CN111229267B - Supported phosphorus-doped metal oxyhydroxide nanosheet material and preparation method and application thereof - Google Patents
Supported phosphorus-doped metal oxyhydroxide nanosheet material and preparation method and application thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 149
- 239000002135 nanosheet Substances 0.000 title claims abstract description 130
- 229910021518 metal oxyhydroxide Inorganic materials 0.000 title claims abstract description 118
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 44
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 44
- 239000011574 phosphorus Substances 0.000 claims abstract description 44
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000001301 oxygen Substances 0.000 claims abstract description 38
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 38
- 238000006243 chemical reaction Methods 0.000 claims abstract description 35
- 238000009396 hybridization Methods 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 17
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000010411 electrocatalyst Substances 0.000 claims abstract description 13
- 229910052751 metal Inorganic materials 0.000 claims abstract description 13
- 239000002184 metal Substances 0.000 claims abstract description 13
- 239000006261 foam material Substances 0.000 claims abstract description 12
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000004202 carbamide Substances 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 10
- 229910000403 monosodium phosphate Inorganic materials 0.000 claims abstract description 10
- 235000019799 monosodium phosphate Nutrition 0.000 claims abstract description 10
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims abstract description 10
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 9
- 150000003839 salts Chemical class 0.000 claims abstract description 9
- 235000019270 ammonium chloride Nutrition 0.000 claims abstract description 7
- 230000008569 process Effects 0.000 claims abstract description 6
- 239000011259 mixed solution Substances 0.000 claims abstract description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 62
- 229910052759 nickel Inorganic materials 0.000 claims description 31
- 239000000243 solution Substances 0.000 claims description 16
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 238000004140 cleaning Methods 0.000 claims description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 9
- 239000006260 foam Substances 0.000 claims description 8
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 8
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 8
- 239000012498 ultrapure water Substances 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 7
- 239000011261 inert gas Substances 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 239000010953 base metal Substances 0.000 claims description 4
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 4
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 229910001960 metal nitrate Inorganic materials 0.000 claims description 4
- 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 4
- 238000010438 heat treatment Methods 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 239000004917 carbon fiber Substances 0.000 claims description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 2
- 238000011282 treatment Methods 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 9
- 230000007613 environmental effect Effects 0.000 abstract description 5
- 239000002360 explosive Substances 0.000 abstract description 3
- 239000007789 gas Substances 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract description 3
- 231100000331 toxic Toxicity 0.000 abstract description 3
- 230000002588 toxic effect Effects 0.000 abstract description 3
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 229910000000 metal hydroxide Inorganic materials 0.000 abstract 1
- 150000004692 metal hydroxides Chemical class 0.000 abstract 1
- 239000001257 hydrogen Substances 0.000 description 13
- 229910052739 hydrogen Inorganic materials 0.000 description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 238000005868 electrolysis reaction Methods 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 230000006872 improvement Effects 0.000 description 6
- 239000010453 quartz Substances 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 229910018916 CoOOH Inorganic materials 0.000 description 5
- OSOVKCSKTAIGGF-UHFFFAOYSA-N [Ni].OOO Chemical compound [Ni].OOO OSOVKCSKTAIGGF-UHFFFAOYSA-N 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- -1 cobalt oxyhydroxide Chemical compound 0.000 description 5
- 238000011161 development Methods 0.000 description 5
- 229910000483 nickel oxide hydroxide Inorganic materials 0.000 description 5
- CUPCBVUMRUSXIU-UHFFFAOYSA-N [Fe].OOO Chemical compound [Fe].OOO CUPCBVUMRUSXIU-UHFFFAOYSA-N 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 229910021519 iron(III) oxide-hydroxide Inorganic materials 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- HTXDPTMKBJXEOW-UHFFFAOYSA-N iridium(IV) oxide Inorganic materials O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 3
- 230000000630 rising effect Effects 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 229910002588 FeOOH Inorganic materials 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 239000002803 fossil fuel Substances 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002064 nanoplatelet Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- 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 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Images
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
-
- 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
-
- 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
-
- 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
-
- 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 supported phosphorus-doped metal oxyhydroxide nanosheet material as well as a preparation method and application thereof. The preparation method comprises the steps of mixing the foam material with a mixed solution of metal salt/ammonium chloride/urea for hydrothermal reaction, mixing the obtained load type metal hydroxide nanosheet material with sodium dihydrogen phosphate for phosphorus hybridization, and obtaining the material. The supported phosphorus-doped metal oxyhydroxide nanosheet material has the advantages of low cost, high activity, good stability, environmental friendliness and the like, is a novel electrocatalyst, can be widely used for oxygen evolution reaction, and has high use value and good application prospect. The preparation method has the advantages of simple process, convenient operation, low cost, no generation of toxic and explosive gas, environmental protection and the like, is suitable for large-scale preparation, is easy to realize industrial production, and is beneficial to industrial application.
Description
Technical Field
The invention belongs to the field of electrocatalytic water decomposition catalysts, relates to an electrocatalyst for oxygen evolution reaction and a preparation method and application thereof, and particularly relates to a supported phosphorus-doped metal oxyhydroxide nanosheet material and a preparation method and application thereof.
Background
With the use of fossil fuels in large quantities, the environmental pollution problem is becoming more serious and the fossil fuel reserves are reduced, so that the development of various renewable energy sources and new energy sources is highly regarded by countries in the world. At present, researches on new energy mainly include solar energy, geothermal energy, nuclear energy, wind energy, tidal energy, hydrogen energy and the like, wherein the hydrogen energy is paid much attention by scientists due to the advantages of wide sources of raw material hydrogen, cleanness, no pollution, high energy density and the like.
Electrolyzed water is considered to be one of the most possible effective ways to realize the industrial production of clean energy hydrogen, and is generally considered by scientists to be an effective means for changing the energy crisis and realizing the development of sustainable hydrogen energy. The electrolytic water reaction is mainly divided into two electrode half reactions: oxygen evolution reactions, which involve the transfer of four electrons and require a high overpotential, and hydrogen evolution reactions, which are also very slow kinetics. Thus, the oxygen evolution reaction is the bottleneck of the whole electrocatalytic water decomposition, which greatly limits the industrial development of the plants including the electrolysis cells and the fuel cells. At present, the most excellent electrocatalytic activity in the oxygen evolution reaction is the oxide of noble metals ruthenium (Ru) and iridium (Ir), which are often used as the benchmark of the oxygen evolution reaction, but the wide application of the noble metals is limited due to the expensive price. Therefore, the obtained electro-catalyst for the oxygen evolution reaction has low cost, high activity, good stability and environmental protection, and has very important significance in reducing the overpotential of the oxygen evolution reaction, improving the efficiency of hydrogen production by water electrolysis, reducing the cost of hydrogen production by water electrolysis, promoting the industrial development of hydrogen production by water electrolysis and the like.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a supported phosphorus-doped metal oxyhydroxide nanosheet material which is low in cost, high in activity, good in stability and environment-friendly, and a preparation method and application thereof.
In order to solve the technical problems, the invention adopts the technical scheme that:
a load type phosphorus doped metal oxyhydroxide nanosheet material takes a foam-like material as a carrier, and the foam-like material is loaded with the phosphorus doped metal oxyhydroxide nanosheet material; the chemical general formula of the phosphorus-doped metal oxyhydroxide nanosheet material is P-MOOH, and M is a metal element.
In the above loaded type phosphorus-doped metal oxyhydroxide nanosheet material, further improvement is that M in the phosphorus-doped metal oxyhydroxide nanosheet material is a base metal element, and the base metal is at least one of Fe, Co and Ni; the foam material is one of foam nickel, foam iron, carbon felt and carbon fiber.
In the supported phosphorus-doped metal oxyhydroxide nanosheet material, the thickness of the supported phosphorus-doped metal oxyhydroxide nanosheet material is further improved to be 30nm to 50 nm.
As a general technical concept, the invention also provides a preparation method of the supported phosphorus doped metal oxyhydroxide nanosheet material, which comprises the following steps:
s1, mixing the foam material with a mixed solution of metal salt/ammonium chloride/urea to perform hydrothermal reaction to obtain a supported metal oxyhydroxide nanosheet material;
s2, mixing the supported metal oxyhydroxide nanosheet material obtained in the step S1 with sodium dihydrogen phosphate for phosphorus hybridization to obtain a supported phosphorus-doped metal oxyhydroxide nanosheet material.
In the above preparation method, a further improvement is that in step S1, the molar ratio of the metal salt, the ammonium chloride and the urea in the mixed solution of the metal salt/the ammonium chloride and the urea is 0.6-0.7: 7-8: 9-10; the metal salt is metal nitrate; the metal nitrate is at least one of ferric nitrate, cobalt nitrate and nickel nitrate.
In a further improvement of the above preparation method, in step S1, the hydrothermal reaction is performed at a temperature of 100 ℃ to 120 ℃; the time of the hydrothermal reaction is 10-12 h.
In a further improvement of the above preparation method, in step S1, the width of the foam material is 1.5cm to 2.2cm, the length is 3.5cm to 4.2cm, and the thickness is 1.0mm to 2.0 mm; the foam-like material further comprises the following treatments before use: and respectively ultrasonically cleaning the foam material in acetone and hydrochloric acid solution with the concentration of 2.5-3.0 mol/L for 5-10 min in sequence, and respectively cleaning the obtained foam material with ethanol and ultrapure water for 3-5 times.
In a further improvement of the above preparation method, in step S2, the phosphorus hybridization is performed under an inert gas atmosphere; the heating rate in the phosphorus hybridization process is 2-5 ℃/min; the temperature of the phosphorus hybridization is 300-400 ℃; the time for phosphorus hybridization was 1 h.
In a further improvement of the above preparation method, in step S2, the phosphorus hybridization is performed in a tube furnace, and the supported metal oxyhydroxide nanosheet material and sodium dihydrogen phosphate are respectively placed at the lower tuyere and the upper tuyere of the tube furnace; the inert gas is nitrogen.
As a general technical concept, the invention also provides an application of the supported phosphorus-doped metal oxyhydroxide nanosheet material or the supported phosphorus-doped metal oxyhydroxide nanosheet material prepared by the preparation method as an electrocatalyst in oxygen evolution reaction.
Compared with the prior art, the invention has the advantages that:
(1) the invention provides a supported phosphorus-doped metal oxyhydroxide nanosheet material, which takes a foamed material as a carrier, wherein the foamed material is loaded with the phosphorus-doped metal oxyhydroxide nanosheet material, wherein the phosphorus-doped metal oxyhydroxide nanosheet material has a chemical general formula of P-MOOH, and M is a metal element. In the invention, the foam material is a metal conductor with a 3D porous structure, has excellent conductivity, can fully contact with electrolyte and enable generated oxygen to be easily desorbed, meanwhile, the phosphorus-doped metal oxyhydroxide nanosheet material is a main active substance of oxygen evolution reaction, can reduce the overpotential of the oxygen evolution reaction, thereby more easily generating the oxygen, can adjust the electronic structure of the metal oxyhydroxide nanosheet material by phosphorus doping, reduces the energy barrier generated by the oxygen, and has very high catalytic activity. On the basis, the phosphorus-doped metal oxyhydroxide nanosheet material is loaded on the foam material, and the phosphorus-doped metal oxyhydroxide nanosheet material with the main catalytic effect can grow on the foam material, so that the problem that a catalyst falls off due to the generation of oxygen in the reaction process can be solved, the catalytic activity and the stability of the material can be remarkably improved, and the material has higher practical application value. The supported phosphorus-doped metal oxyhydroxide nanosheet material has the advantages of low cost, high activity, good stability, environmental friendliness and the like, is a novel electrocatalyst, can be widely used for oxygen evolution reaction, and has high use value and good application prospect.
(2) The invention provides a preparation method of a supported phosphorus-doped metal oxyhydroxide nanosheet material, which comprises the steps of firstly preparing the metal oxyhydroxide nanosheet material by using a hydrothermal reaction method, loading the metal oxyhydroxide nanosheet material on a foamed material to form the supported metal oxyhydroxide nanosheet material, further mixing the supported metal oxyhydroxide nanosheet material with sodium dihydrogen phosphate for phosphorus hybridization, and doping phosphorus into the supported metal oxyhydroxide nanosheet material to obtain the supported phosphorus-doped metal oxyhydroxide nanosheet material with high activity and good stability. In the preparation method, sodium dihydrogen phosphate is used as a phosphorus source, so that toxic and explosive gases such as phosphine and the like generated by other phosphorus sources (such as sodium hypophosphite) due to high-temperature decomposition can be avoided. The preparation method has the advantages of simple process, convenient operation, low cost, no generation of toxic and explosive gas, environmental protection and the like, is suitable for large-scale preparation, is easy to realize industrial production, and is beneficial to industrial application.
(3) The invention provides an application of a supported phosphorus-doped metal oxyhydroxide nanosheet material as an electrocatalyst in oxygen evolution reaction, and the supported phosphorus-doped metal oxyhydroxide nanosheet material is used as the electrocatalyst to carry out the oxygen evolution reaction, so that the overpotential of the oxygen evolution reaction can be reduced, the efficiency of point hydrolysis hydrogen production can be improved, the cost of water electrolysis hydrogen production can be reduced, the industrial development of water electrolysis hydrogen production can be promoted, a new thought is provided for designing a higher-level material to improve the efficiency of water electrolysis hydrogen production, and the method has very important significance.
Drawings
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention.
Fig. 1 is an SEM image of supported phosphorus-doped metal oxyhydroxide nanosheet material prepared in example 1 of the present invention.
FIG. 2 is an EDS diagram of a supported phosphorus-doped metal oxyhydroxide nanosheet material prepared in example 1 of the present invention.
FIG. 3 is an XPS plot of supported phosphorus doped metal oxyhydroxide nanoplatelets prepared in example 1 of the present invention.
Fig. 4 is a thickness distribution diagram of the supported phosphorus-doped metal oxyhydroxide nanosheet material prepared in example 1 of the present invention.
Fig. 5 is an XRD pattern of the supported phosphorus doped metal oxyhydroxide nanosheet material prepared in example 1 of the present invention.
FIG. 6 shows the supported phosphorus-doped metal oxyhydroxide nanosheet material and IrO prepared in example 1 of the present invention2Graph comparing the initial potential of oxygen evolution of the catalyst.
Fig. 7 is a graph showing the stability test result of the supported phosphorus-doped metal oxyhydroxide nanosheet material prepared in example 1 of the present invention.
FIG. 8 is a graph comparing the initial oxygen evolution potentials of the supported phosphorus doped metal oxyhydroxide nanosheets and the supported metal oxyhydroxide nanosheets (CoOOH) prepared in example 2 of the present invention
Fig. 9 is a graph comparing the initial oxygen evolution potentials of the supported phosphorus doped metal oxyhydroxide nanosheet material and the supported metal oxyhydroxide nanosheet material (NiOOH) prepared in example 3 of the present invention.
Detailed Description
The invention is further described below with reference to the drawings and specific preferred embodiments of the description, without thereby limiting the scope of protection of the invention.
The materials and equipment used in the following examples are commercially available. In the examples of the present invention, unless otherwise specified, the processes used were conventional processes, the equipment used were conventional equipment, and the data obtained were average values of three or more experiments.
Example 1:
a supported phosphorus-doped metal oxyhydroxide nanosheet material takes a foamed material as a carrier, and the foamed material is loaded with the phosphorus-doped metal oxyhydroxide nanosheet material, wherein the chemical general formula of the phosphorus-doped metal oxyhydroxide nanosheet material is P-MOOH, and M is Fe element.
In this embodiment, the foam-like material is nickel foam.
In this embodiment, the thickness of the supported phosphorus-doped metal oxyhydroxide nanosheet material is 30nm to 50 nm.
A method for preparing the supported phosphorus-doped metal oxyhydroxide nanosheet material in embodiment 1 of the present invention includes the following steps:
0.6mmol of Fe (NO)3)3·9H2Dissolving O into 30mL of ultrapure water to form a ferric nitrate solution; adding 9 mmol of urea and 8mmol of ammonium fluoride into the ferric nitrate solution, uniformly mixing, magnetically stirring for 30min, and transferring to a reaction kettle; simultaneously, cutting the foamed nickel into corresponding sizes (the length, width and thickness are 20mm multiplied by 40mm multiplied by 1.0mm), respectively ultrasonically cleaning the foamed nickel in acetone and dilute hydrochloric acid solution with the concentration of 3.0mol/L for 10min, respectively cleaning the foamed nickel with ethanol and ultrapure water for three times, drying the cleaned foamed nickel, transferring the dried foamed nickel into a reaction kettle containing the solution, carrying out hydrothermal reaction for 12h at the temperature of 120 ℃, and obtaining foam with a layered iron oxyhydroxide nanosheet material growing after the reaction, namely the supported metal oxyhydroxide nanosheet material; respectively placing foamed nickel and 5g of sodium dihydrogen phosphate which are used for growing the layered iron oxyhydroxide nanosheet material in two quartz boats, respectively placing the quartz boats at a lower air port and an upper air port of a tubular furnace, then heating to 350 ℃ at a rising rate of 2 ℃/min under the protection of inert gas (nitrogen) to perform phosphorus hybridization for 1h, doping phosphorus into the supported metal oxyhydroxide nanosheet material, and naturally cooling to room temperature to obtain the phosphorus-doped layered iron oxyhydroxide nanosheet material, namely the supported phosphorus-doped metal oxyhydroxide nanosheet material.
SEM analysis of the supported phosphorus-doped metal oxyhydroxide nanosheet material prepared in example 1 is shown in FIG. 1. Fig. 1 is an SEM image of supported phosphorus-doped metal oxyhydroxide nanosheet material prepared in example 1 of the present invention. As shown in FIG. 1, the thickness of the supported phosphorus-doped metal oxyhydroxide nanosheet material prepared in example 1 of the present invention is 30-50 nm.
EDS analysis is carried out on the supported phosphorus-doped metal oxyhydroxide nanosheet material prepared in example 1, and the result is shown in FIG. 2. FIG. 2 is an EDS diagram of a supported phosphorus-doped metal oxyhydroxide nanosheet material prepared in example 1 of the present invention. As shown in fig. 2, it can be clearly observed that phosphorus element is doped into the supported metal oxyhydroxide nanosheet material.
The supported phosphorus-doped metal oxyhydroxide nanosheet material prepared in example 1 was subjected to spectroscopic analysis, and the results are shown in fig. 3. FIG. 3 is an XPS plot of supported phosphorus doped metal oxyhydroxide nanoplatelets prepared in example 1 of the present invention. In FIG. 3, A is an XPS total spectrum, B is an Fe 2P spectrum, C is an O1s spectrum, and D is a P2P spectrum. As shown in fig. 3, in the supported phosphorus-doped metal oxyhydroxide nanosheet material prepared in inventive example 1, the doping manner of the phosphorus element is in the form of P — O bond.
Fig. 4 is a thickness distribution diagram of the supported phosphorus-doped metal oxyhydroxide nanosheet material prepared in example 1 of the present invention. As shown in FIG. 4, the thickness distribution of the supported phosphorus-doped metal oxyhydroxide nanosheet material prepared in example 1 of the present invention is between 30-50 nm.
Fig. 5 is an XRD pattern of the supported phosphorus doped metal oxyhydroxide nanosheet material prepared in example 1 of the present invention. As can be seen from fig. 5, the data was found to match well by comparing with the crystal image of FeOOH in the inorganic crystal structure database (JCPDS); meanwhile, the XRD peak of the supported phosphorus doped metal oxyhydroxide nanosheet material prepared in the embodiment 1 of the invention slightly shifts relative to the peak of FeOOH in the database, which indicates that phosphorus element is successfully doped into the supported metal oxyhydroxide nanosheet material, so that the lattice stripes of the crystal are changed; this further demonstrates the success of the preparation of supported phosphorus doped metal oxyhydroxide nanosheets.
An application of the supported phosphorus-doped metal oxyhydroxide nanosheet material prepared in the embodiment 1 of the present invention as an electrocatalyst in an oxygen evolution reaction.
The supported phosphorus doped metal oxyhydroxide nanosheet material prepared in the embodiment 1 of the invention and IrO2Electrochemical performance and stability of the catalyst (a common commercially available OER electrocatalyst) were compared, and oxygen evolution performance of the electrocatalyst was tested in 1.0mol/L NaOH electrolyte at room temperature using CHI 6043e workstation, and the test results are shown in FIGS. 6 and 7.
FIG. 6 shows the supported phosphorus-doped metal oxyhydroxide nanosheet material and IrO prepared in example 1 of the present invention2Graph comparing the initial potential of oxygen evolution of the catalyst. Fig. 7 is a graph showing the stability test result of the supported phosphorus-doped metal oxyhydroxide nanosheet material prepared in example 1 of the present invention. As can be seen from fig. 6 and 7, compared with the commercially available iridium dioxide material, the supported phosphorus-doped metal oxyhydroxide nanosheet material prepared according to the present invention has a lower oxygen evolution overpotential; meanwhile, after the material is continuously operated for 10 hours, the current density of the supported phosphorus-doped metal oxyhydroxide nanosheet material prepared by the method is still not reduced, which indicates that the material has high stability.
Example 2:
a supported phosphorus-doped metal oxyhydroxide nanosheet material takes a foamed material as a carrier, and the foamed material is loaded with the phosphorus-doped metal oxyhydroxide nanosheet material, wherein the chemical general formula of the phosphorus-doped metal oxyhydroxide nanosheet material is P-MOOH, and M is Co element.
In this embodiment, the foam-like material is nickel foam.
In this embodiment, the thickness of the supported phosphorus-doped metal oxyhydroxide nanosheet material is 30nm to 50 nm.
A method for preparing the supported phosphorus-doped metal oxyhydroxide nanosheet material in embodiment 2 of the present invention includes the following steps:
0.6mmol of Co (NO)3)2·6H2Dissolving O into 40mL of ultrapure water to form a cobalt nitrate solution; then adding 10 mmol of urea and 8mmol of ammonium fluoride into the cobalt nitrate solution and mixing uniformly; magnetically stirring for 30min, and transferring to a reaction kettle; simultaneously, cutting the foamed nickel into corresponding sizes (the length, width and thickness are 20mm multiplied by 40mm multiplied by 1.0mm), respectively ultrasonically cleaning the foamed nickel in acetone and dilute hydrochloric acid solution with the concentration of 3.0mol/L for 10min, respectively cleaning the foamed nickel with ethanol and ultrapure water for three times, drying the cleaned foamed nickel, transferring the dried foamed nickel into a reaction kettle containing the solution, reacting the dried foamed nickel for 12h at the temperature of 120 ℃, and obtaining the foamed nickel with the layered cobalt oxyhydroxide nanosheet material after the reaction, namely the foamed nickel with the layered cobalt oxyhydroxide nanosheet material, which is marked as CoOOH; respectively placing foamed nickel and 5g of sodium dihydrogen phosphate which are used for growing the layered cobalt oxyhydroxide nanosheet material in two quartz boats, respectively placing the quartz boats at a lower air port and an upper air port of a tubular furnace, then raising the temperature to 350 ℃ at a rising rate of 2 ℃/min under the protection of inert gas (nitrogen) to perform phosphorus hybridization for 1h, and naturally cooling to obtain the phosphorus-doped layered cobalt oxyhydroxide nanosheet material, namely the supported phosphorus-doped metal oxyhydroxide nanosheet material.
An application of the supported phosphorus-doped metal oxyhydroxide nanosheet material prepared in embodiment 2 of the present invention as an electrocatalyst in oxygen evolution reactions.
The results of comparing the activities of the supported phosphorus-doped metal oxyhydroxide nanosheet material and the supported metal oxyhydroxide nanosheet material (CoOOH) prepared in example 2 of the present invention in the electrocatalytic oxygen evolution reaction are shown in fig. 8. Fig. 8 is a graph comparing the initial oxygen evolution potentials of the supported phosphorus doped metal oxyhydroxide nanosheet material and the supported metal oxyhydroxide nanosheet material (CoOOH) prepared in example 2 of the present invention. As can be seen from fig. 8, compared with simple CoOOH, the supported phosphorus-doped metal oxyhydroxide nanosheet material prepared by the present invention has a lower oxygen evolution overpotential, which indicates that the electrocatalytic oxygen evolution performance of the metal oxyhydroxide is improved by phosphorus doping.
Example 3:
a supported phosphorus-doped metal oxyhydroxide nanosheet material takes a foamed material as a carrier, and the foamed material is loaded with the phosphorus-doped metal oxyhydroxide nanosheet material, wherein the chemical general formula of the phosphorus-doped metal oxyhydroxide nanosheet material is P-MOOH, and M is an Ni element.
In this embodiment, the foam-like material is nickel foam.
In this embodiment, the thickness of the supported phosphorus-doped metal oxyhydroxide nanosheet material is 30nm to 50 nm.
A method for preparing the supported phosphorus-doped metal oxyhydroxide nanosheet material in embodiment 3 of the present invention includes the following steps:
adding 0.7mmol of Ni (NO)3)2·6H2Dissolving O into 40mL of ultrapure water to form a nickel nitrate solution; then adding 10 mmol of urea and 8mmol of ammonium fluoride into the nickel nitrate solution and uniformly mixing; magnetically stirring for 30min, and transferring to a reaction kettle; simultaneously, cutting the foamed nickel into corresponding sizes (the length, width and thickness are 20mm multiplied by 40mm multiplied by 1.0mm), respectively ultrasonically cleaning the foamed nickel in acetone and dilute hydrochloric acid solution with the concentration of 3.0mol/L for 10min, respectively cleaning the foamed nickel with ethanol and ultrapure water for three times, drying the cleaned foamed nickel, transferring the dried foamed nickel into a reaction kettle containing the solution, reacting the dried foamed nickel for 12h at the temperature of 120 ℃, and obtaining the foamed nickel with the layered nickel oxyhydroxide nanosheet material after the reaction, namely the foamed nickel with the layered nickel oxyhydroxide nanosheet material, which is marked as NiOOH; respectively placing foamed nickel and 5g of sodium dihydrogen phosphate which are used for growing the layered nickel oxyhydroxide nanosheet material in two quartz boats, respectively placing the quartz boats at a lower air port and an upper air port of a tubular furnace, then raising the temperature to 350 ℃ at a rising rate of 2 ℃/min under the protection of inert gas (nitrogen) to perform phosphorus hybridization for 1h, and naturally cooling to obtain the phosphorus-doped layered nickel oxyhydroxide nanosheet material, namely the supported phosphorus-doped metal oxyhydroxide nanosheet material.
An application of the supported phosphorus-doped metal oxyhydroxide nanosheet material prepared in the embodiment 3 of the present invention as an electrocatalyst in an oxygen evolution reaction.
The results of comparing the activities of the supported phosphorus-doped metal oxyhydroxide nanosheets and supported metal oxyhydroxide Nanosheets (NiOOH) prepared in example 3 of the present invention in the electrocatalytic oxygen evolution reaction are shown in fig. 9. Fig. 9 is a graph comparing the initial oxygen evolution potentials of the supported phosphorus doped metal oxyhydroxide nanosheet material and the supported metal oxyhydroxide nanosheet material (NiOOH) prepared in example 3 of the present invention. As can be seen from fig. 9, compared with a simple NiOOH nanosheet material, the supported phosphorus-doped metal oxyhydroxide nanosheet material prepared by the method provided by the invention has a lower oxygen evolution overpotential, which indicates that the electrocatalytic oxygen evolution performance of the metal oxyhydroxide is improved by phosphorus doping.
According to the embodiments 1 to 3, the supported phosphorus-doped metal oxyhydroxide nanosheets (including doped layered iron oxyhydroxide nanosheets, phosphorus-doped layered cobalt oxyhydroxide nanosheets and phosphorus-doped layered nickel oxyhydroxide nanosheets) prepared by the method of the present invention exhibit high electrocatalytic activity and stability of oxygen evolution reaction.
The above examples are merely preferred embodiments of the present invention, and the scope of the present invention is not limited to the above examples. All technical schemes belonging to the idea of the invention belong to the protection scope of the invention. It should be noted that modifications and embellishments within the scope of the invention may be made by those skilled in the art without departing from the principle of the invention, and such modifications and embellishments should also be considered as within the scope of the invention.
Claims (10)
1. A load type phosphorus doped metal oxyhydroxide nanosheet material is characterized in that a foamed material is used as a carrier, and the foamed material is loaded with the phosphorus doped metal oxyhydroxide nanosheet material; the chemical general formula of the phosphorus-doped metal oxyhydroxide nanosheet material is P-MOOH, and M is a metal element; m in the phosphorus-doped metal oxyhydroxide nanosheet material is a base metal element, and the base metal is at least one of Fe, Co and Ni.
2. The supported phosphorus doped metal oxyhydroxide nanosheet material of claim 1, wherein the foamed material is one of nickel foam, iron foam, carbon felt, and carbon fiber.
3. The supported phosphorus-doped metal oxyhydroxide nanosheet material of claim 1 or 2, wherein the supported phosphorus-doped metal oxyhydroxide nanosheet material has a thickness of from 30nm to 50 nm.
4. The preparation method of the supported phosphorus-doped metal oxyhydroxide nanosheet material according to any one of claims 1 to 3, comprising the steps of:
s1, mixing the foam material with a mixed solution of metal salt/ammonium chloride/urea to perform hydrothermal reaction to obtain a supported metal oxyhydroxide nanosheet material;
s2, mixing the supported metal oxyhydroxide nanosheet material obtained in the step S1 with sodium dihydrogen phosphate for phosphorus hybridization to obtain a supported phosphorus-doped metal oxyhydroxide nanosheet material.
5. The method according to claim 4, wherein in step S1, the molar ratio of the metal salt, the ammonium chloride and the urea in the mixed solution of the metal salt, the ammonium chloride and the urea is 0.6-0.7: 7-8: 9-10; the metal salt is metal nitrate; the metal nitrate is at least one of ferric nitrate, cobalt nitrate and nickel nitrate.
6. The method according to claim 5, wherein in step S1, the hydrothermal reaction is carried out at a temperature of 100 ℃ to 120 ℃; the time of the hydrothermal reaction is 10-12 h.
7. The method according to claim 6, wherein in the step S1, the foam-like material has a width of 1.5cm to 2.2cm, a length of 3.5cm to 4.2cm, and a thickness of 1.0mm to 2.0 mm; the foam-like material further comprises the following treatments before use: and respectively ultrasonically cleaning the foam material in acetone and hydrochloric acid solution with the concentration of 2.5-3.0 mol/L for 5-10 min in sequence, and respectively cleaning the obtained foam material with ethanol and ultrapure water for 3-5 times.
8. The preparation method according to any one of claims 4 to 7, wherein in the step S2, the phosphorus hybridization is performed under the protection of inert gas; the heating rate in the phosphorus hybridization process is 2-5 ℃/min; the temperature of the phosphorus hybridization is 300-400 ℃; the time for phosphorus hybridization was 1 h.
9. The preparation method according to claim 8, wherein in the step S2, the phosphorus hybridization is carried out in a tube furnace, and the supported metal oxyhydroxide nanosheet material and sodium dihydrogen phosphate are respectively placed at a lower tuyere and an upper tuyere of the tube furnace; the inert gas is nitrogen.
10. Use of the supported phosphorus-doped metal oxyhydroxide nanosheet material of any one of claims 1 to 3 or the supported phosphorus-doped metal oxyhydroxide nanosheet material prepared by the preparation method of any one of claims 4 to 9 as an electrocatalyst in an oxygen evolution reaction.
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| US10196746B2 (en) * | 2016-04-29 | 2019-02-05 | University Of Kansas | Microwave assisted synthesis of metal oxyhydroxides |
| CN109174162B (en) * | 2018-10-26 | 2021-04-20 | 江苏大学 | Iron-doped bimetallic phosphide electrocatalyst and preparation method and application thereof |
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