 73mV; in addition, pd 0.92％ /Ni 0.8 Fe 0.2 (OH) 2 The nano-sheet array structure material can reach 200mA cm under the over-potential of 252mV and 266mV which are quite small -2 And 500mA cm -2 Is a high current density of (a).
FIG. 15 is Pd 0.92％ /Ni 0.8 Fe 0.2 (OH) 2 The nanoplatelet array structure material evaluates the current density time profile of Oxygen Evolution Reaction (OER) electrocatalytic stability at overpotential 243mV, 252mV, 266 mV. After 12h of testing, the current density was maintained above 95%, indicating Pd 0.92％ /Ni 0.8 Fe 0.2 (OH) 2 The nano-sheet array structure has good Oxygen Evolution Reaction (OER) electrocatalytic stability.
FIG. 16 is a capacitance current diagram of Oxygen Evolution Reaction (OER) at different sweep rates. Pd (Pd) 0.92％ /Ni 0.8 Fe 0.2 (OH) 2 The double-layer capacitance of the nano-sheet array structure material is 3.3 mF.cm -2 Greater than Ni 0.8 Fe 0.2 (OH) 2 2.0 mF.cm of (F) -2 Thus, the Pd nano-particles can be loaded to increase the electrochemical active area of Oxygen Evolution Reaction (OER) of the material.
FIG. 17 is an Electrochemical Impedance (EIS) diagram under Oxygen Evolution Reaction (OER) conditions. Pd (Pd) 0.92％ /Ni 0.8 Fe 0.2 (OH) 2 Nano-sheet array structural material ratio Ni 0.8 Fe 0.2 (OH) 2 The semicircle diameter of the catalyst is small, which shows that the catalyst can obviously reduce the resistance and accelerate the catalytic dynamics of oxygen evolution reaction after Pd nano particles are loaded.
Example 4
The application of Pd nanoparticle-loaded nickel-iron double hydroxide nanosheet array structure material as a Hydrogen Evolution Reaction (HER) catalyst.
The specific application method comprises the following steps: pd nano particles with the area of 0.5 multiplied by 0.5cm are used for loading NiFe LDH nano sheet array structural materials to be used as working electrodes, and a carbon rod and an Ag/AgCl electrode are respectively used as a counter electrode and a reference electrode. Electrochemical testing was performed in a 1.0M KOH electrolyte solution at room temperature (25 ℃) using a CHI 760E electrochemical workstation. HER performance was compared based on a commercial Pt/C loaded foam nickel electrode. Ni (Ni) 0.8 Fe 0.2 (OH) 2 Is prepared by omitting H in the raw materials based on example 1 2 PdCl 4 The preparation method is that the product is obtained. At 5.0 mV.s by Linear Sweep Voltammetry (LSV) -1 The polarization curve is obtained at a scan rate of 90% and with an ohmic compensation.
Fig. 18 is a Hydrogen Evolution Reaction (HER) LSV polarization curve for Pd nanoparticle-loaded NiFe LDH nanoplatelet array structure materials with different Pd loadings of 0.69%,0.92% and 1.14%. The mass percent of Pd loading was shown to significantly affect Hydrogen Evolution Reaction (HER) activity, with samples with mass percent of 0.92% Pd loading having better activity than the 0.69% and 1.14% samples.
FIG. 19 is Pd 0.92％ /Ni 0.8 Fe 0.2 (OH) 2 Nanosheet array structural material and Ni 0.8 Fe 0.2 (OH) 2 Hydrogen Evolution Reaction (HER) polarization curves for nanoplatelets, pt/C and nickel foam. Pd (Pd) 0.92％ /Ni 0.8 Fe 0.2 (OH) 2 The nano-sheet array structural material can reach 10mA cm only by 36mV overpotential -2 Current density of (C) over Ni 0.8 Fe 0.2 (OH) 2 The nano-sheet is 126mV smaller; although Pt/C electrodes show outstanding HER activity at low current densities, at high current densities the material is very prone to fall off affecting activity. In addition, pd 0.92％ /Ni 0.8 Fe 0.2 (OH) 2 The nano-sheet array structure material can respectively reach 200mA cm when the overpotential is 186mV and 224mV -2 And 500mA cm -2 Is provided.
FIG. 20 is Pd 0.92％ /Ni 0.8 Fe 0.2 (OH) 2 The nanoplatelet array structure materials evaluate the current density time profile of Hydrogen Evolution Reaction (HER) electrocatalytic stability at overpotential 60mV,186mV and 224 mV. After 12h of testing, the current density was maintained above 94.5%, indicating Pd 0.92％ /Ni 0.8 Fe 0.2 (OH) 2 The nano-sheet array structural material has excellent electrocatalytic stability of Hydrogen Evolution Reaction (HER).
Fig. 21 is a capacitance current plot of Hydrogen Evolution Reaction (HER) at different sweep rates. Pd (Pd) 0.92％ /Ni 0.8 Fe 0.2 (OH) 2 The double-layer capacitance of the nano-sheet array structure material is 14.95 mF.cm -2 Greater than Ni 0.8 Fe 0.2 (OH) 2 7.98 mF.cm -2 Thus, the Pd nano-particles can increase the electrochemical active area of the Hydrogen Evolution Reaction (HER) of the material after being loaded.
Fig. 22 is an Electrochemical Impedance (EIS) diagram under Hydrogen Evolution Reaction (HER) conditions. Pd (Pd) 0.92％ /Ni 0.8 Fe 0.2 (OH) 2 Nano-sheet array structural material ratio Ni 0.8 Fe 0.2 (OH) 2 The semi-circle diameter of the catalyst is small, which shows that the catalyst can obviously reduce resistance and accelerate the catalysis kinetics of Hydrogen Evolution Reaction (HER) after Pd nano particles are loaded.
Example 5
The application of Pd nanoparticle-loaded NiFe LDH nanosheet array structure material as a full-water decomposition reaction catalyst.
The specific application method comprises the following steps: 2 Pd nano-particles with the area of 0.5 multiplied by 0.5cm are loaded on an array structure material of NiFe LDH nano-sheets and are respectively used as a cathode and an anode to be assembled in a double-electrode electrolytic tank, and the full-water decomposition performance is tested in a KOH electrolyte solution with the concentration of 1.0M. At 5.0 mV.s by Linear Sweep Voltammetry (LSV) -1 Obtain polarization curve at 90% of the scanning rate and ohmic compensation, and use RuO 2 And Pt/C as anode and cathode composition pairs, respectively, for comparison.
FIG. 23 is Pd 0.92％ /Ni 0.8 Fe 0.2 (OH) 2 And (3) an LSV polarization curve of the full water splitting of the nano-sheet array structural material. Pd (Pd) 0.92％ /Ni 0.8 Fe 0.2 (OH) 2 The nano sheet array structure material can reach 10mA cm under the voltage of 1.485V -2 And only requires 1.758V to drive 500mA cm -2 Shows excellent all-water cracking catalytic activity. Commercial RuO 2 And Pt/C electrode can not reach 500mA cm because the material is easy to fall off -2 Is a high current density of (a).
FIG. 24 is Pd 0.92％ /Ni 0.8 Fe 0.2 (OH) 2 The nanoplatelet array structure material evaluates the current density time curve of the electrocatalytic stability of total water decomposition. After continuous electrolysis for 12h at constant voltages of 1.4815V, 1.694V and 1.758V, the current density was maintained above 93.4%, indicating Pd 0.92％ /Ni 0.8 Fe 0.2 (OH) 2 The nano-sheet array structural material has excellent durability in a double-electrode electrolytic cell.
The foregoing detailed description of a Pd nanoparticle supported nickel iron double hydroxide nanosheet array structure material, a preparation method and applications thereof with reference to the embodiments is illustrative and not restrictive, and several embodiments can be listed according to the defined scope, so that variations and modifications without departing from the general inventive concept shall fall within the scope of protection of the present invention.
Claims (9)
1. A preparation method of a Pd nanoparticle-supported nickel-iron double hydroxide (NiFe LDH) nanosheet array structure material, which is characterized by comprising the following steps of: adding nickel salt, ferric salt, urea and quaternary ammonium salt into absolute methanol, adding palladium source solution after ultrasonic dissolution, transferring the solution into a reaction kettle after uniform mixing, obliquely placing foam nickel into the solution for solvothermal reaction, cooling to room temperature after the reaction is finished, and washing and drying a product to obtain a Pd nanoparticle-supported nickel-iron double hydroxide (NiFe LDH) nanosheet array structure material;
the quaternary ammonium salt is tetra-n-butyl ammonium bromide;
the solvothermal reaction condition is that the reaction is carried out for 4-8 hours at 120 ℃;
in the Pd nanoparticle supported nickel-iron double hydroxide (NiFe LDH) nanosheet array structure material, ni, fe, O and Pd elements are uniformly distributed, wherein the Pd element distribution density is obviously lower than that of the Ni, fe and O elements.
2. The method of manufacturing according to claim 1, characterized in that: the mass ratio of the substances of the nickel salt, the ferric salt, the urea, the quaternary ammonium salt and the palladium source is as follows: 1.0:0.11-0.67:0.8-1.2:0.062-0.31:0.0075-0.0125.
3. The preparation method according to claim 1 or 2, characterized in that: the nickel salt is nickel nitrate hexahydrate; the ferric salt is ferric nitrate nonahydrate; the palladium source solution is an aqueous solution of chloropalladite.
4. The preparation method according to claim 1 or 2, characterized in that the concentration of the nickel salt in anhydrous methanol is 0.033M.
5. The method according to claim 1 or 2, wherein the palladium source solution has a concentration of 2.256 ×10 - 2 M。
6. A Pd nanoparticle-supported nickel-iron double hydroxide (NiFe LDH) nanosheet array structure material prepared by the preparation method of any one of claims 1-5.
7. The use of the Pd nanoparticle-supported nickel iron double hydroxide (NiFe LDH) nanoplatelet array structure material of claim 6 as an Oxygen Evolution Reaction (OER) electrocatalyst.
8. Use of the Pd nanoparticle-supported nickel iron double hydroxide (NiFe LDH) nanoplatelet array structure material of claim 6 as a Hydrogen Evolution Reaction (HER) electrocatalyst.
9. The use of the Pd nanoparticle-supported nickel iron double hydroxide (NiFe LDH) nanoplatelet array structure material of claim 6 as a full water splitting reaction electrocatalyst.
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| CN116027032B (en) * | 2022-10-27 | 2023-08-25 | 云南大学 | Novel coronavirus detection method, material and application based on photoelectric dual-signal mode |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2015167892A (en) * | 2014-03-05 | 2015-09-28 | 日本碍子株式会社 | Catalyst structure having laminar double hydroxide and manufacturing method therefor |
| CN108447703A (en) * | 2018-03-16 | 2018-08-24 | 安徽师范大学 | A kind of ferronickel double-metal hydroxide@ceria heterogeneous structural nanos sheet material, preparation method and applications |
| CN108777309A (en) * | 2018-05-15 | 2018-11-09 | 北京化工大学 | A kind of monatomic Pd catalyst of support type and preparation method thereof and catalytic applications |
| CN110227485A (en) * | 2019-05-20 | 2019-09-13 | 广东国能中林实业有限公司 | A kind of the water electrolysis hydrogen production energy ruthenium doping iron nickel alloy catalyst and preparation method |
| CN110270348A (en) * | 2019-07-15 | 2019-09-24 | 郑州轻工业学院 | A kind of monatomic catalyst of noble metal and its preparation and application |
| CN110575836A (en) * | 2019-09-05 | 2019-12-17 | 安徽师范大学 | Pt-loaded Fe-doped alpha-phase nickel hydroxide nanosheet array material, and preparation method and application thereof |
| WO2020034007A1 (en) * | 2018-08-16 | 2020-02-20 | Newsouth Innovations Pty Limited | Trimetallic layered double hydroxide composition |
-
2020
- 2020-06-11 CN CN202010531086.6A patent/CN111871426B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2015167892A (en) * | 2014-03-05 | 2015-09-28 | 日本碍子株式会社 | Catalyst structure having laminar double hydroxide and manufacturing method therefor |
| CN108447703A (en) * | 2018-03-16 | 2018-08-24 | 安徽师范大学 | A kind of ferronickel double-metal hydroxide@ceria heterogeneous structural nanos sheet material, preparation method and applications |
| CN108777309A (en) * | 2018-05-15 | 2018-11-09 | 北京化工大学 | A kind of monatomic Pd catalyst of support type and preparation method thereof and catalytic applications |
| WO2020034007A1 (en) * | 2018-08-16 | 2020-02-20 | Newsouth Innovations Pty Limited | Trimetallic layered double hydroxide composition |
| CN110227485A (en) * | 2019-05-20 | 2019-09-13 | 广东国能中林实业有限公司 | A kind of the water electrolysis hydrogen production energy ruthenium doping iron nickel alloy catalyst and preparation method |
| CN110270348A (en) * | 2019-07-15 | 2019-09-24 | 郑州轻工业学院 | A kind of monatomic catalyst of noble metal and its preparation and application |
| CN110575836A (en) * | 2019-09-05 | 2019-12-17 | 安徽师范大学 | Pt-loaded Fe-doped alpha-phase nickel hydroxide nanosheet array material, and preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| 以泡沫镍为基底的纳米片层状Ni~(2+)-Fe~(3+)-V~(3+)LDHs的制备及其电催化析氧性能研究;韩银凤等;《化学试剂》;20200131(第01期);第8-12页 * |
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