CN110745800B - Nitrogen-doped nickel phosphide nanoflower and preparation method and application thereof - Google Patents
Nitrogen-doped nickel phosphide nanoflower and preparation method and application thereof Download PDFInfo
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- CN110745800B CN110745800B CN201911080290.4A CN201911080290A CN110745800B CN 110745800 B CN110745800 B CN 110745800B CN 201911080290 A CN201911080290 A CN 201911080290A CN 110745800 B CN110745800 B CN 110745800B
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- 239000002057 nanoflower Substances 0.000 title claims abstract description 141
- FBMUYWXYWIZLNE-UHFFFAOYSA-N nickel phosphide Chemical compound [Ni]=P#[Ni] FBMUYWXYWIZLNE-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 38
- 239000003054 catalyst Substances 0.000 claims abstract description 24
- 239000001257 hydrogen Substances 0.000 claims abstract description 18
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 18
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000010438 heat treatment Methods 0.000 claims description 54
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical group [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 28
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 28
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 28
- 239000001099 ammonium carbonate Substances 0.000 claims description 28
- 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 26
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 26
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 24
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 21
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 claims description 16
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 8
- 239000004202 carbamide Substances 0.000 claims description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 7
- 229910052698 phosphorus Inorganic materials 0.000 claims description 7
- 239000011574 phosphorus Substances 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 3
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 3
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 3
- 150000002815 nickel Chemical class 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 52
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 34
- 238000003756 stirring Methods 0.000 description 25
- 238000001816 cooling Methods 0.000 description 24
- 229910052573 porcelain Inorganic materials 0.000 description 24
- 238000006243 chemical reaction Methods 0.000 description 17
- 238000001035 drying Methods 0.000 description 13
- 235000019441 ethanol Nutrition 0.000 description 13
- 239000011259 mixed solution Substances 0.000 description 13
- 239000012467 final product Substances 0.000 description 12
- 239000000843 powder Substances 0.000 description 12
- 229910021508 nickel(II) hydroxide Inorganic materials 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- 238000005868 electrolysis reaction Methods 0.000 description 3
- 239000002803 fossil fuel Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000002086 nanomaterial Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 150000003624 transition metals Chemical class 0.000 description 3
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 238000000970 chrono-amperometry Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- 108010020056 Hydrogenase Proteins 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000009189 diving Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
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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
-
- 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
- B01J27/24—Nitrogen compounds
-
- 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—
-
- B01J35/33—
-
- B01J35/60—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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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
- 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
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
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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
Abstract
The invention discloses a nitrogen-doped nickel phosphide nanoflower, a preparation method thereof and application thereof as an electro-catalytic hydrogen evolution catalyst. Compared with the prior art, the method disclosed by the invention is simple to operate and easy for large-scale production, and the prepared nanoflower has the advantages of optimized surface electronic structure, more active sites, good conductivity, high catalytic activity and the like.
Description
Technical Field
The invention relates to a nitrogen-doped nickel phosphide nanoflower and a preparation method and application thereof, belonging to the technical field of electrocatalytic hydrogen evolution catalysts.
Background
At present, the energy source is mainly traditional fossil fuel, but due to the excessive consumption of fossil fuel, serious environmental pollution and increasing demand for energy, people are forced to explore new energy sources to replace traditional fossil fuel. Hydrogen energy has received much attention because of its advantages such as high energy density, abundant reserves, renewability and no environmental pollution. Among various hydrogen production methods (a high-temperature cracking natural gas method, a water gas method and the like), the hydrogen production method by the water electrolysis method has the advantages of simple operation, wide source of reactants, pure product and the like, and meanwhile, the oxygen generated by the anode can be applied to the aspects of spaceflight, medicine, diving and the like. The selection of the catalyst can effectively reduce the overpotential of the reaction, thereby improving the efficiency of the electrocatalytic hydrogen evolution. At present, the Pt group noble metal catalyst is the best catalyst for hydrogen production by water electrolysis, but the defects of high price and limited reserves seriously restrict the large-scale commercial use of the Pt group noble metal catalyst, and the development of other cheaper and efficient transition metal catalysts is very critical in the long run.
In the face of such problems, transition metal alloys, carbides, sulfides, nitrides, phosphides, etc. are widely studied and applied to electrolytic water evolution hydrogen reaction. Among them, the transition metal phosphide has a property similar to that of hydrogenase catalysis, and shows excellent catalytic performance in the electrolytic water hydrogen evolution reaction. In addition, the electronic structure of phosphide can be changed by doping the anions and the cations, so that the adsorption energy of active species is adjusted, and the catalytic activity is improved. At present, metal cation-regulated phosphide nano-materials have been widely researched, but anion (N, O, S) and the like have great challenges in regulating phosphide nano-materials and applying the phosphide nano-materials in electrocatalytic hydrogen evolution reaction.
Disclosure of Invention
The purpose of the invention is as follows: in order to solve the technical problems, the invention aims to provide a nitrogen-doped nickel phosphide nanoflower and a preparation method and application thereof. The preparation method is simple to operate and easy for large-scale production, and the prepared nanoflowers have the advantages of optimized surface electronic structure, multiple active sites, good conductivity, high catalytic activity and the like.
The technical scheme is as follows: in order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of nitrogen-doped nickel phosphide nanoflowers comprises the steps of mixing nickel salt serving as a metal source and oleylamine serving as a morphology directing agent for hydrothermal reaction, then carrying out heat treatment on a hydrothermal reaction product in an air atmosphere, and carrying out heat treatment on the hydrothermal reaction product together with a phosphorus source and a nitrogen source in an inert atmosphere to obtain the nitrogen-doped nickel phosphide nanoflowers.
Preferably, the method comprises the following steps:
the metal source is selected from one of nickel nitrate, nickel chloride or nickel sulfate.
The phosphorus source is sodium hypophosphite, and the nitrogen source is ammonium bicarbonate or urea.
The mass ratio of the hydrothermal reaction product to the phosphorus source is 1 (25-35).
The mass ratio of the hydrothermal reaction product to the nitrogen source is 1 (1-10).
The temperature of the hydrothermal reaction is 160-200 ℃, and the time is 12-18 h.
The temperature of the heat treatment in the air atmosphere is 300-400 ℃, the temperature is raised by adopting a program, the temperature raising rate is 2-10 ℃/min, and the holding time after temperature raising is 40-80 min.
The temperature for heat treatment together with the phosphorus source and the nitrogen source in the inert atmosphere is 300-450 ℃, the temperature is raised by adopting a program, the temperature raising rate is 2-10 ℃/min, and the holding time after temperature raising is 40-80 min.
The invention also provides the nitrogen-doped nickel phosphide nanoflower prepared by the preparation method.
The invention finally provides the application of the nitrogen-doped nickel phosphide nanoflower as an electrocatalytic hydrogen evolution catalyst.
The principle of the invention is as follows: nickel nitrate is used as a metal source, oleylamine is used as a morphology directing agent to generate Ni (OH)2The nanometer flower is oxidized, and then nitrogen and phosphorized at low temperature to prepare the nitrogen-doped nickel phosphide nanometer flower. The catalyst is a nanoflower, has regular shape and is phosphide. In addition, the doping of nitrogen can regulate and control the electronic structure of the catalyst, regulate the adsorption capacity to active species, and the obtained catalyst has higher electrocatalytic activity and stability.
The nitrogen-doped nickel phosphide nanoflower prepared by the method has the following advantages:
1) the nanoflower structure can provide more active sites, and is beneficial to the transmission and diffusion of electrolyte;
2) the nitrogen doping can change the electronic structure of the nickel phosphide and adjust the adsorption capacity of active species, thereby improving the catalytic performance of the catalyst;
3) the catalyst is phosphide and has stable composition; the structure is stable, and the coating has durability, thereby having better electrochemical stability.
Has the advantages that: compared with the prior art, the invention has the following advantages:
1) the invention is simple and convenient and can realize scaleProduced first oxidized and then low temperature nitrogen, phosphorus Ni (OH)2Preparing nitrogen-doped nickel phosphide nanoflower by a precursor method;
2) the reactants selected in the method are cheap and easy to obtain, the method has simple and feasible process, low cost and simple equipment, and can realize large-scale production;
3) the product obtained by the method has a nanoflower structure, is regular in shape, is phosphide, has the characteristics of more active sites, high electrocatalytic activity, high stability and the like, is a very potential catalyst for hydrogen evolution by electrolysis, and has wide application prospect in the future energy industry.
Drawings
FIG. 1 is an SEM image of nitrogen-doped nickel phosphide nanoflowers prepared by the method of example 1;
FIG. 2 is a low power TEM spectrum of nitrogen-doped nickel phosphide nanoflowers prepared by the method of example 1;
FIG. 3 is a high power TEM spectrum of nitrogen-doped nickel phosphide nanoflowers prepared by the method of example 1;
FIG. 4 is an XRD pattern of nitrogen-doped nickel phosphide nanoflowers prepared by the method of example 1;
FIG. 5 is an XPS spectrum of N for nitrogen-doped nickel phosphide nanoflowers prepared by the method of example 1;
FIG. 6 is an XRD pattern of the nickel phosphide nanoflower prepared by the method of comparative example 2, 3, 4 and 5;
FIG. 7 shows nitrogen-doped nickel phosphide prepared by the method of example 1 and Ni (OH) prepared by the methods of comparative examples 1 and 22An alkaline hydrogen evolution performance test map of the nickel phosphide nanoflower;
FIG. 8 is an alkaline hydrogen evolution cycle stability test pattern of nitrogen-doped nickel phosphide nanoflower prepared by the method of example 1;
FIG. 9 is an alkaline hydrogen evolution chronoamperometric test pattern of nitrogen-doped nickel phosphide nanoflowers prepared by the method of example 1;
Detailed Description
The technical solution of the present invention is further described in detail by the following specific examples.
Example 1
A preparation method of nitrogen-doped nickel phosphide nanoflower comprises the following steps:
1)Ni(OH)2preparing the nanoflower: dissolving nickel nitrate in absolute ethyl alcohol, fully dissolving, adding oleylamine and ethanol mixed solution in the stirring process, stirring for 30min, transferring to a 50mL reaction kettle, carrying out hydrothermal reaction at 180 ℃ in an oven for 15h, and carrying out centrifugal drying to obtain Ni (OH)2A nanoflower;
2) preparing NiO nanoflower: ni (OH)2And (3) placing the nanoflower in a porcelain boat, heating to 300 ℃ at the speed of 2 ℃/min in the air atmosphere for heat treatment, keeping the temperature for 60min, and cooling to obtain the NiO nanoflower.
3) Preparing nitrogen-doped nickel phosphide nanoflower: respectively placing sodium hypophosphite, ammonium bicarbonate and the powder prepared in the step 1) at the front end, the middle part and the tail end of the porcelain boat according to the mass ratio of 1:30 of the NiO nanoflower to the sodium hypophosphite and 1:2 of the ammonium bicarbonate, heating to 400 ℃ by a program of 2 ℃/min in an inert atmosphere for heat treatment, keeping the temperature for 60min, and then cooling to obtain a final product.
Example 2
A preparation method of nitrogen-doped nickel phosphide nanoflower comprises the following steps:
1)Ni(OH)2preparing the nanoflower: dissolving nickel nitrate in absolute ethyl alcohol, fully dissolving, adding oleylamine and ethanol mixed solution in the stirring process, stirring for 30min, transferring to a 50mL reaction kettle, carrying out hydrothermal reaction at 180 ℃ in an oven for 15h, and carrying out centrifugal drying to obtain Ni (OH)2A nanoflower;
2) preparing NiO nanoflower: ni (OH)2And (3) placing the nanoflower in a porcelain boat, heating to 300 ℃ at the speed of 2 ℃/min in the air atmosphere for heat treatment, keeping the temperature for 60min, and cooling to obtain the NiO nanoflower.
3) Preparing nitrogen-doped nickel phosphide nanoflower: respectively placing sodium hypophosphite, ammonium bicarbonate and the powder prepared in the step 1) at the front end, the middle part and the tail end of the porcelain boat according to the mass ratio of 1:30 of the NiO nanoflower to the sodium hypophosphite and 1:1 of the ammonium bicarbonate, heating to 400 ℃ by a program of 2 ℃/min in an inert atmosphere for heat treatment, keeping the temperature for 60min, and then cooling to obtain a final product.
Example 3
A preparation method of nitrogen-doped nickel phosphide nanoflower comprises the following steps:
1)Ni(OH)2preparing the nanoflower: dissolving nickel nitrate in absolute ethyl alcohol, fully dissolving, adding oleylamine and ethanol mixed solution in the stirring process, stirring for 30min, transferring to a 50mL reaction kettle, carrying out hydrothermal reaction at 180 ℃ in an oven for 15h, and carrying out centrifugal drying to obtain Ni (OH)2A nanoflower;
2) preparing NiO nanoflower: ni (OH)2And (3) placing the nanoflower in a porcelain boat, heating to 300 ℃ at the speed of 2 ℃/min in the air atmosphere for heat treatment, keeping the temperature for 60min, and cooling to obtain the NiO nanoflower.
3) Preparing nitrogen-doped nickel phosphide nanoflower: respectively placing sodium hypophosphite, ammonium bicarbonate and the powder prepared in the step 1) at the front end, the middle part and the tail end of the porcelain boat according to the mass ratio of 1:30 of the NiO nanoflower to the sodium hypophosphite and 1:5 of the ammonium bicarbonate, heating to 400 ℃ by a program of 2 ℃/min in an inert atmosphere for heat treatment, keeping the temperature for 60min, and then cooling to obtain a final product.
Example 4
A preparation method of nitrogen-doped nickel phosphide nanoflower comprises the following steps:
1)Ni(OH)2preparing the nanoflower: dissolving nickel nitrate in absolute ethyl alcohol, fully dissolving, adding oleylamine and ethanol mixed solution in the stirring process, stirring for 30min, transferring to a 50mL reaction kettle, carrying out hydrothermal reaction at 180 ℃ in an oven for 15h, and carrying out centrifugal drying to obtain Ni (OH)2A nanoflower;
2) preparing NiO nanoflower: ni (OH)2And (3) placing the nanoflower in a porcelain boat, heating to 300 ℃ at the speed of 2 ℃/min in the air atmosphere for heat treatment, keeping the temperature for 60min, and cooling to obtain the NiO nanoflower.
3) Preparing nitrogen-doped nickel phosphide nanoflower: respectively placing sodium hypophosphite, ammonium bicarbonate and the powder prepared in the step 1) at the front end, the middle part and the tail end of the porcelain boat according to the mass ratio of 1:30 of the NiO nanoflower to the sodium hypophosphite and 1:10 of the ammonium bicarbonate, heating to 400 ℃ by a program of 2 ℃/min in an inert atmosphere for heat treatment, keeping the temperature for 60min, and then cooling to obtain a final product.
Example 5
A preparation method of nitrogen-doped nickel phosphide nanoflower comprises the following steps:
1)Ni(OH)2preparing the nanoflower: dissolving nickel nitrate in absolute ethyl alcohol, fully dissolving, adding oleylamine and ethanol mixed solution in the stirring process, stirring for 30min, transferring to a 50mL reaction kettle, carrying out hydrothermal reaction at 180 ℃ in an oven for 15h, and carrying out centrifugal drying to obtain Ni (OH)2A nanoflower;
2) preparing NiO nanoflower: ni (OH)2And (3) placing the nanoflower in a porcelain boat, heating to 300 ℃ at the speed of 2 ℃/min in the air atmosphere for heat treatment, keeping the temperature for 60min, and cooling to obtain the NiO nanoflower.
3) Preparing nitrogen-doped nickel phosphide nanoflower: respectively placing sodium hypophosphite, ammonium bicarbonate and the powder prepared in the step 1) at the front end, the middle part and the tail end of the porcelain boat according to the mass ratio of 1:30 of the NiO nanoflower to the sodium hypophosphite and 1:2 of the ammonium bicarbonate, heating to 400 ℃ by a program of 5 ℃/min in an inert atmosphere for heat treatment, keeping the temperature for 60min, and then cooling to obtain a final product.
Example 6
A preparation method of nitrogen-doped nickel phosphide nanoflower comprises the following steps:
1)Ni(OH)2preparing the nanoflower: dissolving nickel nitrate in absolute ethyl alcohol, fully dissolving, adding oleylamine and ethanol mixed solution in the stirring process, stirring for 30min, transferring to a 50mL reaction kettle, carrying out hydrothermal reaction at 180 ℃ in an oven for 15h, and carrying out centrifugal drying to obtain Ni (OH)2A nanoflower;
2) preparing NiO nanoflower: ni (OH)2And (3) placing the nanoflower in a porcelain boat, heating to 300 ℃ at the speed of 2 ℃/min in the air atmosphere for heat treatment, keeping the temperature for 60min, and cooling to obtain the NiO nanoflower.
3) Preparing nitrogen-doped nickel phosphide nanoflower: respectively placing sodium hypophosphite, ammonium bicarbonate and the powder prepared in the step 1) at the front end, the middle part and the tail end of the porcelain boat according to the mass ratio of 1:30 of the NiO nanoflower to the sodium hypophosphite and 1:2 of the ammonium bicarbonate, heating to 400 ℃ by a program of 10 ℃/min in an inert atmosphere for heat treatment, keeping the temperature for 60min, and then cooling to obtain a final product.
Example 7
A preparation method of nitrogen-doped nickel phosphide nanoflower comprises the following steps:
1)Ni(OH)2preparing the nanoflower: dissolving nickel nitrate in absolute ethyl alcohol, fully dissolving, adding oleylamine and ethanol mixed solution in the stirring process, stirring for 30min, transferring to a 50mL reaction kettle, carrying out hydrothermal reaction at 180 ℃ in an oven for 15h, and carrying out centrifugal drying to obtain Ni (OH)2A nanoflower;
2) preparing NiO nanoflower: ni (OH)2And (3) placing the nanoflower in a porcelain boat, heating to 300 ℃ at the speed of 2 ℃/min in the air atmosphere for heat treatment, keeping the temperature for 60min, and cooling to obtain the NiO nanoflower.
3) Preparing nitrogen-doped nickel phosphide nanoflower: respectively placing sodium hypophosphite, ammonium bicarbonate and the powder prepared in the step 1) at the front end, the middle part and the tail end of the porcelain boat according to the mass ratio of 1:30 of the NiO nanoflower to the sodium hypophosphite and 1:2 of the ammonium bicarbonate, heating to 300 ℃ by a program of 2 ℃/min in an inert atmosphere for heat treatment, keeping the temperature for 60min, and then cooling to obtain a final product.
Example 8
A preparation method of nitrogen-doped nickel phosphide nanoflower comprises the following steps:
1)Ni(OH)2preparing the nanoflower: dissolving nickel nitrate in anhydrous alcohol, fully dissolving, and stirringAdding mixed solution of oleylamine and ethanol, stirring for 30min, transferring to a 50mL reaction kettle, performing hydrothermal reaction in an oven at 180 ℃ for 15h, and centrifugally drying to obtain Ni (OH)2A nanoflower;
2) preparing NiO nanoflower: ni (OH)2And (3) placing the nanoflower in a porcelain boat, heating to 300 ℃ at the speed of 2 ℃/min in the air atmosphere for heat treatment, keeping the temperature for 60min, and cooling to obtain the NiO nanoflower.
3) Preparing nitrogen-doped nickel phosphide nanoflower: respectively placing sodium hypophosphite, ammonium bicarbonate and the powder prepared in the step 1) at the front end, the middle part and the tail end of the porcelain boat according to the mass ratio of 1:30 of the NiO nanoflower to the sodium hypophosphite and 1:2 of the ammonium bicarbonate, heating to 350 ℃ by a program of 2 ℃/min in an inert atmosphere for heat treatment, keeping the temperature for 60min, and then cooling to obtain a final product.
Example 9
A preparation method of nitrogen-doped nickel phosphide nanoflower comprises the following steps:
1)Ni(OH)2preparing the nanoflower: dissolving nickel nitrate in absolute ethyl alcohol, fully dissolving, adding oleylamine and ethanol mixed solution in the stirring process, stirring for 30min, transferring to a 50mL reaction kettle, carrying out hydrothermal reaction at 180 ℃ in an oven for 15h, and carrying out centrifugal drying to obtain Ni (OH)2A nanoflower;
2) preparing NiO nanoflower: ni (OH)2And (3) placing the nanoflower in a porcelain boat, heating to 300 ℃ at the speed of 2 ℃/min in the air atmosphere for heat treatment, keeping the temperature for 60min, and cooling to obtain the NiO nanoflower.
3) Preparing nitrogen-doped nickel phosphide nanoflower: respectively placing sodium hypophosphite, ammonium bicarbonate and the powder prepared in the step 1) at the front end, the middle part and the tail end of the porcelain boat according to the mass ratio of 1:30 of the NiO nanoflower to the sodium hypophosphite and 1:2 of the ammonium bicarbonate, heating to 450 ℃ by a program of 2 ℃/min in an inert atmosphere for heat treatment, keeping the temperature for 60min, and then cooling to obtain a final product.
Example 10
A preparation method of nitrogen-doped nickel phosphide nanoflower comprises the following steps:
1)Ni(OH)2preparing the nanoflower: dissolving nickel nitrate in absolute ethyl alcohol, fully dissolving, adding oleylamine and ethanol mixed solution in the stirring process, stirring for 30min, transferring to a 50mL reaction kettle, carrying out hydrothermal reaction at 180 ℃ in an oven for 15h, and carrying out centrifugal drying to obtain Ni (OH)2A nanoflower;
2) preparing NiO nanoflower: ni (OH)2And (3) placing the nanoflower in a porcelain boat, heating to 300 ℃ at the speed of 2 ℃/min in the air atmosphere for heat treatment, keeping the temperature for 60min, and cooling to obtain the NiO nanoflower.
3) Preparing nitrogen-doped nickel phosphide nanoflower: respectively placing sodium hypophosphite, urea and the powder prepared in the step 1) at the front end, the middle part and the tail end of the porcelain boat according to the mass ratio of 1:30 of the NiO nanoflower to the sodium hypophosphite and 1:2 of the urea, heating to 400 ℃ by a program of 2 ℃/min in an inert atmosphere, carrying out heat treatment, keeping the temperature for 60min, and then cooling to obtain a final product.
Example 11
A preparation method of nitrogen-doped nickel phosphide nanoflower comprises the following steps:
1)Ni(OH)2preparing the nanoflower: dissolving nickel chloride in absolute ethyl alcohol, fully dissolving, adding oleylamine and ethanol mixed solution in the stirring process, stirring for 30min, transferring to a 50mL reaction kettle, carrying out hydrothermal reaction at 180 ℃ in an oven for 15h, and carrying out centrifugal drying to obtain Ni (OH)2A nanoflower;
2) preparing NiO nanoflower: ni (OH)2And (3) placing the nanoflower in a porcelain boat, heating to 300 ℃ at the speed of 2 ℃/min in the air atmosphere for heat treatment, keeping the temperature for 60min, and cooling to obtain the NiO nanoflower.
3) Preparing nitrogen-doped nickel phosphide nanoflower: respectively placing sodium hypophosphite, ammonium bicarbonate and the powder prepared in the step 1) at the front end, the middle part and the tail end of the porcelain boat according to the mass ratio of 1:30 of the NiO nanoflower to the sodium hypophosphite and 1:2 of the ammonium bicarbonate, heating to 400 ℃ by a program of 2 ℃/min in an inert atmosphere for heat treatment, keeping the temperature for 60min, and then cooling to obtain a final product.
Example 12
Dissolving nickel sulfate of nitrogen-doped nickel phosphide nanoflower in absolute ethyl alcohol, fully dissolving, adding oleylamine and ethanol mixed solution in the stirring process, stirring for 30min, transferring to a 50mL reaction kettle, carrying out hydrothermal reaction at 180 ℃ in an oven for 15h, and carrying out centrifugal drying to obtain Ni (OH)2A nanoflower;
2) preparing NiO nanoflower: ni (OH)2And (3) placing the nanoflower in a porcelain boat, heating to 300 ℃ at the speed of 2 ℃/min in the air atmosphere for heat treatment, keeping the temperature for 60min, and cooling to obtain the NiO nanoflower.
3) Preparing nitrogen-doped nickel phosphide nanoflower: respectively placing sodium hypophosphite, ammonium bicarbonate and the powder prepared in the step 1) at the front end, the middle part and the tail end of the porcelain boat according to the mass ratio of 1:30 of the NiO nanoflower to the sodium hypophosphite and 1:2 of the ammonium bicarbonate, heating to 400 ℃ by a program of 2 ℃/min in an inert atmosphere for heat treatment, keeping the temperature for 60min, and then cooling to obtain a final product.
Comparative example 1
Ni (OH) was prepared in the same manner as in the first step of example 12The difference of the nanoflower is that the second step of phosphating is not performed in the embodiment, specifically: dissolving nickel nitrate in absolute ethyl alcohol, fully dissolving, adding oleylamine and ethanol mixed solution in the stirring process, stirring for 30min, transferring to a 50mL reaction kettle, carrying out hydrothermal reaction at 180 ℃ in an oven for 15h, and carrying out centrifugal drying to obtain Ni (OH)2A nanoflower;
comparative example 2
Preparing nickel phosphide nanoflower: in contrast to example 1, no ammonium bicarbonate or urea was added during the second phosphating step.
Comparative example 3
Preparing nickel phosphide nanoflower: in contrast to example 7, no ammonium bicarbonate or urea was added during the second phosphating step.
Comparative example 4
Preparing nickel phosphide nanoflower: in contrast to example 8, no ammonium bicarbonate or urea was added during the second phosphating step.
Comparative example 5
Preparing nickel phosphide nanoflower: in contrast to example 9, no ammonium bicarbonate or urea was added during the second phosphating step.
The samples prepared in the above examples and comparative examples were physically characterized by means of TEM, HRTEM, SEM, XRD, XPS, etc. From the SEM (fig. 1) and low power TEM (fig. 2) spectra, it can be seen that the nitrogen-doped nickel phosphide catalyst prepared according to the method described in example 1 is a nanoflower structure, which provides more active sites and facilitates electrolyte transport and diffusion. From a further enlarged HRTEM (fig. 3) pattern, the lattice fringe spacing of the nitrogen-doped nickel phosphide nanoflowers was 0.588nm, corresponding to Ni5P4The (100) crystal plane of the phase. FIG. 4 is an XRD pattern of nitrogen-doped nickel phosphide nanoflower prepared according to example 1, and diffraction peaks and Ni are compared with those of a standard pattern5P4(JCPDS, 18-0883) Standard cards were completely identical, demonstrating Ni5P4The successful formation of. FIG. 5 is an XPS spectrum of N for nitrogen doped nickel phosphide nanoflowers where the formation of Ni-N bonds indicates successful doping of the N element. The catalyst synthesized according to example 1 was therefore nitrogen-doped Ni5P4And (4) nano flowers. FIG. 6 is an XRD pattern of nickel phosphide nanoflowers prepared according to comparative examples 2, 3, 4 and 5, and it can be seen that Ni is present at a phosphating temperature of 300 deg.C2A P phase; with increasing temperature, at 350 ℃, Ni appears5P4A phase, in this case Ni2P-Ni5P4Mixing the phases; when the temperature is raised to 400-450 ℃, the obtained product is completely Ni5P4A phase. FIG. 7 is a nitrogen-doped Ni5P4、Ni5P4And Ni (OH)2Hydrogen evolution performance test of (1), nitrogen doping of Ni5P4The nanometer flower catalyst reaches 10mA cm-2Only 96mV being requiredOverpotential is obviously superior to that of non-nitrogen-doped Ni5P4And non-phosphatized Ni (OH)2A catalyst. FIG. 8 is a nitrogen-doped Ni5P4The results of the cycle stability test of the nanoflower catalyst show that the performance of the catalyst is not substantially attenuated after 1000 cycles. FIG. 9 is a nitrogen-doped Ni5P4The results of chronoamperometry of the nanoflower catalyst showed that the catalyst performance did not substantially decay after 9 hours of chronoamperometry. The result shows that the material has wide application prospect as the electrolytic water hydrogen evolution catalyst.
Claims (8)
1. A preparation method of nitrogen-doped nickel phosphide nano flowers is characterized by comprising the steps of mixing nickel salt serving as a metal source and oleylamine serving as a morphology guiding agent, carrying out hydrothermal reaction at the temperature of 160-: (1-10).
2. The method for preparing nitrogen-doped nickel phosphide nanoflower according to claim 1, wherein the metal source is one selected from nickel nitrate, nickel chloride and nickel sulfate.
3. The method of claim 1, wherein the phosphorus source is sodium hypophosphite and the nitrogen source is ammonium bicarbonate or urea.
4. The method for preparing nitrogen-doped nickel phosphide nanoflower according to claim 1, wherein the hydrothermal reaction time is 12-18 h.
5. The method for preparing nitrogen-doped nickel phosphide nanoflower according to claim 1, wherein the heat treatment is carried out in air atmosphere, the temperature rise rate is 2-10 ℃/min, and the holding time after temperature rise is 40-80 min.
6. The method for preparing nitrogen-doped nickel phosphide nanoflower according to claim 1, wherein the heat treatment is carried out in the inert atmosphere together with a phosphorus source and a nitrogen source, the temperature is raised by a program at a rate of 2-10 ℃/min, and the holding time after the temperature is raised is 40-80 min.
7. The nitrogen-doped nickel phosphide nanoflower prepared by the preparation method of any one of claims 1 to 6.
8. The use of the nitrogen-doped nickel phosphide nanoflower as defined in claim 7 as an electrocatalytic hydrogen evolution catalyst.
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