CN111111718A - Preparation method of multi-metal phosphorus-doped electrocatalyst derived based on binary LDH - Google Patents
Preparation method of multi-metal phosphorus-doped electrocatalyst derived based on binary LDH Download PDFInfo
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- CN111111718A CN111111718A CN201911167906.1A CN201911167906A CN111111718A CN 111111718 A CN111111718 A CN 111111718A CN 201911167906 A CN201911167906 A CN 201911167906A CN 111111718 A CN111111718 A CN 111111718A
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 30
- 239000002184 metal Substances 0.000 title claims abstract description 30
- 239000010411 electrocatalyst Substances 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims description 23
- 239000000463 material Substances 0.000 claims abstract description 64
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 39
- 238000010438 heat treatment Methods 0.000 claims abstract description 32
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 25
- 239000004744 fabric Substances 0.000 claims abstract description 24
- 239000012046 mixed solvent Substances 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract 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 abstract description 13
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000004202 carbamide Substances 0.000 claims abstract description 13
- 239000008367 deionised water Substances 0.000 claims abstract description 13
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 13
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims abstract description 13
- 238000001816 cooling Methods 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 11
- 150000001868 cobalt Chemical class 0.000 claims abstract description 7
- 150000002751 molybdenum Chemical class 0.000 claims abstract description 7
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 6
- 239000011574 phosphorus Substances 0.000 claims abstract description 6
- 239000012298 atmosphere Substances 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 10
- 238000011144 upstream manufacturing Methods 0.000 claims description 10
- 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
- 229940011182 cobalt acetate Drugs 0.000 claims description 3
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 3
- 229940044175 cobalt sulfate Drugs 0.000 claims description 3
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 3
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 3
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical group [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 2
- PDKHNCYLMVRIFV-UHFFFAOYSA-H molybdenum;hexachloride Chemical group [Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Mo] PDKHNCYLMVRIFV-UHFFFAOYSA-H 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- WHDPTDWLEKQKKX-UHFFFAOYSA-N cobalt molybdenum Chemical compound [Co].[Co].[Mo] WHDPTDWLEKQKKX-UHFFFAOYSA-N 0.000 abstract description 4
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 11
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 description 8
- 241000446313 Lamella Species 0.000 description 8
- 229910015224 MoCl2 Inorganic materials 0.000 description 8
- 230000000877 morphologic effect Effects 0.000 description 8
- 239000000376 reactant Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 239000007769 metal material Substances 0.000 description 6
- 229910000510 noble metal Inorganic materials 0.000 description 6
- 239000012300 argon atmosphere Substances 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- -1 electrolyzers Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 230000004888 barrier function Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- HTXDPTMKBJXEOW-UHFFFAOYSA-N iridium(IV) oxide Inorganic materials O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 2
- 239000008204 material by function Substances 0.000 description 2
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(IV) oxide Inorganic materials O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 1
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- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000005087 graphitization Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
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- 238000012546 transfer Methods 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
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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
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
- B01J27/19—Molybdenum
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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
- 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
- B01J35/61—Surface area
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Abstract
The invention discloses a multi-element metal phosphorus-doped electrocatalyst derived based on binary LDH, which comprises the following steps: 1) mixing ethylene glycol and deionized water to obtain a mixed solvent; 2) dissolving cobalt salt, molybdenum salt and urea in a mixed solvent, and uniformly stirring to obtain a solution A; 3) adding hydrophilic carbon cloth into the solution A, and reacting to obtain CoMo-LDH-CF; 4) and (3) placing the CoMo-LDH-CF material in a tube furnace, placing a magnetic boat filled with sodium hypophosphite on the upper part of the tube furnace, heating and preserving heat in an inert atmosphere, and cooling to room temperature to obtain the Co and Mo bimetallic-containing binary LDH-derived metal phosphorus-doped electrocatalyst CoMo-P-CF. According to the invention, after a cobalt-molybdenum bimetallic LDH material grown on carbon cloth is synthesized by a hydrothermal method, the cobalt-molybdenum bimetallic LDH material is subjected to high-temperature heat treatment and reacts with sodium hypophosphite to obtain the binary phosphorus doped electro-catalytic material containing Co and Mo bimetallic with large specific surface area and regular structure, and the material has accurate and controllable composition and good conductivity.
Description
Technical Field
The invention belongs to the field of material chemistry, and particularly relates to a preparation method of a multi-element metal phosphorus-doped electrocatalyst derived based on binary LDH.
Background
With the rapid development of social economy, energy and environment become increasingly concerned problems, and the consumption proportion of renewable energy sources such as solar energy, wind energy and the like in the total energy consumption of human society is gradually increased. However, since such renewable energy sources have a certain intermittency and fluctuation in the conversion and use processes of electric energy, technologies such as rechargeable batteries, electrochemical capacitors, electrolyzers, fuel cells and the like, such as electrochemical energy storage and conversion, will play a very important role in realizing efficient and sustainable energy utilization. Despite their different operating principles, these electrochemical devices are made up of similar key functional components, and the electrochemical properties (e.g., redox and catalytic activity) of the functional materials used in these components will determine the overall performance of the device. Therefore, the preparation of functional materials with excellent electrochemical properties has become an important research direction in the electrochemical field.
Double metal hydroxides (LDHs) are host-guest compounds with special structures and functions, and have received wide attention due to their high surface area caused by their layered structures and various properties brought by different metal ions. LDH materials and derivatives thereof generally have very excellent catalytic properties and have very important development potential in the electrochemical field.
The Oxygen Evolution Reaction (OER) is a four-electron process with very slow kinetics, in acidic media water is oxidized to oxygen and hydrogen ions, while in neutral and alkaline electrolytes hydroxyl ions are oxidized to water and oxygen. OER processes often occur through multi-step reactions, with the transfer of a single electron in each individual step. Thus, the accumulation of energy barriers at each individual step eventually makes the OER kinetics become particularly slow, leading to large overpotentials. To overcome the energy barrier during OER, and to achieve a smaller overpotential, electrocatalyst materials must be designed for high stability and low cost. Although IrO2And RuO2The noble metal-based materials have high stability to OER over a relatively wide pH range, but their rarity and high cost are major obstacles to their commercialization progress.
In recent years, non-noble gold has been reported in the literatureBelongs to a base material applied to OER electrocatalysis test research. And IrO2And RuO2Compared with noble metal-based materials, non-noble metal-based materials are low in price and easily available in raw materials. However, reports on non-noble metal-based materials as the OER catalyst are still very limited, and the research on the non-noble metal-based materials is still limited due to the excessively high overpotential in the application process of the OER catalyst. The non-noble metal-based material formed by utilizing the synergistic effect of different metal atoms can also optimize the catalytic activity of the material, and meanwhile, the material performance can be further improved by doping P element to form doping.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides a preparation method of a binary LDH-derived multi-metal phosphorus-doped electrocatalyst with good OER (organic electroluminescent) electrocatalytic performance.
The technical scheme adopted by the invention for solving the technical problems is as follows: a binary LDH-derived multi-metal phosphorus-doped electrocatalyst, comprising the steps of:
1) mixing ethylene glycol and deionized water to obtain a mixed solvent;
2) dissolving cobalt salt, molybdenum salt and urea in the mixed solvent obtained in the step 1), and uniformly stirring to obtain a solution A;
3) adding hydrophilic carbon cloth into the solution A, and reacting at the temperature of 120-200 ℃ for 10-20h to obtain CoMo-LDH-CF;
4) placing the CoMo-LDH-CF material obtained in the step 3) in a tube furnace, placing a magnetic boat containing 20-200mg of sodium hypophosphite upstream of the tube furnace, heating to 200-500 ℃ at the heating rate of 1-10 ℃/min in an inert atmosphere, preserving the heat for 1-5h, and cooling to room temperature to obtain the Co and Mo bimetallic-containing metal LDH-derived metal phosphorus doped electrocatalyst CoMo-P-CF.
Preferably, the volume ratio of the deionized water to the ethylene glycol in the step 1) is 1: 4-9.
Preferably, in the step 2), the cobalt salt is cobalt acetate, cobalt sulfate or cobalt chloride, or a combination of two or three of them, and the molybdenum salt is molybdenum chloride.
Preferably, the mass ratio of the cobalt salt to the molybdenum salt in the step 2) is 1-5:1, and the mass of the urea is 50-200 mg.
Preferably, the hydrophilic carbon cloth in the step 3) is 1cm by 4 cm.
Preferably, the inert atmosphere in the step 4) is nitrogen or argon.
The invention aims to further find a binary LDH-derived multi-metal phosphorus-doped electrocatalyst with simple preparation method, low cost and excellent catalytic performance, firstly synthesizes an LDH material CoMo-LDH-CF growing on carbon cloth, and carries out heat treatment on the material at the temperature of 200-500 ℃ to obtain a carbon nano composite material derived from a bimetallic organic framework material with high graphitization degree, and the material has the characteristics of large specific surface area, regular structure, uniform doping and uniform distribution, and is an electrocatalytic material with excellent performance
The invention has the beneficial effects that: after a cobalt-molybdenum double-metal LDH material grown on carbon cloth is synthesized by a hydrothermal method, the cobalt-molybdenum double-metal LDH material is subjected to high-temperature heat treatment and reacts with sodium hypophosphite to obtain a binary phosphorus-doped electro-catalytic material containing Co and Mo double metals with large specific surface area and regular structure, the material has accurately controllable composition and good conductivity, the material has nanosheets which are thinner than LDH reported in most of documents at present, Co and Mo double-metal LDH with higher yield can be obtained by the method under the same feeding, in addition, the doping of P greatly improves the performance of the LDH material, and after the P is doped, the OER performance of a sample is more excellent than that of most of reported LDH, and the electro-catalytic material is very high in electrochemical stability and excellent in performance.
Drawings
FIG. 1 is a scanning electron microscope picture of a sample CoMo-LDH-CF composite material prepared in example 1 of the present invention.
FIG. 2 is a scanning electron microscope image of a prepared sample CoMo-P-CF binary phosphorus doped electro-catalytic material prepared in example 1 of the present invention.
FIG. 3 is a LSV plot of a CoMo-P-CF binary phosphorus doped electrocatalytic material prepared in example 1 of the present invention.
FIG. 4 is Tafel diagram of CoMo-P-CF binary phosphorus doped electrocatalytic material prepared in example 1 of the present invention.
Detailed Description
In order to make the technical solutions of the present invention better understood, 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, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
(1) Preparation of CoMo-LDH-CF:
(a) mixing 20mL of ethylene glycol and 5mL of deionized water to obtain a mixed solvent;
(b) 40mg of CoCl2·6H2O、20mg MoCl2And 120mg of urea are dissolved in the mixed solvent in the step (a) and are uniformly stirred to obtain a solution A;
(c) pouring the solution A into a reaction kettle, adding 1cm by 4cm of hydrophilic carbon cloth, and reacting for 15 hours in an oven at 180 ℃ to obtain CoMo-LDH-CF-1;
(2) preparation of CoMo-P-CF:
and (2) placing the CoMo-LDH-CF-1 material obtained in the step (1) in a tube furnace, placing a magnetic boat containing 100mg of sodium hypophosphite upstream of the material, heating the reactants to 400 ℃ at the heating rate of 6 ℃/min in a nitrogen atmosphere, preserving the heat for 3h, and cooling to room temperature to obtain the Co and Mo bimetallic-containing metal phosphorus-doped electrocatalyst CoMo-P-CF-1 derived from the binary LDH.
As can be seen by combining the figures 1 and 2, the CoMo-LDH-CF-1 material which grows uniformly on the carbon cloth base is obtained, the LDH lamella is thin, the sample CoMo-P-CF-1 obtained after high-temperature heat treatment realizes uniform P doping, and the morphological framework of the original CoMo-LDH-CF material is well maintained.
It can be seen from the combination of FIGS. 3 and 4 that the sample CoMo-P-CF-1 has an overpotential of 359mV and a Tafel slope of 65mV dec at a current of 10mA-1The performance of the catalyst is excellent when the catalyst is used for producing oxygen by electrolyzing water. This illustrates the samples prepared according to the inventionThe material has excellent electro-catalytic performance, which mainly depends on the high dispersion of Co and Mo bi-metals in the material in the whole body and the synergistic effect of the bi-metals, and the characteristics of large specific surface area, high porosity and the like of the material provide a structural basis for the excellent electro-catalytic performance.
Example 2
(1) Preparation of CoMo-LDH-CF:
(a) mixing 20mL of ethylene glycol and 5mL of deionized water to obtain a mixed solvent;
(b) 60mg of CoCl2·6H2O、20mg MoCl2And 120mg of urea are dissolved in the mixed solvent in the step (a) and are uniformly stirred to obtain a solution A;
(c) pouring the solution A into a reaction kettle, adding 1cm by 4cm of hydrophilic carbon cloth, and reacting for 15 hours in an oven at 120 ℃ to obtain CoMo-LDH-CF-2;
(2) preparation of CoMo-P-CF:
and (2) placing the CoMo-LDH-CF-2 material obtained in the step (1) in a tube furnace, placing a magnetic boat containing 100mg of sodium hypophosphite upstream of the material, heating the reactants to 400 ℃ at the heating rate of 6 ℃/min in a nitrogen atmosphere, preserving the heat for 3h, and cooling to room temperature to obtain the Co and Mo bimetallic-containing metal-phosphorus-doped electrocatalyst CoMo-P-CF-2 derived from the binary LDH.
The CoMo-LDH-CF-2 material which grows uniformly on the carbon cloth base is obtained, LDH lamella is thin and uniform, the sample CoMo-P-CF-2 obtained after high-temperature heat treatment realizes uniform P doping, the morphological framework of the original LDH material is well maintained, and the electrocatalysis test result shows that the performance is excellent.
Example 3
(1) Preparation of CoMo-LDH-CF:
(a) mixing 20mL of ethylene glycol and 5mL of deionized water to obtain a mixed solvent;
(b) 80mg of CoCl2·6H2O、20mg MoCl2And 120mg of urea are dissolved in the mixed solvent in the step (a) and are uniformly stirred to obtain a solution A;
(c) pouring the solution A into a reaction kettle, adding 1cm by 4cm of hydrophilic carbon cloth, and reacting for 15 hours in an oven at 180 ℃ to obtain CoMo-LDH-CF-3;
(2) preparation of CoMo-P-CF:
and (2) placing the CoMo-LDH-CF-3 material obtained in the step (1) in a tube furnace, placing a magnetic boat containing 100mg of sodium hypophosphite upstream of the material, heating the reactants to 400 ℃ at the heating rate of 6 ℃/min in a nitrogen atmosphere, preserving the heat for 3h, and cooling to room temperature to obtain the Co and Mo bimetallic-containing metal phosphorus-doped electrocatalyst CoMo-P-CF-3 derived from the binary LDH.
The CoMo-LDH-CF-3 material which grows uniformly on the carbon cloth base is obtained, LDH lamella is thin and uniform, the sample CoMo-P-CF-3 obtained after high-temperature heat treatment realizes uniform P doping, the morphological framework of the original LDH material is well maintained, and the electrocatalysis test result shows that the performance is excellent.
Example 4
(1) Preparation of CoMo-LDH-CF:
(a) mixing 18mL of ethylene glycol and 2mL of deionized water to obtain a mixed solvent;
(b) 80mg of CoCl2·6H2O、20mg MoCl2And 50mg of urea are dissolved in the mixed solvent in the step (a) and are uniformly stirred to obtain a solution A;
(c) pouring the solution A into a reaction kettle, adding 1cm by 4cm of hydrophilic carbon cloth, and reacting for 15 hours in an oven at 200 ℃ to obtain CoMo-LDH-CF-4;
(2) preparation of CoMo-P-CF:
and (2) placing the CoMo-LDH-CF-4 material obtained in the step (1) in a tube furnace, placing a magnetic boat containing 200mg of sodium hypophosphite upstream of the material, heating the reactants to 400 ℃ at the heating rate of 10 ℃/min in an argon atmosphere, preserving the temperature for 3h, and cooling to room temperature to obtain the Co and Mo bimetallic-containing metal phosphorus-doped electrocatalyst CoMo-P-CF-5 derived from the binary LDH.
The CoMo-LDH-CF-4 material which grows uniformly on the carbon cloth base is obtained, LDH lamella is thin and uniform, the sample CoMo-P-CF-4 obtained after high-temperature heat treatment realizes uniform P doping, the morphological framework of the original LDH material is well maintained, and the electrocatalysis test result shows that the performance is excellent.
Example 5
(1) Preparation of CoMo-LDH-CF:
(a) mixing 20mL of ethylene glycol and 4mL of deionized water to obtain a mixed solvent;
(b) 80mg of CoCl2·6H2O、20mg MoCl2And 200mg of urea are dissolved in the mixed solvent in the step (a) and are uniformly stirred to obtain a solution A;
(c) pouring the solution A into a reaction kettle, adding 1cm by 4cm of hydrophilic carbon cloth, and reacting in an oven at 130 ℃ for 20 hours to obtain CoMo-LDH-CF-5;
(2) preparation of CoMo-P-CF:
and (2) placing the CoMo-LDH-CF-5 material obtained in the step (1) in a tube furnace, placing a magnetic boat containing 20mg of sodium hypophosphite upstream of the material, heating the reactants to 400 ℃ at the heating rate of 10 ℃/min in an argon atmosphere, preserving the temperature for 3h, and cooling to room temperature to obtain the Co and Mo bimetallic-containing metal phosphorus-doped electrocatalyst CoMo-P-CF-5 derived from the binary LDH.
The CoMo-LDH-CF-5 material which grows uniformly on the carbon cloth base is obtained, LDH lamella is thin and uniform, the sample CoMo-P-CF-5 obtained after high-temperature heat treatment realizes uniform P doping, the morphological framework of the original LDH material is well maintained, and the electrocatalysis test result shows that the performance is excellent.
Example 6
(1) Preparation of CoMo-LDH-CF:
(a) mixing 20mL of ethylene glycol and 4mL of deionized water to obtain a mixed solvent;
(b) 80mg of CoCl2·6H2O、20mg MoCl2And 120mg of urea are dissolved in the mixed solvent in the step (a) and are uniformly stirred to obtain a solution A;
(c) pouring the solution A into a reaction kettle, adding 1cm by 4cm of hydrophilic carbon cloth, and reacting in an oven at 120 ℃ for 20 hours to obtain CoMo-LDH-CF-6;
(2) preparation of CoMo-P-CF:
and (2) placing the CoMo-LDH-CF-6 material obtained in the step (1) in a tube furnace, placing a magnetic boat containing 150mg of sodium hypophosphite upstream of the material, heating the reactants to 200 ℃ at the heating rate of 2 ℃/min in a nitrogen atmosphere, preserving the temperature for 5h, and cooling to room temperature to obtain the Co and Mo bimetallic-containing metal-phosphorus-doped electrocatalyst CoMo-P-CF-6 derived from the binary LDH.
The CoMo-LDH-CF-6 material which grows uniformly on the carbon cloth base is obtained, LDH lamella is thin and uniform, the sample CoMo-P-CF-6 obtained after high-temperature heat treatment realizes uniform P doping, the morphological framework of the original LDH material is well maintained, and the electrocatalysis test result shows that the performance is excellent.
Example 7
(1) Preparation of CoMo-LDH-CF:
(a) mixing 20mL of ethylene glycol and 4mL of deionized water to obtain a mixed solvent;
(b) 60mg of CoCl2·6H2O、20mg MoCl2And 200mg of urea are dissolved in the mixed solvent in the step (a) and are uniformly stirred to obtain a solution A;
(c) pouring the solution A into a reaction kettle, adding 1cm by 4cm of hydrophilic carbon cloth, and reacting in an oven at 180 ℃ for 20 hours to obtain CoMo-LDH-CF-7;
(2) preparation of CoMo-P-CF:
and (2) placing the CoMo-LDH-CF-7 material obtained in the step (1) in a tube furnace, placing a magnetic boat containing 150mg of sodium hypophosphite upstream of the material, heating the reactants to 500 ℃ at the heating rate of 2 ℃/min in an argon atmosphere, preserving the temperature for 1h, and cooling to room temperature to obtain the Co and Mo bimetallic-containing metal-phosphorus-doped electrocatalyst CoMo-P-CF-7 derived from the binary LDH.
The CoMo-LDH-CF-7 material which grows uniformly on the carbon cloth base is obtained, LDH lamella is thin and uniform, the sample CoMo-P-CF-7 obtained after high-temperature heat treatment realizes uniform P doping, the morphological framework of the original LDH material is well maintained, and the electrocatalysis test result shows that the performance is excellent.
Example 8
(1) Preparation of CoMo-LDH-CF:
(a) mixing 20mL of ethylene glycol and 4mL of deionized water to obtain a mixed solvent;
(b) 70mg of CoCl2·6H2O、20mg MoCl2And 120mg of urea solutionUniformly stirring in the mixed solvent in the step (a) to obtain a solution A;
(c) pouring the solution A into a reaction kettle, adding 1cm by 4cm of hydrophilic carbon cloth, and reacting in an oven at 200 ℃ for 12 hours to obtain CoMo-LDH-CF-8;
(2) preparation of CoMo-P-CF:
and (2) placing the CoMo-LDH-CF-8 material obtained in the step (1) in a tube furnace, placing a magnetic boat containing 150mg of sodium hypophosphite upstream of the material, heating the reactants to 500 ℃ at the heating rate of 5 ℃/min in an argon atmosphere, preserving the temperature for 1h, and cooling to room temperature to obtain the Co and Mo bimetallic-containing metal phosphorus-doped electrocatalyst CoMo-P-CF-8 derived from the binary LDH.
The CoMo-LDH-CF-8 material which grows uniformly on the carbon cloth base is obtained, LDH lamella is thin and uniform, the sample CoMo-P-CF-8 obtained after high-temperature heat treatment realizes uniform P doping, the morphological framework of the original LDH material is well maintained, and the electrocatalysis test result shows that the performance is excellent.
The foregoing detailed description is intended to illustrate and not limit the invention, which is intended to be within the spirit and scope of the appended claims, and any changes and modifications that fall within the true spirit and scope of the invention are intended to be covered by the following claims.
Claims (6)
1. A preparation method of a multi-metal phosphorus-doped electrocatalyst derived based on binary LDH is characterized by comprising the following steps:
1) mixing ethylene glycol and deionized water to obtain a mixed solvent;
2) dissolving cobalt salt, molybdenum salt and urea in the mixed solvent obtained in the step 1), and uniformly stirring to obtain a solution A;
3) adding hydrophilic carbon cloth into the solution A, and reacting at the temperature of 120-200 ℃ for 10-20h to obtain CoMo-LDH-CF;
4) placing the CoMo-LDH-CF material obtained in the step 3) in a tube furnace, placing a magnetic boat containing 20-200mg of sodium hypophosphite upstream of the tube furnace, heating to 200-500 ℃ at the heating rate of 1-10 ℃/min in an inert atmosphere, preserving the heat for 1-5h, and cooling to room temperature to obtain the Co and Mo bimetallic-containing metal LDH-derived metal phosphorus doped electrocatalyst CoMo-P-CF.
2. The method of preparing the binary LDH-derived multi-metal phosphorus-doped electrocatalyst according to claim 1, wherein: the volume ratio of the deionized water to the ethylene glycol in the step 1) is 1: 4-9.
3. The method of preparing the binary LDH-derived multi-metal phosphorus-doped electrocatalyst according to claim 1, wherein: in the step 2), the cobalt salt is cobalt acetate, cobalt sulfate or cobalt chloride or a combination of two or three of the cobalt acetate, the cobalt sulfate and the cobalt chloride, and the molybdenum salt is molybdenum chloride.
4. The method of preparing the binary LDH-derived multi-metal phosphorus-doped electrocatalyst according to claim 1, wherein: in the step 2), the mass ratio of the cobalt salt to the molybdenum salt is 1-5:1, and the mass of the urea is 50-200 mg.
5. The method of preparing the binary LDH-derived multi-metal phosphorus-doped electrocatalyst according to claim 1, wherein: the hydrophilic carbon cloth in the step 3) is 1cm by 4 cm.
6. The method of preparing the binary LDH-derived multi-metal phosphorus-doped electrocatalyst according to claim 1, wherein: the inert atmosphere in the step 4) is nitrogen or argon.
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