CN111889118A - Cu-loaded nickel hydroxy phosphite core-shell nanowire structural material and preparation method and application thereof - Google Patents
Cu-loaded nickel hydroxy phosphite core-shell nanowire structural material and preparation method and application thereof Download PDFInfo
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- 239000011258 core-shell material Substances 0.000 title claims abstract description 79
- 239000000463 material Substances 0.000 title claims abstract description 72
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- WINMCMQFDGNIPW-UHFFFAOYSA-N P(OO)([O-])[O-].[Ni+2] Chemical group P(OO)([O-])[O-].[Ni+2] WINMCMQFDGNIPW-UHFFFAOYSA-N 0.000 title abstract description 3
- 239000010949 copper Substances 0.000 claims abstract description 108
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 16
- 239000001257 hydrogen Substances 0.000 claims abstract description 16
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- 239000001301 oxygen Substances 0.000 claims abstract description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000010411 electrocatalyst Substances 0.000 claims abstract description 8
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- 238000006243 chemical reaction Methods 0.000 claims description 41
- 229910052759 nickel Inorganic materials 0.000 claims description 26
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 7
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 claims description 7
- 150000001879 copper Chemical class 0.000 claims description 6
- 150000002815 nickel Chemical class 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 4
- 238000006460 hydrolysis reaction Methods 0.000 claims description 4
- 239000012046 mixed solvent Substances 0.000 claims description 4
- FTFFLIUWGVSVCY-UHFFFAOYSA-N OP([O-])([O-])[O-].[Ni+3] Chemical group OP([O-])([O-])[O-].[Ni+3] FTFFLIUWGVSVCY-UHFFFAOYSA-N 0.000 claims description 3
- 238000004729 solvothermal method Methods 0.000 claims description 3
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical group FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims description 2
- SXTLQDJHRPXDSB-UHFFFAOYSA-N copper;dinitrate;trihydrate Chemical group O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SXTLQDJHRPXDSB-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 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
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 abstract description 15
- 238000000354 decomposition reaction Methods 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 7
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 229910052802 copper Inorganic materials 0.000 abstract description 6
- 230000005540 biological transmission Effects 0.000 abstract description 3
- 230000004888 barrier function Effects 0.000 abstract description 2
- 230000003993 interaction Effects 0.000 abstract description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract 1
- 238000010521 absorption reaction Methods 0.000 abstract 1
- 238000011068 loading method Methods 0.000 description 31
- 230000010287 polarization Effects 0.000 description 13
- 239000006260 foam Substances 0.000 description 12
- 238000004502 linear sweep voltammetry Methods 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 9
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 8
- 238000000157 electrochemical-induced impedance spectroscopy Methods 0.000 description 6
- 239000003792 electrolyte Substances 0.000 description 6
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(IV) oxide Inorganic materials O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 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
- 238000010586 diagram Methods 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- 238000000634 powder X-ray diffraction Methods 0.000 description 4
- 230000027756 respiratory electron transport chain Effects 0.000 description 4
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 4
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- 238000012546 transfer Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910021205 NaH2PO2 Inorganic materials 0.000 description 2
- 239000000370 acceptor Substances 0.000 description 2
- 239000003990 capacitor Substances 0.000 description 2
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
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- 238000001000 micrograph Methods 0.000 description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(II) nitrate Inorganic materials [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 2
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- DQSQLDJLCOSKBY-UHFFFAOYSA-N OP([O-])([O-])[O-].[Ni+2].[Ni+2] Chemical compound OP([O-])([O-])[O-].[Ni+2].[Ni+2] DQSQLDJLCOSKBY-UHFFFAOYSA-N 0.000 description 1
- IMILPNAEYBRQMF-UHFFFAOYSA-N P(OO)([O-])[O-].[Ni+2].[Ni+2].OOP([O-])[O-] Chemical compound P(OO)([O-])[O-].[Ni+2].[Ni+2].OOP([O-])[O-] IMILPNAEYBRQMF-UHFFFAOYSA-N 0.000 description 1
- OSOVKCSKTAIGGF-UHFFFAOYSA-N [Ni].OOO Chemical compound [Ni].OOO OSOVKCSKTAIGGF-UHFFFAOYSA-N 0.000 description 1
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- 229910000483 nickel oxide hydroxide Inorganic materials 0.000 description 1
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- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical class O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 1
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- 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
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- B01J35/33—
-
- B01J35/40—
-
- 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 Cu-loaded nickel hydroxy phosphite core-shell nanowire structural material and a preparation method and application thereof11(HPO3)8(OH)6Core-shell nanowire structural materials; in the structure, the copper shell layer wrapped outside the nanowire can enhance the conductivity, accelerate the electron transmission rate, expose more active sites, improve the hydrophilicity and facilitate the absorption of water moleculesAnd rapid release of gaseous products; strong electron interaction on an interface in the heterostructure can reduce energy barrier of H-OH bond splitting and improve electrocatalytic activity; the catalyst is used as an electrocatalyst for oxygen evolution, hydrogen evolution or total-water decomposition reaction, and has the advantages of high catalytic activity, good durability, simple preparation process and low cost.
Description
Technical Field
The invention belongs to the field of a preparation method of a nano material and electrocatalysis application, and particularly relates to a Cu-loaded nickel hydroxyphosphite core-shell nanowire structural material as well as a preparation method and application thereof.
Background
With the accelerated development of the industry, the rapid consumption of fossil fuels and the increasing environmental pollution become problems to be solved in the current society. Hydrogen has the advantages of cleanness, high efficiency, renewability and the like, and is one of the most potential energy sources for replacing fossil fuels. Electrochemical water splitting is an environmentally friendly method for producing hydrogen, but because the corresponding anodic Oxygen Evolution Reaction (OER) and cathodic Hydrogen Evolution Reaction (HER) have large overpotentials, it still needs to consume large energy to drive. Therefore, it is critical to develop highly active bifunctional catalysts to drive both HER and OER simultaneously.
Nickel nickel hydroxy phosphite Ni11(HPO3)8(OH)6The crystal structure of (A) is a three-dimensional octahedral array structure consisting of triangular and hexagonal holes, which is beneficial to effective electron transfer and exposure of active sites in electrolyte. Two proton acceptors, hydroxyl and phosphite, can accelerate the rapid transfer of protons and electrons. When the nickel-based phosphite material is used for carrying out OER catalytic reaction, a small amount of nickel oxyhydroxide species are easily generated on the surface, and the improvement of the OER catalytic activity is facilitated. In Ni2+Under the synergistic effect of the cations, phosphite anions can promote HER reaction, and the remarkable characteristics enable the nickel-based phosphite material to have good application prospect in electrocatalytic water decomposition.
Nickel nickel hydroxyphosphite Ni in the prior art11(HPO3)8(OH)6Catalyst preparation method is complex and single Ni11(HPO3)8(OH)6The conductivity of (2) is poor, the OER and HER catalytic activities are still low, and the industrial application of full water decomposition cannot be realized.
Disclosure of Invention
In order to solve the technical problem, the invention provides a Cu loaded Ni11(HPO3)8(OH)6A core-shell nanowire structural material, a preparation method and application thereof. With bubblesTaking nickel foam as a substrate, and designing and synthesizing Cu-loaded Ni in a mixed solvent of deionized water and isopropanol by a one-step liquid phase method11(HPO3)8(OH)6The core-shell nanowire structure has simple synthesis process and low cost, and can be applied to OER, HER and total hydrolysis. The Cu nano film wrapped by the shell layer enhances the conductivity of the catalyst, provides a channel for electron transportation, improves the hydrophilicity of the catalyst and accelerates the reaction kinetics.
The invention provides Cu loaded Ni11(HPO3)8(OH)6The preparation method of the core-shell nanowire structural material comprises the following steps:
dissolving copper salt, nickel salt and hypophosphite in a mixed solvent of water and isopropanol, transferring the solution to a reaction kettle, obliquely placing foamed nickel in the solution, carrying out solvothermal reaction, cooling to room temperature after the reaction is finished, washing and drying a product to obtain Cu-loaded Ni11(HPO3)8(OH)6Core-shell nanowire structural materials.
Further, the copper salt is copper nitrate trihydrate; the nickel salt is nickel nitrate hexahydrate; the hypophosphite is sodium hypophosphite.
The ratio of the copper salt, the nickel salt and the hypophosphite is 0.2-0.6: 1-2: 2, preferably 0.4:2: 2.
The concentration of the hypophosphite salt in water and isopropanol was 0.05M.
The volume ratio of the solvent water to the isopropanol is 1-3: 3-1, and preferably 2: 2.
The solvent thermal reaction condition is that the reaction is carried out for 4 to 8 hours at 160 ℃, and the reaction is preferably carried out for 6 hours at 160 ℃.
The foam Nickel (NF) needs to be cleaned before use, and the specific cleaning steps are as follows: soaking in 6M hydrochloric acid for 15min to remove the outer oxide film, and cleaning with deionized water and anhydrous ethanol for 3-5 times; when in use, the foam nickel is cut into the size of 2 multiplied by 3 cm.
The washing is 3-5 times by using deionized water and absolute ethyl alcohol respectively.
The drying is naturally drying in air atmosphere.
The invention also provides Cu-loaded Ni prepared by the preparation method11(HPO3)8(OH)6Core-shell nanowire structural material made of Ni11(HPO3)8(OH)6The nano wire is used as a core, and the Cu nano thin layer is wrapped in Ni11(HPO3)8(OH)6The nanowire forms a shell structure; when the Cu supporting amount is 9.2%, the Cu supports Ni11(HPO3)8(OH)6The shape of the core-shell nanowire structural material is formed by combining nanowires with the average size of 10 nm.
The invention also provides the Cu loaded Ni11(HPO3)8(OH)6The core-shell nanowire structural material is applied as an electrocatalyst for oxygen evolution reaction or hydrogen evolution reaction or total water decomposition reaction.
The Cu carries Ni11(HPO3)8(OH)6When the core-shell nanowire structural material is applied as an Oxygen Evolution Reaction (OER) electrocatalyst, the specific method comprises the following steps: ni-loaded Cu prepared on foamed nickel11(HPO3)8(OH)6The core-shell nanowire structural material was cut into a size of 0.5 × 0.5cm as a working electrode, and a 1M KOH solution was used as an electrolyte, and tested using a CHI 760E electrochemical workstation. Platinum wire and Ag/AgCl electrodes were used as counter and reference electrodes, respectively. Linear Sweep Voltammetry (LSV) at 5.0mV · s-1The polarization curve is obtained at a scanning rate of 90% with ohmic compensation; stability was obtained by measuring the current density time curve at constant voltage. Electrochemically active area (ECSA) was determined by scanning at different scan rates (20, 40, 60, 80, 100, 120 and 140mV · s) without significant faraday region-1) Measuring the electric double layer capacitance (C) of a capacitordl) Carrying out evaluation; at 105Electrochemical Impedance Spectroscopy (EIS) tests were performed between the frequency range of Hz to 0.01 Hz. Respectively with commercial RuO2Ni supported on foamed nickel and prepared on foamed nickel11(HPO3)8(OH)6The nanowires were used as working electrodes and the OER performance was measured for comparison.
The Cu negativeCarrying Ni11(HPO3)8(OH)6When the core-shell nanowire structural material is applied as a Hydrogen Evolution Reaction (HER) electrocatalyst, the specific method comprises the following steps: ni-loaded Cu prepared on foamed nickel11(HPO3)8(OH)6The core-shell nanowire structural material was cut into a size of 0.5 × 0.5cm as a working electrode, and a 1M KOH solution was used as an electrolyte, and tested using a CHI 760E electrochemical workstation. Carbon rods and Ag/AgCl electrodes were used as counter and reference electrodes, respectively. Linear Sweep Voltammetry (LSV) at 5.0mV · s-1The polarization curve is obtained at a scanning rate of 90% with ohmic compensation; stability was obtained by measuring the current density time curve at constant voltage. Electrochemically active area (ECSA) was determined by scanning at different scan rates (20, 40, 60, 80, 100, 120 and 140mV · s) without significant faraday region-1) Measuring the electric double layer capacitance (C) of a capacitordl) Carrying out evaluation; at 105Electrochemical Impedance Spectroscopy (EIS) tests were performed between the frequency range of Hz to 0.01 Hz. Ni prepared separately with commercial Pt/C loading on and on nickel foam11(HPO3)8(OH)6Nanowires were used as working electrodes and HER performance was measured separately for comparison.
The Cu carries Ni11(HPO3)8(OH)6When the core-shell nanowire structural material is applied as an all-water decomposition reaction electrocatalyst, the specific method comprises the following steps: ni-loaded Cu prepared on foamed nickel11(HPO3)8(OH)6The core-shell nanowire structural material is cut into 2 pieces with the size of 0.5 multiplied by 0.5cm and respectively used as a cathode and an anode to be assembled in a double-electrode electrolytic cell, and the full-water decomposition performance is tested through an LSV polarization curve compensated by 90% iR and a current density time curve under constant voltage. As a comparison, the noble metal RuO supported on nickel foam in a two-electrode electrolyzer was investigated2LSV polarization curves as anode and Pt/C as cathode.
In the invention, the supported Cu nanometer thin shell layer reduces the resistance of the catalyst and accelerates the effective electron transfer and the release of gas products. And Ni11(HPO3)8(OH)6Due to the unique threeThe angular and hexagonal micropore channels can expose more active sites to the electrolyte, and realize rapid interface charge transfer. Cu and Ni11(HPO3)8(OH)6The strong electron interaction on the formed phase interface can reduce the energy barrier of H-OH bond splitting and improve the electrocatalytic activity. The hydroxyl and phosphite proton acceptors can form hydrogen bonds with water molecules, so that the surface of the catalyst has higher wettability, the electrolyte penetration is facilitated, and the charge transfer between the electrolyte and the catalyst is further enhanced, thereby improving the catalytic activity.
Compared with the prior art, the invention adopts a simple chemical liquid phase method, H2PO2 -Partial hydrolysis of ions to produce OH-Ions, OH-Ions subsequently with unhydrolyzed H2PO2 -Ion generation of pH by disproportionation3Molecule and HPO3 2-Ions. HPO3 2-The ions further react with Ni2+Ions and OH-Ion reaction to produce Ni11(HPO3)8(OH)6. In addition H in solution2PO2 -Can mix Cu2+Reducing into simple substance Cu, wrapping in Ni11(HPO3)8(OH)6Outside the nanowire, clear and stable Cu-loaded Ni is formed11(HPO3)8(OH)6Core-shell nanowire structures. The Cu loaded Ni provided by the invention11(HPO3)8(OH)6The core-shell nanowire structural material has excellent catalytic activity and stability for oxygen evolution reaction, hydrogen evolution reaction and total hydrolysis reaction, is simple in preparation process, environment-friendly and low in cost, and has a great value for researching the practical application of a water decomposition electro-catalysis electrode material.
Drawings
FIG. 1 shows Ni loaded Cu prepared in example 111(HPO3)8(OH)6An X-ray powder diffraction (XRD) pattern of the core-shell nanowire structural material;
FIG. 2 shows Ni loaded Cu prepared in example 111(HPO3)8(OH)6An energy dispersive X-ray spectroscopy (EDX) plot of core-shell nanowire structural material;
FIG. 3 shows Ni loaded Cu prepared in example 111(HPO3)8(OH)6A Scanning Electron Microscope (SEM) image of the core-shell nanowire structural material;
FIG. 4 shows Ni loaded Cu prepared in example 111(HPO3)8(OH)6Transmission Electron Microscope (TEM) images of core shell nanowire structural materials;
FIG. 5 shows Ni loading Cu prepared in example 111(HPO3)8(OH)6High resolution lattice fringe (HRTEM) images of core-shell nanowire structured materials;
FIG. 6 shows Ni loading Cu prepared in example 111(HPO3)8(OH)6A scanning electron microscope image and a corresponding element distribution image of the core-shell nanowire structural material;
FIG. 7 shows Ni loading of Cu in example 111(HPO3)8(OH)6A contact angle measurement result graph of the core-shell nanowire structural material;
FIG. 8 shows Cu-loaded Ni with Cu loadings of 4.8% and 13.2% prepared in example 211(HPO3)8(OH)6An X-ray powder diffraction (XRD) pattern of the core-shell nanowire structural material;
FIG. 9 shows Cu-loaded Ni with Cu loadings of 4.8% and 13.2% prepared in example 211(HPO3)8(OH)6An energy dispersive X-ray spectroscopy (EDX) plot of core-shell nanowire structural material;
FIG. 10 shows Cu-supported Ni with Cu loading of 4.8% prepared in example 211(HPO3)8(OH)6A Scanning Electron Microscope (SEM) image of the core-shell nanowire structural material;
FIG. 11 shows Cu-supported Ni with Cu loading of 13.2% prepared in example 211(HPO3)8(OH)6A Scanning Electron Microscope (SEM) image of the core-shell nanowire structural material;
fig. 12 shows the different Cu contents (4.8%, 9.2% and 13) prepared in example 1 and example 2.2%) Cu supported Ni11(HPO3)8(OH)6LSV plot of Oxygen Evolution Reaction (OER) of core-shell nanowire structural material;
FIG. 13 shows Ni loading of Cu in example 311(HPO3)8(OH)6LSV plot of core-shell nanowire structural material Oxygen Evolution Reaction (OER) (inset is polarization curve at high current density);
FIG. 14 shows Ni loading of Cu in example 311(HPO3)8(OH)6A current density time curve of core-shell nanowire structural material Oxygen Evolution Reaction (OER);
FIG. 15 shows Ni loading of Cu in example 311(HPO3)8(OH)6A capacitance-current diagram of core-shell nanowire structural material Oxygen Evolution Reaction (OER) under different sweep rates;
FIG. 16 shows Ni loading of Cu in example 311(HPO3)8(OH)6Impedance plot of core-shell nanowire structural material Oxygen Evolution Reaction (OER);
FIG. 17 shows Ni loadings in Cu of different Cu contents (4.8%, 9.2% and 13.2%) prepared in examples 1 and 211(HPO3)8(OH)6LSV plot of Hydrogen Evolution Reaction (HER) of core-shell nanowire structural material;
FIG. 18 shows Ni loading of Cu in example 411(HPO3)8(OH)6LSV plot of core-shell nanowire structural material Hydrogen Evolution Reaction (HER) (inset is polarization curve at high current density);
FIG. 19 shows Ni loading of Cu in example 411(HPO3)8(OH)6A current density time curve diagram of a core-shell nanowire structural material Hydrogen Evolution Reaction (HER);
FIG. 20 shows Ni loading of Cu in example 411(HPO3)8(OH)6An impedance plot of a core-shell nanowire structural material Hydrogen Evolution Reaction (HER);
FIG. 21 shows Ni loading of Cu in example 511(HPO3)8(OH)6Polarization curve diagram of core-shell nanowire structural material for total water decomposition in two-electrode system (the inset isPolarization curves at high current densities);
FIG. 22 shows Ni loading of Cu in example 511(HPO3)8(OH)6The current density time curve of the core-shell nanowire structural material in the two-electrode system is completely decomposed.
Detailed Description
The invention is described in detail below with reference to the following examples and the accompanying drawings.
Example 1
Cu loaded Ni11(HPO3)8(OH)6The preparation method of the core-shell nanowire structural material comprises the following steps:
soaking foamed nickel with the size of 2 x 3cm in 6M hydrochloric acid solution for 15min, washing with deionized water and absolute ethyl alcohol for 3 times respectively, and drying at room temperature for later use. Accurately measure 20mL of deionized water and 20mL of isopropanol, add to a small clean beaker, and then respectively weigh 0.4mmol of Cu (NO)3)2·3H2O，2mmol Ni(NO3)2·6H2O and 2mmol NaH2PO2·6H2Adding O into a small beaker, and continuously stirring for 20min to obtain a uniform solution. Transferring the solution to a 50mL stainless steel reaction kettle with polytetrafluoroethylene as a lining, obliquely inserting the pretreated foamed nickel into the solution, sealing and reacting in a 160 ℃ oven for 6 hours, naturally cooling to room temperature after the reaction is finished, respectively cleaning the foamed nickel covering the sample with deionized water and absolute ethyl alcohol for 3 times, then drying the foamed nickel in a vacuum drying oven at 60 ℃ for 8 hours to obtain the Cu-loaded Ni11(HPO3)8(OH)6Core-shell nanowire structural materials.
The product obtained in example 1 was subjected to phase characterization by X-ray powder diffractometer, and the results are shown in FIG. 1, in which all diffraction peaks are similar to hexagonal phase Ni in JCPDS No.44-1327 card11(HPO3)8(OH)6Coincidentally, two new peaks corresponding to elemental Cu appeared after Cu loading (JCPDS No. 65-9023).
The product obtained in example 1 was analyzed by energy dispersive X-ray spectroscopy (EDX), as shown in FIG. 2, Cu, Ni and P elementsThe atomic percent of the element is 0.2:1.0:0.62, which shows that Cu is loaded on Ni11(HPO3)8(OH)6On the core-shell nanowires, the Cu loading was calculated to be 9.2% accordingly.
The sample prepared in example 1 was subjected to morphological analysis using a Scanning Electron Microscope (SEM), as shown in fig. 3, indicating that the sample consisted of nanowires with an average size of 10 nm.
The morphology of the sample was further observed using a Transmission Electron Microscope (TEM) and the results are shown in fig. 4, further indicating that the sample consists of nanowires with a mean size of 10 nm.
High Resolution Transmission Electron Microscope (HRTEM) images of core-shell nanowires are shown in fig. 5, showing two sets of adjacent lattice fringes, wherein the lattice planes with interplanar spacing d of 0.209nm correspond to the (111) plane of Cu; the facets with an interplanar spacing d of 0.414nm correspond to Ni11(HPO3)8(OH)6The (210) face of (A) is made of Ni11(HPO3)8(OH)6The nano wire is used as a core, and the Cu nano thin layer is wrapped in Ni11(HPO3)8(OH)6The nanowire forms a shell structure.
FIG. 6 shows Cu supporting Ni11(HPO3)8(OH)6Scanning electron microscope images of the core-shell nanowires and corresponding element distribution images. The uniform distribution of Ni, P, O and Cu elements in the material is shown, wherein the distribution density of the Cu element is obviously lower than that of the Ni, P and O elements.
Cu-loaded Ni was measured by the contact angle method11(HPO3)8(OH)6Surface wettability of core-shell nanowire structures. FIG. 7 shows the Ni loading by dropping water droplets onto Cu11(HPO3)8(OH)6Profile of water drop at the rear instant of film surface, showing Ni loading of Cu11(HPO3)8(OH)6The contact angle of the membrane was 25 ° indicating the hydrophilicity of the product.
Example 2
Cu-loaded Ni11(HPO3)8(OH)6The preparation method of the core-shell nanowire structural material comprises the following steps:
accurate and accurate20mL of deionized water and 20mL of isopropyl alcohol were measured and added to a small clean beaker, and 0.2mmol or 0.6mmol of Cu (NO) was then weighed out, respectively3)2·3H2O，2mmol Ni(NO3)2·6H2O and 2mmol NaH2PO2·6H2Adding O into a small beaker, and stirring uniformly. Obliquely inserting the dried foamed nickel into a stainless steel reaction kettle with a lining of 50mL polytetrafluoroethylene, transferring the solution into the reaction kettle after the solution is fully dissolved, and reacting for 6 hours in an oven at 160 ℃ after sealing. After the reaction is completed, naturally cooling to room temperature, washing the foam nickel covering the sample with deionized water and absolute ethyl alcohol for several times, and then drying the foam nickel in a vacuum drying oven at 60 ℃ for 8h, wherein Cu (NO) is added3)2·3H2When the amount of O added was 0.2mmol, Cu-supported Ni having a Cu supporting amount of 4.8% was obtained11(HPO3)8(OH)6Core-shell nanowire structural materials; cu (NO)3)2·3H2When the amount of O added was 0.6mmol, Cu-supported Ni having a Cu supporting amount of 13.2% was obtained11(HPO3)8(OH)6Core-shell nanowire structural materials.
The phase of the product obtained in example 2 was characterized by X-ray powder diffractometer, and the results are shown in FIG. 8, in which all diffraction peaks are associated with hexagonal phase Ni11(HPO3)8(OH)6(JCPDS No.44-1327) and elemental Cu (JCPDS No. 65-9023).
The synthesized core-shell nanowires were analyzed using energy dispersive X-ray spectroscopy (EDX), and as shown in fig. 9, the atomic percentages of Cu, Ni, and P elements were 0.1:1.0:0.83 and 0.3:1.0:0.61, respectively, from which Cu loading amounts were calculated to be 4.8% and 13.2%.
The morphology of the sample prepared in example 2 was analyzed using a Scanning Electron Microscope (SEM), and FIGS. 10 and 11 are Cu-loaded Ni with Cu loadings of 4.8% and 13.2%, respectively11(HPO3)8(OH)6SEM images of (a) show that the samples are all composed of core-shell nanowires.
Example 3
Cu loaded Ni11(HPO3)8(OH)6Core-shell nanowire junctionUse of a structural material as an Oxygen Evolution Reaction (OER) catalyst.
The specific application method comprises the following steps: cu of 0.5X 0.5cm in area was loaded with Ni11(HPO3)8(OH)6The core-shell nanowire structural material was used as a working electrode, and a platinum wire and an Ag/AgCl electrode were used as a counter electrode and a reference electrode, respectively, for testing in a 1.0M KOH electrolyte solution using a CHI 760E electrochemical workstation. Respectively with commercial RuO2Ni supported on foamed nickel and prepared on foamed nickel11(HPO3)8(OH)6Nanowires as working electrodes, OER Performance was measured separately as a comparison, Ni on foam Nickel11(HPO3)8(OH)6The preparation of the nanowires is based on example 1, and Cu (NO) in the raw material is omitted3)2·3H2O is prepared. Linear Sweep Voltammetry (LSV) at 5.0mV · s-1And the polarization curve was obtained at 90% ohmic compensation.
FIG. 12 is Cu-supported Ni with different Cu contents of 4.8%, 9.2% and 13.2%11(HPO3)8(OH)6Oxygen Evolution Reaction (OER) polarization curves of core-shell nanowires. It is shown that Cu loading significantly affects OER activity, with samples with 9.2% Cu loading being better than samples with 4.8% and 13.2%.
FIG. 13 shows Cu supporting Ni11(HPO3)8(OH)6Core-shell nanowire structural material and Ni11(HPO3)8(OH)6Nanowire, RuO2Oxygen Evolution Reaction (OER) polarization curve with nickel foam, it can be seen that Cu supports Ni11(HPO3)8(OH)6The core-shell nanowire structural material can realize 50mA cm only by using an overpotential with a low voltage of 251mV-2Current density of (2) to Ni11(HPO3)8(OH)6And commercial RuO2122mV and 77mV less.
Further, Cu carries Ni11(HPO3)8(OH)6The core-shell nanowire structural material can reach 800mA cm under the overpotential of 292mV-2FIG. 14 isThe OER electrocatalytic stability is evaluated by adopting current density time curves under overpotentials of 220, 270 and 283mV, and as can be seen from the figure, the current density is maintained to be more than 97 percent of the initial current density after 13 hours of continuous electrolytic reaction, and the OER electrocatalytic stability is excellent.
FIG. 15 is a graph of capacitance current at different sweep rates, evaluating the electrochemically active area of a material with double layer capacitance, Cu loaded with Ni11(HPO3)8(OH)6The electric double layer capacitance was 3.70 mF. cm-2Is greater than Ni11(HPO3)8(OH)61.45 mF. cm-2Indicating that Cu loading increases the electrochemically active surface area of the sample.
The Electrochemical Impedance (EIS) plot of FIG. 16 shows Cu loaded with Ni11(HPO3)8(OH)6The semi-circle diameter of the core-shell nanowire structural material is small, which shows that the Cu load improves the conductivity of the catalyst and is beneficial to promoting electron transfer.
Example 4
Cu loaded Ni11(HPO3)8(OH)6The application of the core-shell nanowire structural material as a Hydrogen Evolution Reaction (HER) catalyst.
The specific application method comprises the following steps: cu of 0.5X 0.5cm in area was loaded with Ni11(HPO3)8(OH)6The core-shell nanowire structural material was used as a working electrode, a carbon rod and an Ag/AgCl electrode were used as a counter electrode and a reference electrode, respectively, and the test was performed in a 1.0M KOH electrolyte solution using a CHI 760E electrochemical workstation. Ni prepared separately with commercial Pt/C loading on and on nickel foam11(HPO3)8(OH)6Nanowires as working electrodes, whose HER catalytic properties were measured separately as a comparison, Ni on nickel foam11(HPO3)8(OH)6The preparation of the nanowires is based on example 1, and Cu (NO) in the raw material is omitted3)2·3H2O is prepared. Linear Sweep Voltammetry (LSV) at 5.0mV · s-1And the polarization curve was obtained at 90% ohmic compensation.
FIG. 17 is a drawing showingCu-supported Ni with different Cu contents of 4.8%, 9.2% and 13.2%11(HPO3)8(OH)6Hydrogen Evolution Reaction (HER) polarization curve of core-shell nanowires. It is shown that the Cu loading significantly affected the HER activity of the catalyst, with the 9.2% Cu loading sample being optimal.
FIG. 18 shows Cu supporting Ni11(HPO3)8(OH)6Core-shell nanowire structural material and Ni11(HPO3)8(OH)6Hydrogen Evolution Reaction (HER) polarization curves for nanowires, Pt/C and nickel foam, as can be seen from the figure, Cu loaded with Ni11(HPO3)8(OH)6The core-shell nanowire structure can reach 10mA cm under the overpotential of 68mV-2Current density much less than Ni11(HPO3)8(OH)6130mV of catalyst. Although Pt/C electrodes show outstanding HER activity at low current densities, at high current densities the material is very prone to flaking off and activity is affected. Further, Cu carries Ni11(HPO3)8(OH)6The core-shell nanowire structure can reach 800 mA-cm under a small overpotential of 274mV-2High current density.
HER electrocatalytic stability was evaluated using current density time curves at constant overpotentials 118, 223 and 251mV, as shown in fig. 19, with current densities maintained above the initial 98.2% over 13 hours of continuous electrolysis, and excellent HER stability was exhibited at both low and high current densities.
FIG. 20 is an Electrochemical Impedance (EIS) diagram showing Ni loading of Cu11(HPO3)8(OH)6The semi-circle diameter of the core-shell nanowire structural material is small, which shows that the Cu load improves the conductivity of the catalyst and is beneficial to promoting electron transfer.
Example 5
Cu loaded Ni11(HPO3)8(OH)6The application of the core-shell nanowire structural material as a catalyst for full-water decomposition reaction.
The specific application method comprises the following steps: 2 pieces of Cu with an area of 0.5X 0.5cm were loaded with Ni11(HPO3)8(OH)6The core-shell nanowire structure is respectively used as an anode and a cathode to be assembled in a double-electrode electrolytic cell, and the full-water decomposition performance is tested in a 1.0M KOH electrolyte solution. And with RuO2And Pt/C as the anode and cathode respectively to form an electrical pair for comparison.
Fig. 21 is a 90% iR compensated LSV polarization curve. As can be seen from the figure, Cu carries Ni11(HPO3)8(OH)6The core-shell nanowire structural material can reach 10mA cm under the voltage of 1.491V-2The current density of (1) is required to drive the motor at 200mA · cm with a voltage of only 1.69V-2High current density. Despite the commercial RuO2The electric couple composed of Pt and C has slightly high activity under low current density, but can not reach 500mA cm because the material is easy to fall off-2High current density.
FIG. 22 is a current density time curve at a constant voltage, from which it can be seen that Cu carries Ni11(HPO3)8(OH)6The core-shell nanowire structural material is continuously electrolyzed at constant voltage of 1.518, 1.69 and 1.771V for 13 hours without obvious attenuation, and the current density is kept above the initial 96.5 percent, which shows that the core-shell nanowire structural material has excellent durability in a double-electrode electrolytic cell.
The above detailed description of a Cu supported nickel hydroxyphosphite core-shell nanowire structural material and its preparation method and application with reference to the examples is illustrative and not restrictive, and several examples can be cited within the scope of the invention, so that variations and modifications thereof can be made without departing from the general concept of the invention and are intended to be within the scope of the invention.
Claims (10)
1. A preparation method of a Cu-loaded nickel hydroxyphosphite core-shell nanowire structural material is characterized by comprising the following steps:
dissolving copper salt, nickel salt and hypophosphite in a mixed solvent of water and isopropanol, transferring the solution to a reaction kettle, obliquely placing foamed nickel in the solution, carrying out solvothermal reaction, cooling to room temperature after the reaction is finished, washing and drying a product to obtain Cu-loaded Ni11(HPO3)8(OH)6Core-shell nanowire structural materials.
2. The method according to claim 1, wherein the copper salt is copper nitrate trihydrate; the nickel salt is nickel nitrate hexahydrate; the hypophosphite is sodium hypophosphite.
3. The method according to claim 1 or 2, wherein the ratio of the amounts of the copper salt, the nickel salt and the hypophosphite is 0.2-0.6: 1-2: 2.
4. The production method according to claim 1 or 2, wherein the concentration of the hypophosphite is 0.05M in a mixed solvent of water and isopropanol.
5. The method according to claim 1 or 2, wherein the volume ratio of the water to the isopropyl alcohol is 1 to 3:3 to 1.
6. The method according to claim 1 or 2, wherein the solvothermal reaction is carried out at 160 ℃ for 4 to 8 hours.
7. The Cu-supported Ni prepared by the preparation method according to any one of claims 1 to 611(HPO3)8(OH)6Core-shell nanowire structural materials.
8. The Cu loaded Ni of claim 711(HPO3)8(OH)6The core-shell nanowire structural material is applied as an Oxygen Evolution Reaction (OER) electrocatalyst.
9. The Cu loaded Ni of claim 711(HPO3)8(OH)6The application of the core-shell nanowire structural material as a Hydrogen Evolution Reaction (HER) electrocatalyst.
10The Cu-supported Ni of claim 711(HPO3)8(OH)6The application of the core-shell nanowire structural material as an electrocatalyst for total hydrolysis reaction.
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