CN111424285B - Preparation method for constructing catalytic electrode by taking foamed cobalt as substrate under low-temperature condition - Google Patents
Preparation method for constructing catalytic electrode by taking foamed cobalt as substrate under low-temperature condition Download PDFInfo
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- 239000010941 cobalt Substances 0.000 title claims abstract description 90
- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 90
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 90
- 239000000758 substrate Substances 0.000 title claims abstract description 61
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000002135 nanosheet Substances 0.000 claims abstract description 47
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 40
- 229910018916 CoOOH Inorganic materials 0.000 claims abstract description 29
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000003513 alkali Substances 0.000 claims abstract description 20
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 20
- 229910052742 iron Inorganic materials 0.000 claims abstract description 11
- FBMUYWXYWIZLNE-UHFFFAOYSA-N nickel phosphide Chemical compound [Ni]=P#[Ni] FBMUYWXYWIZLNE-UHFFFAOYSA-N 0.000 claims abstract description 6
- VAKIVKMUBMZANL-UHFFFAOYSA-N iron phosphide Chemical compound P.[Fe].[Fe].[Fe] VAKIVKMUBMZANL-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000006260 foam Substances 0.000 claims description 32
- 239000000243 solution Substances 0.000 claims description 32
- 238000000034 method Methods 0.000 claims description 28
- 238000010438 heat treatment Methods 0.000 claims description 20
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 10
- 239000012670 alkaline solution Substances 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 8
- 229910052786 argon Inorganic materials 0.000 claims description 6
- 230000001681 protective effect Effects 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 15
- 239000003054 catalyst Substances 0.000 abstract description 9
- 239000012467 final product Substances 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 230000000593 degrading effect Effects 0.000 abstract 1
- 239000003344 environmental pollutant Substances 0.000 abstract 1
- 239000013067 intermediate product Substances 0.000 abstract 1
- 231100000719 pollutant Toxicity 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 12
- 239000001257 hydrogen Substances 0.000 description 12
- 229910052739 hydrogen Inorganic materials 0.000 description 12
- 229910052573 porcelain Inorganic materials 0.000 description 12
- 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 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 238000004140 cleaning Methods 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 238000004502 linear sweep voltammetry Methods 0.000 description 8
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 8
- 238000009210 therapy by ultrasound Methods 0.000 description 8
- 238000011144 upstream manufacturing Methods 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 6
- 239000002243 precursor Substances 0.000 description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 4
- 239000012300 argon atmosphere Substances 0.000 description 4
- 238000007664 blowing Methods 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- UGKDIUIOSMUOAW-UHFFFAOYSA-N iron nickel Chemical compound [Fe].[Ni] UGKDIUIOSMUOAW-UHFFFAOYSA-N 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- 239000011574 phosphorus Substances 0.000 description 4
- 230000010287 polarization Effects 0.000 description 4
- 238000002203 pretreatment Methods 0.000 description 4
- 239000010453 quartz Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- -1 cobalt oxyhydroxide Chemical compound 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
Images
Classifications
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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
-
- 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—
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C8/06—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases
- C23C8/08—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases only one element being applied
-
- 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
- C25B11/02—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form
- C25B11/03—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form perforated or foraminous
- C25B11/031—Porous electrodes
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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
- C25B11/055—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
- C25B11/057—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material consisting of a single element or compound
-
- 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
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
-
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
- Y02P20/133—Renewable energy sources, e.g. sunlight
Abstract
The invention relates to a preparation method for constructing a catalytic electrode by taking foamed cobalt as a substrate under a low-temperature condition, which is characterized by comprising the following steps of: (1) performing alkali treatment on a foamed cobalt substrate (abbreviated as CF) to generate a CoOOH hexagonal nanosheet on the surface; (2) phosphating at the temperature of 250 ℃ and 600 ℃ for less than or equal to 6 hours to obtain flaky CoP hexagonal nanosheets; (3) immersing the sample into a solution containing iron and/or nickel, and filling iron and nickel in the gaps and the surfaces of the nanosheets; (4) and (3) repeating the step (2) on the sample treated in the step (3) to carry out secondary phosphorization, so that iron phosphide and/or nickel phosphide is generated by iron and nickel filled in the gaps and the surface of the nanosheets. The electrolyzed water catalyst has the advantages of simple preparation method, cheap raw materials, low processing cost, no need of precise and complex equipment, and rapid realization of scale production, and the intermediate product CoOOH/CF can also be prepared in large scale as an intermediate or a final product for degrading pollutants and (photo) electrochemically decomposing water.
Description
Technical Field
The invention relates to the field of nano material preparation, in particular to a preparation method for constructing a catalytic electrode by using foamed cobalt as a substrate under a low-temperature condition.
Background
The technology for producing hydrogen by electrolyzing water in alkaline electrolyte has wide prospect, the technical method is simple, the purity of the produced hydrogen is high, and the technology can be directly used for future hydrogen energy automobiles and the like. The problems of environmental pollution, resource exhaustion and the like caused by fossil energy can be effectively relieved.
The key of the hydrogen production by electrolyzing water is to find a non-noble metal catalyst which is cheap, has high catalytic activity and stability and can be comparable with a noble metal catalyst. The cobalt is low in price and rich in mineral products, and the cobalt-based catalyst has a large number of active sites and can stably exist in an alkaline solution, so that the cobalt-based catalyst is widely applied to preparation of an electrolytic water catalytic electrode.
At present, the cobalt-based catalytic electrode is mainly loaded on a substrate such as foamed nickel, carbon cloth and the like, and the electrode has the defects of low mechanical strength, easy falling of a catalyst and the like. Foamed cobalt has the advantages of high mechanical strength, relatively stable in alkaline solution, and contains a large amount of cobalt as an active site. However, the operations such as the oxidation process, the phosphorization process and the like are required to be carried out at a higher temperature, so that the production cost is increased, and the high temperature can influence the conductivity of the foamed cobalt, so that the foamed cobalt is rarely used as an electrolytic water catalyst. Therefore, the preparation method for preparing the cobalt-based electrode under the low-temperature condition and effectively improving the catalytic activity and the stability has better application prospect.
Disclosure of Invention
The invention aims to provide a preparation method for constructing a catalytic electrode by using foamed cobalt as a substrate under a low-temperature condition, so as to solve the problems that the cobalt-based electrode needs high temperature in the oxidation and phosphorization processes in the prior art, so that the cost is increased, and the high temperature can seriously influence the conductivity of the cobalt-based electrode.
In order to achieve the purpose, the preparation method for constructing the catalytic electrode by taking the foamed cobalt as the substrate under the low-temperature condition adopts the following technical scheme: a preparation method for constructing a catalytic electrode by taking foamed cobalt as a substrate under a low-temperature condition comprises the following steps:
(1) carrying out alkali treatment on the foamed cobalt substrate in an alkaline solution, and heating the foamed cobalt substrate subjected to alkali treatment at the temperature of 20-120 ℃ for 36 hours or less to generate CoOOH hexagonal nanosheets on the surface of the foamed cobalt substrate;
(2) carrying out phosphating treatment on the foam cobalt-based plate treated in the step (1) in a protective gas atmosphere, wherein the phosphating treatment temperature is 250-600 ℃, and the phosphating time is less than or equal to 6 hours, so that hexagonal CoP nanosheets are generated on the surface of the foam cobalt-based plate;
(3) immersing the foamed cobalt substrate treated in the step (2) into a solution containing iron element and/or nickel element for treatment, wherein the total molar concentration of the iron element and the nickel element in the solution is 0.02-1M, and then heating at 20-200 ℃ for 0.5-16 hours to enable the solution to be filled in the gaps and the surfaces of the nanosheets;
(4) and (3) repeating the step (2) on the foamed cobalt substrate treated in the step (3) to carry out secondary phosphorization, so that iron phosphide and/or nickel phosphide is generated by iron and/or nickel filled in the gaps and the surface of the nanosheets.
And (4) before the step (4), repeating the content of the step (3) again on the foamed cobalt substrate treated in the step (3).
The solution in the step (3) adopts FeCl with the molar concentration of 0.05M3And NiCl at a molar concentration of 0.05M2The solution was mixed.
And (3) immersing the foamed cobalt substrate into a solution containing iron and/or nickel, stirring for 10 seconds, heating at 80 ℃, and heating for 4 hours.
Argon is adopted as the protective gas in the step (2), the phosphating temperature is 300 ℃, and the phosphating time is 1 hour.
In the step (1), the alkali treatment is to select NaOH solution with the molar concentration of 0.01-10M, blow off the surface liquid of the foam cobalt substrate after the alkali treatment, and heat the foam cobalt substrate in the air for 12 hours at the temperature of 80 ℃.
The invention has the beneficial effects that: the invention utilizes the alkali treatment technology to generate the CoOOH nano-sheet at low temperature, can be easier to phosphorize, and reduces the time and temperature for subsequent phosphorization. Furthermore, the intermediate hydroxides and oxyhydroxides can be produced on a large scale as pollutant-degrading, (photo) electrochemical catalysts or precursors.
Drawings
FIG. 1 is a scanning electron microscope image of CF in a first embodiment of the method for preparing a catalytic electrode on a cobalt foam substrate at low temperature according to the present invention;
FIG. 2 is a scanning electron micrograph of CoOOH/CF in the first embodiment;
FIG. 3 is a scanning electron micrograph of CoP/CF in the first embodiment;
FIG. 4 is a scanning electron micrograph of NiFeP-CoP/CF in the first example;
FIG. 5 is an LSV plot of oxygen evolution for pure Co, CoOOH/CF, CoP/CF, NiFeP-CoP/CF in example one, and for NiP-CoP/CF in example five and FeP-CoP/CF in example six; also the oxygen evolution LSV profile compared to commercial electrodes RuO2 and Pt/C (20 wt%);
FIG. 6 is a graph of hydrogen evolution LSV for pure Co, CoOOH/CF, CoP/CF, NiFeP-CoP/CF in example one, and NiP-CoP/CF in example five and FeP-CoP/CF in example six; also shown is the hydrogen evolution LSV plot compared to commercial electrodes RuO2 and Pt/C (20 wt%).
Detailed Description
The present invention will be described in further detail with reference to the following examples, which are provided for illustrative purposes and are not intended to limit the scope of the present invention.
Example one
(1) And (3) performing alkali treatment on the foamed cobalt substrate (noted as CF) in an alkaline solution to generate a CoOOH (cobalt oxyhydroxide) nanosheet array on the surface of the foamed cobalt substrate.
Specifically, a foam cobalt substrate (the length and the height are respectively 2.5cm multiplied by 1.5cm multiplied by 0.1cm) is selected for pretreatment, and the pretreatment method is that absolute ethyl alcohol is used for cleaning for 10 minutes in a numerical control ultrasonic cleaner to remove organic matters on the surface; ultrasonic treatment is carried out for 2 minutes by using sulfuric acid with the molar concentration of 0.5M to remove oxides, and then the surface liquid is blown off by washing with deionized water and absolute ethyl alcohol. As a pretreatment before the alkali treatment.
The specific alkali treatment method comprises the following steps: placing the pretreated foam cobalt-based plate in a NaOH solution with the molar concentration of 4.0M for ultrasonic treatment for 1 minute, then placing the plate in a glass bottle, heating the plate at the temperature of 80 ℃ for 12 hours, cleaning the plate with deionized water and absolute ethyl alcohol after heating, blowing off surface liquid, and growing a CoOOH nanosheet array on the surface of the foam cobalt through alkali treatment, wherein the CoOOH nanosheet array is marked as CoOOH/CF.
(2) And (4) carrying out phosphating treatment to enable the surface of the foam cobalt to generate a CoP nanosheet array.
In particular, sodium hypophosphite is selected as a phosphorus source, and PH is generated at high temperature3Contact of gas with reactantsCorresponding phosphides are formed. The phosphorization step is as follows: the precursor of the CoOOH nanosheet array is placed on the upstream side of a downstream porcelain boat, 1g of sodium hypophosphite is placed on the downstream side of the upstream porcelain boat, and the two porcelain boats are placed in the middle of a quartz tube. Introducing argon for 30 minutes, raising the temperature to 300 ℃ at the speed of 5 ℃/minute, maintaining the temperature for 1 hour under the argon atmosphere, and naturally cooling to room temperature after heating to obtain a sheet CoP array which is marked as CoP/CF.
(3) And (3) immersing the foamed cobalt substrate treated in the step (2) into a solution containing iron element and nickel element for treatment, so that the solution is filled in the gaps and the surfaces of the parts of the nano sheets.
Specifically, the foamed cobalt growing the flaky CoP array is taken as a substrate, and the process of loading iron nickel phosphide is as follows: substrate for growing chip CoP array NiCl with molar concentration of 0.05M2And FeCl with a molar concentration of 0.05M3The mixed solution was immersed and stirred for 10 seconds, heated in an oven at 80 ℃ for 4 hours, and the above process was repeated.
(4) And (3) repeating the step (2) on the foamed cobalt substrate treated in the step (3) to carry out secondary phosphorization, so that iron and nickel filled in the gaps and the surface of the nanosheets generate iron phosphide and nickel phosphide.
Specifically, phosphorization is carried out according to the phosphorization method of the CoP nanosheet array in the step (2), and a corresponding phosphide is synthesized and is marked as NiFeP-CoP/CF.
Example two
(1) And (3) performing alkali treatment on the foamed cobalt substrate (noted as CF) in an alkaline solution to generate CoOOH nanosheets on the surface of the foamed cobalt substrate.
Specifically, a foam cobalt substrate (the length and the height are respectively 2.5cm multiplied by 1.5cm multiplied by 0.1cm) is selected for pretreatment, and the pretreatment method is that absolute ethyl alcohol is used for cleaning for 10 minutes in a numerical control ultrasonic cleaner to remove organic matters on the surface; ultrasonic treatment is carried out for 2 minutes by using sulfuric acid with the molar concentration of 0.5M to remove oxides, and then the surface liquid is blown off by washing with deionized water and absolute ethyl alcohol.
Placing the pretreated foam cobalt-based plate in a NaOH solution with the molar concentration of 0.01M for ultrasonic treatment for 1 minute, then placing the plate in a glass bottle, heating the plate at the temperature of 20 ℃ for 36 hours, cleaning the plate with deionized water and absolute ethyl alcohol after heating, blowing off surface liquid, and growing a CoOOH nanosheet array on the surface of the foam cobalt through alkali treatment, wherein the CoOOH nanosheet array is marked as CoOOH/CF.
(2) And (4) carrying out phosphating treatment to enable the surface of the foam cobalt to generate a CoP nano sheet.
In particular, sodium hypophosphite is selected as a phosphorus source, and PH is generated at high temperature3The gas and reactant contact to form the corresponding phosphide. The phosphorization step is as follows: the precursor of the CoOOH nanosheet array is placed on the upstream side of a downstream porcelain boat, 1g of sodium hypophosphite is placed on the downstream side of the upstream porcelain boat, and the two porcelain boats are placed in the middle of a quartz tube. Introducing argon for 30 minutes, raising the temperature to 600 ℃ at the speed of 5 ℃/minute, maintaining the temperature for 6 hours under the argon atmosphere, and naturally cooling to room temperature after heating to obtain a sheet CoP array which is marked as CoP/CF.
(3) And (3) immersing the foam cobalt-based plate treated in the step (2) into a solution containing nickel element for treatment, so that the solution is filled in the gaps and the surfaces of the nanosheets.
Specifically, the foamed cobalt growing the flaky CoP array is taken as a substrate, and the process of loading iron nickel phosphide is as follows: the substrate on which the chip CoP array grows is NiCl with the molar concentration of 0.02M2The solution was soaked and stirred for 10 seconds, heated in an oven at 20 ℃ for 16 hours, and the above process was repeated.
(4) And (3) repeating the step (2) on the foamed cobalt substrate treated in the step (3) to carry out secondary phosphorization, so that nickel filled in the gaps and the surface of the nanosheets generates nickel phosphide.
Specifically, phosphorization is carried out according to the phosphorization method of the CoP nanosheet array in the step (2), and a corresponding phosphide is synthesized and is marked as NiP-CoP/CF.
EXAMPLE III
(1) And (3) performing alkali treatment on the foamed cobalt substrate (noted as CF) in an alkaline solution to generate CoOOH nanosheets on the surface of the foamed cobalt substrate.
Specifically, a foam cobalt substrate (the length and the height are respectively 2.5cm multiplied by 1.5cm multiplied by 0.1cm) is selected for pretreatment, and the pretreatment method is that absolute ethyl alcohol is used for cleaning for 10 minutes in a numerical control ultrasonic cleaner to remove organic matters on the surface; ultrasonic treatment is carried out for 2 minutes by using sulfuric acid with the molar concentration of 0.5M to remove oxides, and then the surface liquid is blown off by washing with deionized water and absolute ethyl alcohol.
Placing the pretreated foam cobalt-based plate in a NaOH solution with the molar concentration of 0.01M for ultrasonic treatment for 1 minute, then placing the plate in a glass bottle, heating the plate at the temperature of 120 ℃ for 1 hour, cleaning the plate with deionized water and absolute ethyl alcohol after heating, blowing off surface liquid, and growing a CoOOH nanosheet array on the surface of the foam cobalt through alkali treatment, wherein the CoOOH nanosheet array is marked as CoOOH/CF.
(2) And (4) carrying out phosphating treatment to enable the surface of the foam cobalt to generate a CoP nano sheet.
In particular, sodium hypophosphite is selected as a phosphorus source, and PH is generated at high temperature3The gas and reactant contact to form the corresponding phosphide. The phosphorization step is as follows: the precursor of the CoOOH nanosheet array is placed on the upstream side of a downstream porcelain boat, 1g of sodium hypophosphite is placed on the downstream side of the upstream porcelain boat, and the two porcelain boats are placed in the middle of a quartz tube. Introducing argon for 30 minutes, raising the temperature to 250 ℃ at the speed of 5 ℃/minute, maintaining the temperature for 2 hours under the argon atmosphere, and naturally cooling to room temperature after heating to obtain a sheet CoP array which is marked as CoP/CF.
(3) And (3) immersing the foam cobalt-based plate treated in the step (2) into a solution containing iron element for treatment, so that the solution is filled in the gaps and the surfaces of the nanosheets.
Specifically, the foamed cobalt growing the flaky CoP array is taken as a substrate, and the process of loading iron nickel phosphide is as follows: FeCl with molar concentration of 0.02M on substrate for growing sheet CoP array2The solution is soaked and stirred for 10 seconds, heated in an oven for 0.5 hour at 20 ℃, and the process is repeated.
(4) And (3) repeating the step (2) on the foamed cobalt substrate treated in the step (3) to carry out secondary phosphorization, so that iron filled in the gaps and the surface of the nanosheets generates iron phosphide.
Specifically, phosphorization is carried out according to the phosphorization method of the CoP nanosheet array in the step (2), and a corresponding phosphide is synthesized and is marked as FeP-CoP/CF.
Example four
(1) And (3) performing alkali treatment on the foamed cobalt substrate (noted as CF) in an alkaline solution to generate CoOOH nanosheets on the surface of the foamed cobalt substrate.
Specifically, a foam cobalt substrate (the length and the height are respectively 2.5cm multiplied by 1.5cm multiplied by 0.1cm) is selected for pretreatment, and the pretreatment method is that absolute ethyl alcohol is used for cleaning for 10 minutes in a numerical control ultrasonic cleaner to remove organic matters on the surface; ultrasonic treatment is carried out for 2 minutes by 0.5M sulfuric acid to remove oxides, and then the surface liquid is blown off by washing with deionized water and absolute ethyl alcohol.
Placing the pretreated foam cobalt-based plate in a NaOH solution with the molar concentration of 10M for ultrasonic treatment for 1 minute, then placing the foam cobalt-based plate in a glass bottle, heating the foam cobalt-based plate at the temperature of 20 ℃ for 36 hours, cleaning the foam cobalt-based plate by using deionized water and absolute ethyl alcohol after heating, blowing off surface liquid, and growing a CoOOH nanosheet array on the surface of the foam cobalt through alkali treatment, wherein the CoOOH nanosheet array is marked as CoOOH/CF.
(2) And (4) carrying out phosphating treatment to enable the surface of the foam cobalt to generate a CoP nano sheet.
In particular, sodium hypophosphite is selected as a phosphorus source, and PH is generated at high temperature3The gas and reactant contact to form the corresponding phosphide. The phosphorization step is as follows: the precursor of the CoOOH nanosheet array is placed on the upstream side of a downstream porcelain boat, 1g of sodium hypophosphite is placed on the downstream side of the upstream porcelain boat, and the two porcelain boats are placed in the middle of a quartz tube. Introducing argon for 30 minutes, raising the temperature to 300 ℃ at the speed of 5 ℃/minute, maintaining the temperature for 6 hours in the argon atmosphere, and naturally cooling to room temperature after heating to obtain a sheet CoP array which is marked as CoP/CF.
(3) And (3) immersing the foam cobalt-based plate treated in the step (2) into a solution containing nickel element for treatment, wherein the solution is filled in the gaps and the surfaces of the nanosheets.
Specifically, the foamed cobalt growing the flaky CoP array is taken as a substrate, and the process of loading iron nickel phosphide is as follows: substrate for growing chip CoP array NiCl with molar concentration of 1M2The solution is soaked and stirred for 10 seconds, heated in an oven at 200 ℃ for 2 hours, and the process is repeated.
(4) And (3) repeating the step (2) on the foamed cobalt substrate treated in the step (3) to carry out secondary phosphorization, so that nickel filled in the gaps and the surface of the nanosheets generates nickel phosphide.
Specifically, phosphorization is carried out according to the phosphorization method of the CoP nanosheet array in the step (2), and a corresponding phosphide is synthesized and is marked as NiCoP/CF.
EXAMPLE five
The only difference from example one is that FeCl with a molar concentration of 0.05M is added3And NiCl at a molar concentration of 0.05M2The mixed solution is changed into NiCl with the molar concentration of 0.1M2Solution, the final product was designated NiP-CoP/CF.
EXAMPLE six
The only difference from example one is that FeCl with a molar concentration of 0.05M is added3And NiCl at a molar concentration of 0.05M2The mixed solution is changed into FeCl with the molar concentration of 0.1M2The solution, the final product was designated FeP-CoP/CF.
And selecting a part of the foamed cobalt substrate obtained in each step in the first embodiment to perform the morphology of the nanosheets on the surface of the scanning electron microscope, as shown in fig. 1-4, and generating a nanosheet array on the surface of the foamed cobalt. After the iron and nickel are loaded, the phosphorized surface is slightly smoother than that before phosphorization, and the iron and nickel are proved to be filled in gaps and surfaces.
Pure Co, CoOOH/CF, CoP/CF, NiFeP-CoP/CF in the first embodiment, NiP-CoP/CF in the fifth embodiment, FeP-CoP/CF in the sixth embodiment and RuO as a commercial electrode are selected2LSV curves were compared with Pt/C (20 wt%) electrodes. In a traditional three-electrode electrolytic cell system, a 1.0MKOH solution is used as an electrolyte to perform oxygen evolution and hydrogen evolution electrolytic water performance tests (linear sweep voltammetry LSV, the result of which is a polarization curve, called LSV for short). Fig. 5 and 6 are oxygen evolution and hydrogen evolution polarization curves for all the above samples under alkaline conditions, the polarization curves showing the relationship between electrode potential and polarization current density. Fig. 5 and 6 show the current density on the ordinate and the voltage on the abscissa. Generally, at a certain current density, the lower the absolute value of the voltage, the lower the voltage required to reach a certain current density, the better the performance of the catalyst. With commercial noble metal RuO2And Pt as a reference, the oxygen evolution performance of NiFeP-CoP/CF is better than that of RuO2The difference between the two is very obvious,; under the condition of high absolute value of hydrogen evolution current densityThe hydrogen evolution performance of NiFeP-CoP/CF is comparable to that of Pt/CF, and even at higher absolute current densities, the performance tends to exceed that of Pt/CF. The hydrogen evolution and oxygen evolution performances of the NiFeP-CoP/CF are also more excellent than those of other samples; meanwhile, compared with a pure foam cobalt substrate, the catalytic performance of hydrogen evolution and oxygen evolution is obviously improved.
Claims (6)
1. A preparation method for constructing a catalytic electrode by taking foamed cobalt as a substrate under a low-temperature condition is characterized by comprising the following steps of:
(1) carrying out alkali treatment on the foamed cobalt substrate in an alkaline solution, and heating the foamed cobalt substrate subjected to alkali treatment at the temperature of 20-120 ℃ for 36 hours or less to generate CoOOH hexagonal nanosheets on the surface of the foamed cobalt substrate;
(2) carrying out phosphating treatment on the foam cobalt-based plate treated in the step (1) in a protective gas atmosphere, wherein the phosphating treatment temperature is 250-600 ℃, and the phosphating time is less than or equal to 6 hours, so that hexagonal CoP nanosheets are generated on the surface of the foam cobalt-based plate;
(3) immersing the foamed cobalt substrate treated in the step (2) into a solution containing iron element and/or nickel element for treatment, wherein the total molar concentration of the iron element and the nickel element in the solution is 0.02-1M, and then heating at 20-200 ℃ for 0.5-16 hours to enable the solution to be filled in the gaps and the surfaces of the nanosheets;
(4) and (3) repeating the step (2) on the foamed cobalt substrate treated in the step (3) to carry out secondary phosphorization, so that iron phosphide and/or nickel phosphide is generated by iron and/or nickel filled in the gaps and the surface of the nanosheets.
2. The method for preparing the catalytic electrode constructed by taking the foamed cobalt as the substrate under the low-temperature condition as claimed in claim 1, wherein the method comprises the following steps: and (4) before the step (4), repeating the content of the step (3) again on the foamed cobalt substrate treated in the step (3).
3. The method for preparing the catalytic electrode constructed by taking the foamed cobalt as the substrate under the low-temperature condition as claimed in claim 1, wherein the method comprises the following steps: the solution in the step (3) adopts FeCl with the molar concentration of 0.05M3And NiCl at a molar concentration of 0.05M2The solution was mixed.
4. The method for preparing the catalytic electrode constructed by taking the foamed cobalt as the substrate under the low-temperature condition as claimed in claim 1, wherein the method comprises the following steps: and (3) immersing the foamed cobalt substrate into a solution containing iron and/or nickel, stirring for 10 seconds, heating at 80 ℃, and heating for 4 hours.
5. The method for preparing the catalytic electrode constructed by taking the foamed cobalt as the substrate under the low-temperature condition as claimed in claim 1, wherein the method comprises the following steps: argon is adopted as the protective gas in the step (2), the phosphating temperature is 300 ℃, and the phosphating time is 1 hour.
6. The method for preparing the catalytic electrode constructed by taking the foamed cobalt as the substrate under the low-temperature condition as claimed in claim 1, wherein the method comprises the following steps: in the step (1), the alkali treatment is to select NaOH solution with the molar concentration of 0.01-10M, blow off the surface liquid of the foam cobalt substrate after the alkali treatment, and heat the foam cobalt substrate in the air for 12 hours at the temperature of 80 ℃.
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