CN110562942A - Porous nanometer flower-shaped Ni2preparation method of P material and Ni2P material - Google Patents
Porous nanometer flower-shaped Ni2preparation method of P material and Ni2P material Download PDFInfo
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- CN110562942A CN110562942A CN201910826262.6A CN201910826262A CN110562942A CN 110562942 A CN110562942 A CN 110562942A CN 201910826262 A CN201910826262 A CN 201910826262A CN 110562942 A CN110562942 A CN 110562942A
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- 239000000463 material Substances 0.000 title claims abstract description 83
- 238000000034 method Methods 0.000 title claims abstract description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 107
- 238000002360 preparation method Methods 0.000 claims abstract description 49
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 22
- 239000002904 solvent Substances 0.000 claims abstract description 7
- 238000001338 self-assembly Methods 0.000 claims abstract description 6
- 239000002243 precursor Substances 0.000 claims abstract description 3
- 239000002057 nanoflower Substances 0.000 claims description 57
- 150000001875 compounds Chemical class 0.000 claims description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- 239000011259 mixed solution Substances 0.000 claims description 15
- 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 13
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 239000011261 inert gas Substances 0.000 claims description 6
- 150000002815 nickel Chemical class 0.000 claims description 6
- 229920000428 triblock copolymer Polymers 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 238000003786 synthesis reaction Methods 0.000 claims description 3
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 238000004140 cleaning Methods 0.000 claims description 2
- 238000007710 freezing Methods 0.000 claims description 2
- 230000008014 freezing Effects 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
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical group 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
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 claims description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 2
- 238000011144 upstream manufacturing Methods 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 10
- 230000003197 catalytic effect Effects 0.000 abstract description 10
- 239000001301 oxygen Substances 0.000 abstract description 10
- 229910052760 oxygen Inorganic materials 0.000 abstract description 10
- 229910001868 water Inorganic materials 0.000 abstract description 10
- 238000006243 chemical reaction Methods 0.000 abstract description 6
- 239000000376 reactant Substances 0.000 abstract description 4
- 230000005540 biological transmission Effects 0.000 abstract description 3
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- 150000002816 nickel compounds Chemical class 0.000 abstract description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract 1
- 230000009286 beneficial effect Effects 0.000 abstract 1
- 229910052698 phosphorus Inorganic materials 0.000 abstract 1
- 239000011574 phosphorus Substances 0.000 abstract 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 8
- 239000001257 hydrogen Substances 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- 239000000243 solution Substances 0.000 description 6
- 238000005868 electrolysis reaction Methods 0.000 description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 239000010411 electrocatalyst Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 229910052573 porcelain Inorganic materials 0.000 description 2
- 238000001075 voltammogram Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229910021397 glassy carbon Inorganic materials 0.000 description 1
- HTXDPTMKBJXEOW-UHFFFAOYSA-N iridium(IV) oxide Inorganic materials O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- FBMUYWXYWIZLNE-UHFFFAOYSA-N nickel phosphide Chemical compound [Ni]=P#[Ni] FBMUYWXYWIZLNE-UHFFFAOYSA-N 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(IV) oxide Inorganic materials O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
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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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
-
- 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
- B01J37/28—Phosphorising
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/08—Other phosphides
-
- 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
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
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- 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
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Abstract
The invention provides porous nano flower-shaped Ni2The preparation method of the P material comprises the steps of preparing a nickel precursor by a solvent volatilization induced self-assembly method, then roasting to obtain a nickel compound, and further carrying out phosphating treatment by using a phosphorus source to obtain Ni2And P material. Another aspect of the present invention provides a Ni2And P material. Ni prepared by the invention2the P material is applied to the electrolytic water oxygen evolution reaction and has quicker performanceCatalytic dynamic performance and good catalytic stability. The preparation method has the advantages of simple operation, stable material shape and structure, and porous structure, and is beneficial to contact of reactants and a catalyst in the catalytic reaction process and material transmission of the reactants and products.
Description
Technical Field
The invention belongs to the technical field of porous materials and catalysis, and particularly relates to porous nanoflower-shaped Ni2Preparation method of P material and Ni prepared by using same2And P material.
Technical Field
Hydrogen is a clean energy, and with the serious environmental pollution and the consumption of fossil energy, hydrogen is considered as an ideal new energy source which can replace fossil energy. The hydrogen production by water electrolysis is the simplest and feasible hydrogen production method in the hydrogen production methods. In order to save cost and accelerate reaction, the water electrolysis efficiency is often improved by designing a high-efficiency catalyst. The electrolysis of water includes hydrogen evolution reaction at the cathode and oxygen evolution reaction at the anode, the best hydrogen evolution catalyst is still platinum and platinum-based catalyst at present, and the best oxygen evolution catalyst is RuO2And IrO2a catalyst. However, the catalyst is expensive, which increases the cost of the catalyst and limits the wide application of the catalyst in industry.
Disclosure of Invention
The invention aims to provide porous nanoflower Ni aiming at the technical analysis2the preparation method of the P material provides an effective catalyst for oxygen evolution reaction, and has the advantages of high product purity, good crystallinity, high activity and simple preparation method.
In one aspect of the invention, porous nanoflower Ni is provided2The preparation method of the P material comprises the following steps:
(1) The porous nanoflower Ni2of P materialThe preparation method comprises the following steps:
1) Synthesis of nickel-containing compounds: adding a triblock copolymer P123 (with the molecular weight of 5800) into a mixed solution containing acid and alcohol, completely dissolving at a certain temperature, adding nickel salt, completely dissolving, volatilizing the solvent at a certain temperature to induce self-assembly for 2-6 h, cooling to room temperature, cleaning, drying at a certain temperature, and roasting the obtained product to obtain a nickel-containing compound;
2) And (3) phosphating treatment: taking the nickel-containing compound in the step 1) and sodium hypophosphite (NaH)2PO2·H2O) roasting at a certain temperature, cooling to room temperature to obtain Ni2And P material.
(2) The porous nanoflower Ni as in (1)2The preparation method of the P material comprises the following steps of: 1000-3000 mg.
(3) A porous nanoflower Ni as described in (1) to (2)2The preparation method of the P material comprises the step of preparing the P material, wherein the nickel salt is nickel chloride, nickel sulfate or nickel nitrate hexahydrate.
(4) A porous nanoflower Ni as described in (1) to (3)2The preparation method of the P material comprises the step 1), wherein the acid used in the step 1) is one or more of nitric acid, concentrated nitric acid, sulfuric acid or hydrochloric acid, and the preferable dosage is 1-5 mL.
(5) A porous nanoflower Ni as described in (1) to (4)2The preparation method of the P material comprises the following steps of 1): one or more of ethanol, propanol, isopropanol or butanol, preferably 10-20 mL.
(5) A porous nanoflower Ni as described in (1) to (4)2The preparation method of the P material comprises the step of adding the nickel salt in an amount of more than 0.01 mol.
(7) A porous nanoflower Ni as described in (1) to (6)2The preparation method of the P material, wherein, in the step 1), the triblock copolymer P123 (molecular weight: 5800) is added into a mixed solution containing acid and alcohol, and completely dissolved at a certain temperature, wherein the temperature is as follows: room temperature or other temperatures, preferred temperatures are: 30-60 ℃.
(8) A porous nanoflower Ni as described in (1) to (7)2the preparation method of the P material comprises the following steps of 1), wherein the temperature of the volatile solvent is 30-200 ℃, and the preferable temperature is as follows: the roasting time is preferably 10-13h at 100-160 ℃.
(9) A porous nanoflower Ni as described in (1) to (8)2The preparation method of the P material is characterized in that in the step 1), the mixed solution is heated to volatilize the solvent to induce self-assembly for 2-6 hours, after the mixed solution is cooled to room temperature, the mixed solution is washed by ethanol and centrifugally separated, the drying environment is air, and the drying environment is preferably a vacuum environment in a vacuum or freezing state, and the drying temperature is preferably 30-60 ℃.
(10) The preparation method of the porous nanoflower-shaped Ni2P material according to the steps (1) to (9), characterized in that in the step 1), the temperature of the dried product is gradually increased at a certain rate during roasting, preferably, the temperature increase rate is 2-10 ℃/min, and the roasting temperature is 100-300 ℃.
(11) a porous nanoflower Ni as described in (1) to (10)2The preparation method of the P material comprises the following steps of (1: 60) - (3: 20) using amount ratio of nickel-containing compounds to sodium hypophosphite, preferably: 10-30 mg, the dosage of sodium hypophosphite is: 200-600 mg.
(12) A porous nanoflower Ni as described in (1) to (11)2The preparation method of the P material comprises the following steps of 2), putting a nickel-containing compound and sodium hypophosphite into an environment isolated from the outside,
(13) A porous nanoflower Ni as described in (1) to (12)2The preparation method of the P material is characterized in that the nickel-containing compound and the sodium hypophosphite are surrounded by inert gas or vacuum.
(14) A porous nanoflower Ni as described in (1) to (13)2The preparation method of the P material comprises the following step of preparing the P material, wherein the inert gas is one or more of nitrogen, helium and argon.
(15) A porous nanoflower Ni as described in (1) to (14)2The preparation method of the P material is characterized in that the inert gas is a continuously flowing gas, and the sodium hypophosphite is placed in the nickel-containing compoundUpstream of the gas flow direction.
(16) A porous nanoflower Ni as described in (1) to (15)2the preparation method of the P material is characterized in that in the step 2), the roasting temperature is 200-400 ℃.
(17) A porous nanoflower Ni as described in (1) to (16)2The preparation method of the P material comprises the step of gradually heating to 200-400 ℃ at a heating rate of 1-5 ℃/min.
(18) A porous nanoflower Ni as described in (1) to (17)2The preparation method of the P material comprises the step of roasting for 1-4 hours.
Another aspect of the present invention provides a Ni2P material, wherein the Ni2P is a porous nanoflower-like structure.
The invention has the advantages that: ni2the P material is a porous nanoflower-shaped structure, so that contact between reactants and a catalyst is facilitated, substance transmission of the reactants and products is facilitated, and meanwhile, more catalytic active sites are provided by the loose and porous nanoflower structure, so that catalytic activity is effectively improved. The product has high purity, activity and crystallinity, and simple preparation method, has better catalytic activity and catalytic stability in oxygen evolution reaction, and has practical significance and important value in the fields of developing novel oxygen evolution catalysts and the like. In addition, the nickel phosphide has good hydrogen evolution or oxygen evolution catalytic performance in the water electrolysis process, has good conductivity, catalytic performance and stability, is low in cost, and has higher cost performance when used as a water electrolysis reaction catalyst.
Drawings
FIG. 1 shows porous nanoflower Ni prepared by the method for preparing the porous nanoflower Ni2P material in example 1 of the invention2X-ray diffraction pattern (XRD pattern) of P material;
FIG. 2 is a Scanning Electron Microscope (SEM) picture of a porous nanoflower Ni2P material prepared by the preparation method of the porous nanoflower Ni2P material in example 1 of the invention;
FIG. 3 is a Scanning Electron Microscope (SEM) picture of a nickel-containing compound before phosphating by the preparation method of the porous nanoflower Ni2P material;
FIG. 4 is a Transmission Electron Microscope (TEM) picture of a porous nanoflower Ni2P material prepared by the preparation method of the porous nanoflower Ni2P material of example 1 of the present invention;
FIG. 5 is a linear sweep voltammogram (LSV graph) of oxygen evolution performance when the porous nanoflower Ni2P material prepared by the preparation method of the porous nanoflower Ni2P material of example 1 of the present invention is used as a catalyst;
FIG. 6 is Tafel plot of oxygen evolution performance of porous nanoflower Ni2P material prepared by the preparation method of porous nanoflower Ni2P material of example 1 of the present invention as catalyst;
Fig. 7 is an LSV diagram before and after 1000 cyclic voltammetric scanning (CV) cycles of the porous nanoflower Ni2P material prepared by the method for preparing the porous nanoflower Ni2P material of example 1 of the present invention as a catalyst.
Detailed Description
Example 1:
Materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
Porous nanoflower Ni of the example2The preparation method of the P material adopts a method of a nickel-containing compound precursor, and comprises the following steps:
(1) synthesis of nickel-containing compounds: 1.45g of triblock copolymer P123 (molecular weight: 5800) was added to a mixed solution containing 1.53mL of concentrated nitric acid and 13mL of n-butanol, and after complete dissolution in a constant temperature water bath at 40 ℃, 0.01mol of nickel nitrate (Ni (NO) was added3)2·6H2O), magnetically stirring for 10-30min to completely dissolve the nickel-containing compound, transferring the mixed solution into a 120 ℃ oven, heating for 3.5h, cooling to room temperature, washing with ethanol for 3-4 times, centrifugally separating to obtain a product, putting the product into a 40 ℃ vacuum oven for overnight drying, and putting the obtained material into a muffle furnace to bake for 12h at 150 ℃ (the heating rate is 5 ℃/min) to obtain the nickel-containing compound.
(2) And (3) phosphating treatment: placing 20mg of the above nickel oxide in a porcelain ark, placing in a ceramic ark, and continuously introducing N2Then at the air inlet end in the tube furnaceThe solution is placed in a reactor containing 400mg of sodium hypophosphite (NaH)2PO2·H2O) porcelain ark, sodium hypophosphite (NaH)2PO2·H2O) is placed in N in comparison with the nickel-containing compound2Upstream in the direction of flow. Setting a tubular furnace program, heating to 300 ℃ at a constant heating rate (2 ℃/min), roasting at the temperature for 2h, and cooling to room temperature to obtain Ni2A P catalyst material.
in the examples, FIG. 1 is porous nanoflower Ni2The XRD pattern of the P material has four strong diffraction peaks at 40.8, 44.6, 47.3 and 54.2 degrees, which are respectively assigned to Ni2The (111), (201), (210) and (300) crystal planes of P (JCPDS No.03-0953) confirm that Ni is obtained after the phosphating treatment2And P material. As shown in FIG. 2, after the phosphating treatment, the structure of the material containing the nickel compound is changed from a relatively flat nano flower (FIG. 3) to a porous and loose nano flower-like structure (FIG. 2). As shown in FIG. 4, it can be further observed that Ni was treated by phosphating2The P material has a porous structure that increases the active sites of the catalyst, thereby enabling improved catalytic activity.
Porous nanoflower Ni to be produced using the method2The preparation method of the electrocatalyst working electrode by using the P material comprises the following steps: taking 4mgNi2Adding the P catalyst into a mixed solution containing 16 mu L of Nafion solution (5 wt.%), 264 mu L of isopropanol and 520 mu L of deionized water, and carrying out ultrasonic treatment for 10-20 min to obtain a working electrode solution. Then, the working electrode solution (12 μ L) was dropped onto a freshly ground and clean rotating disk glassy carbon electrode and dried. The prepared electrode is used as a working electrode, a 1mol/L KOH solution is used as an electrolyte, a counter electrode is a carbon rod, and a reference electrode is an Hg/HgO electrode respectively, so that a three-electrode system is constructed.
For using porous nanoflower Ni2And (3) carrying out an electrocatalyst performance test on the three-electrode system of the P material, wherein the adopted electrocatalyst performance test adopts a three-electrode system CHI760E electrochemical workstation, and the electrolyte is KOH solution (1 mol/L).
FIGS. 5 and 6 show the porous nanoflower Ni2P material as catalystAnd the agent is tested in oxygen evolution performance in 1 mol/LKOH. As can be seen from the linear sweep voltammogram 5, when the current reached 10mA/cm2The required potential is about 1.62V. As can be seen from FIG. 6 Tafel, the Tafel slope is 84mV/dec, indicating that the nanoflower Ni is present2The P material has faster catalytic kinetics when used as a catalyst. From FIG. 7, nano flower-like Ni2When the P material is used as a catalyst, the LSV graph before and after 1000 cycles of cyclic voltammetry scanning (CV) shows that the two lines have small change, which indicates the nano flower-shaped Ni2The P material has good catalytic stability.
Claims (19)
1. Porous nanometer flower-shaped Ni2The preparation method of the P material is characterized by adopting a method of preparing a nickel-containing compound precursor, and comprises the following steps:
1) Synthesis of nickel-containing compounds: adding a triblock copolymer P123 (molecular weight: 5800) into a mixed solution containing an acid and an alcohol, completely dissolving at a stable temperature, and adding a nickel salt to completely dissolve; heating the mixed solution, volatilizing the solvent to induce self-assembly for 2-6 h, cooling, cleaning, drying, and roasting the obtained product to obtain a nickel-containing compound;
2) And (3) phosphating treatment: taking the nickel-containing compound in the step 1) and sodium hypophosphite (NaH)2PO2·H2O) roasting, cooling to obtain Ni2And P material.
2. Porous nanoflower Ni according to claim 12The preparation method of the P material is characterized in that in the step 1), the dosage of the triblock copolymer P123 is 1-3 g.
3. Porous nanoflower Ni according to claim 12The preparation method of the P material is characterized in that the nickel salt is nickel chloride, nickel sulfate or nickel nitrate hexahydrate.
4. Porous nanoflower Ni according to claim 12The preparation method of the P material is characterized by comprising the following stepsIn the step 1), the acid is one or more of nitric acid, concentrated nitric acid, sulfuric acid or hydrochloric acid, and the dosage is 1-5 mL.
5. Porous nanoflower Ni according to claim 12The preparation method of the P material is characterized in that in the step 1), the used alcohol is as follows: one or more of ethanol, propanol, isopropanol or butanol, with the dosage of 10-20 mL.
6. Porous nanoflower Ni according to claim 12The preparation method of the P material is characterized in that in the step 1), the amount of the added nickel salt is more than 0.01 mol.
7. Porous nanoflower Ni according to claim 12The method for producing the P material is characterized in that, in the step 1), the temperature at which the triblock copolymer P123 (molecular weight: 5800) is dissolved after being added to a mixed solution containing an acid and an alcohol is: the temperature is room temperature or stable at 30-60 ℃.
8. Porous nanoflower Ni according to claim 12The preparation method of the P material is characterized in that in the step 1), the heating is carried out at the temperature of 100-160 ℃, and the solvent is volatilized to induce self-assembly.
9. Porous nanoflower Ni according to claim 12The preparation method of the P material is characterized in that in the step 1), the mixed solution is heated, the solvent is volatilized, the self-assembly is induced for 2-6 hours, the mixed solution is cooled to the room temperature, then the mixed solution is washed by ethanol and centrifugally separated, and then the mixed solution is dried in an air environment, a vacuum environment or a freezing state.
10. Porous nanoflower Ni according to claim 12The preparation method of the P material is characterized in that in the step 1), the temperature of the dried product is gradually increased at the speed of 2-10 ℃/min during roasting, and the roasting temperature is 100-300 ℃.
11. Porous nanoflower Ni according to claim 12The preparation method of the P material is characterized in that in the step 2), the usage ratio of the nickel-containing compound to the sodium hypophosphite is 1: 60-3: 20.
12. Porous nanoflower Ni according to claim 12The preparation method of the P material is characterized in that in the step 2), the nickel-containing compound and the sodium hypophosphite are placed in an environment isolated from the outside.
13. Porous nanoflower Ni according to claim 122The preparation method of the P material is characterized in that the nickel-containing compound and the sodium hypophosphite in the step 2) are surrounded by inert gas or are in vacuum.
14. porous nanoflower Ni according to claim 132The preparation method of the P material is characterized in that the inert gas in the step 2) is one or more of nitrogen, helium and argon.
15. Porous nanoflower Ni according to claim 142The preparation method of the P material is characterized in that the inert gas in the step 2) is a gas flowing continuously, and the sodium hypophosphite is arranged at the upstream of the gas flowing direction compared with the nickel-containing compound.
16. Porous nanoflower Ni according to claim 12The preparation method of the P material is characterized in that the roasting temperature in the step 2) is 200-400 ℃.
17. A porous nanoflower Ni according to claim 1 or any one of claim 11 to claim 162The preparation method of the P material is characterized in that in the step 2), the temperature is gradually increased to 200-400 ℃ at the temperature increase rate of 1-5 ℃/min.
18. the method of claim 16porous nanoflower Ni2The preparation method of the P material is characterized in that the roasting time is 1-4 h.
19. Ni2P material, characterized in that said Ni2P is a porous nanoflower-like structure.
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