CN110714209A - Cobalt-nickel hydroxide sleeve type modified carbon fiber composite material and preparation method and application thereof - Google Patents
Cobalt-nickel hydroxide sleeve type modified carbon fiber composite material and preparation method and application thereof Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 65
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 33
- XTOOSYPCCZOKMC-UHFFFAOYSA-L [OH-].[OH-].[Co].[Ni++] Chemical compound [OH-].[OH-].[Co].[Ni++] XTOOSYPCCZOKMC-UHFFFAOYSA-L 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title abstract description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000001301 oxygen Substances 0.000 claims abstract description 40
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 40
- 239000000463 material Substances 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 23
- 230000007935 neutral effect Effects 0.000 claims abstract description 18
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 16
- 229920000049 Carbon (fiber) Polymers 0.000 claims abstract description 15
- 239000004917 carbon fiber Substances 0.000 claims abstract description 15
- 239000000758 substrate Substances 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims abstract description 13
- 230000003197 catalytic effect Effects 0.000 claims abstract description 12
- 239000011159 matrix material Substances 0.000 claims abstract description 11
- 239000000853 adhesive Substances 0.000 claims abstract description 6
- 230000001070 adhesive effect Effects 0.000 claims abstract description 6
- 239000007772 electrode material Substances 0.000 claims abstract description 6
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 6
- 238000011160 research Methods 0.000 claims abstract description 6
- 238000011065 in-situ storage Methods 0.000 claims abstract description 4
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 56
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 52
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 50
- 229910052799 carbon Inorganic materials 0.000 claims description 40
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 32
- 239000010941 cobalt Substances 0.000 claims description 21
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 21
- 239000003792 electrolyte Substances 0.000 claims description 21
- 239000008367 deionised water Substances 0.000 claims description 20
- 229910021641 deionized water Inorganic materials 0.000 claims description 20
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 17
- 229910017052 cobalt Inorganic materials 0.000 claims description 17
- 239000008055 phosphate buffer solution Substances 0.000 claims description 16
- 229910052759 nickel Inorganic materials 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 13
- 229910021397 glassy carbon Inorganic materials 0.000 claims description 12
- 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 claims description 11
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 11
- 239000004202 carbamide Substances 0.000 claims description 11
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical class [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 claims description 10
- 238000005868 electrolysis reaction Methods 0.000 claims description 10
- 230000008569 process Effects 0.000 claims description 10
- 238000003760 magnetic stirring Methods 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- 238000012360 testing method Methods 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 8
- 239000003575 carbonaceous material Substances 0.000 claims description 8
- 238000002484 cyclic voltammetry Methods 0.000 claims description 8
- 239000010411 electrocatalyst Substances 0.000 claims description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 8
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 8
- 238000011068 loading method Methods 0.000 claims description 6
- 238000010408 sweeping Methods 0.000 claims description 6
- 238000001075 voltammogram Methods 0.000 claims description 6
- 229910001429 cobalt ion Inorganic materials 0.000 claims description 5
- 239000003344 environmental pollutant Substances 0.000 claims description 5
- 231100000719 pollutant Toxicity 0.000 claims description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- 229920000297 Rayon Polymers 0.000 claims description 4
- 230000008859 change Effects 0.000 claims description 4
- 239000004744 fabric Substances 0.000 claims description 4
- 239000010439 graphite Substances 0.000 claims description 4
- 229910002804 graphite Inorganic materials 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- 238000005303 weighing Methods 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- -1 cobalt-nickel hydroxide sleeve-modified carbon fiber Chemical class 0.000 claims description 3
- 230000007613 environmental effect Effects 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 230000020477 pH reduction Effects 0.000 claims description 3
- 239000002243 precursor Substances 0.000 claims description 3
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 238000004140 cleaning Methods 0.000 claims description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 2
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 2
- 229940044175 cobalt sulfate Drugs 0.000 claims description 2
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 2
- 238000005520 cutting process Methods 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 2
- 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 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 230000006798 recombination Effects 0.000 claims description 2
- 238000005215 recombination Methods 0.000 claims description 2
- 230000002441 reversible effect Effects 0.000 claims description 2
- 239000012266 salt solution Substances 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 239000004332 silver Substances 0.000 claims description 2
- 238000012430 stability testing Methods 0.000 claims description 2
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 2
- 230000001788 irregular Effects 0.000 claims 1
- 238000012545 processing Methods 0.000 abstract description 3
- 230000002195 synergetic effect Effects 0.000 abstract description 2
- 230000002194 synthesizing effect Effects 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 24
- 239000003054 catalyst Substances 0.000 description 15
- 239000003795 chemical substances by application Substances 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 12
- 239000000203 mixture Substances 0.000 description 12
- 238000002156 mixing Methods 0.000 description 9
- 239000002253 acid Substances 0.000 description 8
- 238000001816 cooling Methods 0.000 description 7
- 230000003301 hydrolyzing effect Effects 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- 239000000843 powder Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 239000011230 binding agent Substances 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229920000557 Nafion® Polymers 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 239000010842 industrial wastewater Substances 0.000 description 2
- 230000001678 irradiating effect Effects 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910000000 metal hydroxide Inorganic materials 0.000 description 2
- 150000004692 metal hydroxides Chemical class 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 229910003266 NiCo Inorganic materials 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- NVIVJPRCKQTWLY-UHFFFAOYSA-N cobalt nickel Chemical compound [Co][Ni][Co] NVIVJPRCKQTWLY-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000004299 exfoliation Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 150000004679 hydroxides Chemical class 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
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000002905 metal composite material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 150000003623 transition metal compounds Chemical class 0.000 description 1
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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
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/75—Cobalt
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
-
- B01J35/33—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- 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
- 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
Abstract
The invention discloses a cobalt-nickel hydroxide sleeve type modified carbon fiber composite material and a preparation method and application thereof. The material comprises a three-dimensional conductive matrix material and a catalytic active component compounded on the surface of the matrix; the two components form a sleeve type integrated electrode material without an adhesive. The preparation method comprises the following steps: divalent metal ions are subjected to in-situ growth of hydroxide on a carbon fiber substrate by a one-step hydrothermal method, and the hydroxide serving as a composite material is directly applied to neutral environment oxygen evolution research: the active component and the matrix are compounded to form the sleeve type integrated electrode material without the adhesive. The one-step method for synthesizing the cobalt-nickel hydroxide sleeve type modified carbon fiber composite material has the advantages of definite active components, high electrocatalytic efficiency, cheap and easily-obtained substrate material and easiness in processing, improves the electrocatalytic conductivity and active sites under the synergistic effect of the active components and the substrate material, and fully exerts the excellent performances of hydroxide and carbon fiber felt in the aspect of electrocatalysis.
Description
Technical Field
The invention relates to a cobalt-nickel hydroxide sleeve type modified carbon fiber composite material and a preparation method and application thereof, belonging to the technical field of catalytic materials.
Background
With the continuous consumption of fossil energy and the continuous increase of environmental problems, people have increasingly growing requirements on clean energy and green development. The electrocatalytic anode Oxygen Evolution Reaction (OER) plays an important role in the field of new energy resources, such as electrocatalytic decomposition of water for hydrogen evolution, fuel cells and the like. However, the oxygen evolution reaction involves four electron transfer, a kinetic lag process. At present, noble metals such as ruthenium, iridium and the like and oxides thereof have high electrocatalytic activity and can improve oxygen evolution efficiency, but the commercial application of the noble metals is limited by factors such as high price, low reserves and the like. Therefore, the research and development of a non-noble metal OER catalyst which is convenient for production and application is still one of the important directions of scientific research.
The research of iron-based transition metal compound on OER electrocatalytic mechanism shows that the low-valence element compound such as cobalt hydroxide Co (OH)2Etc., which are further converted to their corresponding oxyhydroxide forms such as cobalt oxyhydroxide (CoOOH), etc., during the electrocatalytic process, and these oxyhydroxides are believed to be the true active sites for electrocatalytic oxygen Evolution [ direct oxygen Evolution of Structural Evolution of Metal charogenide in electrocatalytic Water Oxidation [ J]. ACS nano 2018, 12 (12):12369-12379.]. It has been reported that the cobalt-nickel layered hydroxide has excellent electrocatalytic activity [ Hyd ] for anodic oxygen evolution reaction in alkaline electrolysis environmentrothermalcontinuous flow synthesis and exfoliation of NiCo layered double hydroxidenanosheets for enhanced oxygen evolution catalysis [J]. Nano letters 2015, 15(2):1421-7.]. However, the oxygen evolution efficiency under neutral electrolytes has been rarely studied; in the practical application process, the catalyst material also has the problems of poor conductivity, easy agglomeration, poor stability and the like. In the traditional water electrolysis system research, the electrocatalytic powder material is often fixed on a conductive substrate by using a binder to perform oxygen evolution reaction, the use of the binder inevitably introduces interface transmission resistance in the processing process, covers active sites on the surface of the material, limits the permeation and diffusion of reactants in an electrode, influences the exertion of the catalytic performance of the material, increases the difficulty of electrode preparation, and severely limits the actual production and application of the oxygen evolution electrocatalyst.
Disclosure of Invention
The invention aims to provide a cobalt-nickel hydroxide sleeve type modified carbon fiber composite material. The catalytic active component of the composite material is a layered hydroxide, the specific surface area is large, and the catalytic activity is high in a neutral electrolytic environment; the catalyst substrate is selected from low-cost carbon fibers, has wide sources, acid and alkali resistance and chemical stability, and is suitable for industrial use.
The second purpose of the invention is to provide a preparation method of a cobalt-nickel hydroxide sleeve type modified carbon fiber composite material. In order to overcome the problems of poor conductivity of metal hydroxide and easy agglomeration and performance reduction in the preparation process, the metal hydroxide directly grows vertically on a conductive carbon material substrate by a one-step hydrothermal synthesis method in the preparation process, the proportion of cobalt and nickel of precursors is regulated, the reaction temperature and time are optimized, the optimal active loading capacity on the substrate is selected, and the high efficiency of electrocatalytic oxygen evolution and the stability of practical application are ensured. The synthesis method is simple to operate, green, environment-friendly and easy to control, and can be used for large-scale production.
The third purpose of the invention is to provide the application of the cobalt-nickel hydroxide sleeve type modified carbon fiber composite material in electrocatalytic oxygen evolution in neutral media and pollutant-added environments. The composite material can be used as an anode in a neutral medium to electrolyze water to prepare oxygen.
The invention provides a sleeve type modified carbon fiber composite material of cobalt-nickel hydroxide, a three-dimensional conductive matrix material; a catalytic active component compounded on the surface of the substrate; a sleeve type integrated electrode material without an adhesive.
The matrix material comprises one of conductive polyacrylonitrile carbon felt (PAN), Activated Carbon Felt (ACF), viscose-based graphite felt (RGF), carbon fiber cloth (CC) and the like, and the diameter of the carbon fiber is 5 ~ 20 mu m.
The catalytic active component is layered cobalt-nickel hydroxide wrapping carbon fibers, the thickness of the layered cobalt-nickel hydroxide is 2 ~ 5 mu m, and the metal atom recombination quantity on the unit mass of the carbon materials is 1 ~ 6 mmol.
The invention provides a preparation method of a cobalt-nickel hydroxide sleeve type modified carbon fiber composite material, which comprises the following steps: divalent cobalt and nickel metal ions are subjected to in-situ growth of hydroxide on a carbon fiber substrate by a one-step hydrothermal method, and the hydroxide is directly applied to neutral environment oxygen evolution research as a composite material: the active component and the matrix are compounded to form the sleeve type integrated electrode material without the adhesive. The sleeve type loading of the active component and the matrix not only improves the dispersibility and the catalytic activity of the catalyst, but also avoids the addition of a binder, simplifies the process conditions and improves the performance.
The preparation method specifically comprises the following steps:
cutting a carbon material with the volume of 3 ~ 8 cm, the width of 2 ~ 5 cm and the thickness of 0.1 ~ 1 cm, such as one of polyacrylonitrile carbon felt, activated carbon felt, viscose-based graphite felt and carbon fiber cloth, sequentially carrying out ultrasonic cleaning in acetone, ethanol and deionized water, drying, immersing a carbon substrate in 20 ~ 50 mL of concentrated nitric acid, carrying out hydrothermal reaction, carrying out acidification treatment, improving the hydrophilicity of the carbon material, increasing oxygen-containing groups and facilitating the loading of active components.
Weighing cobalt and nickel ion salts, dissolving the cobalt and nickel ion salts in a mixed solution of 0.2 ~ 0.6.6 mol/L urea and 0.005 ~ 0.05.05 mol/L ammonium fluoride under magnetic stirring, wherein the molar ratio of cobalt to nickel elements is (10 ~ 0.1.1)/1, the molar ratio of the total of metal ion salts to urea to ammonium fluoride is 1-3: 2-6: 0.05-0.5, immersing an acidified carbon felt in a precursor metal salt solution, reacting at the hydrothermal temperature of 70 ~ 180 ℃ for 4 ~ 24 h, and cleaning and drying the composite material by deionized water to obtain the cobalt-nickel hydroxide sleeve type modified carbon fiber composite material.
In the above preparation method, the carbon felt material is advantageous in that it is shaped, provides an irregularly shaped carrier, and has conductivity.
In the preparation method, the soluble metal cobalt ion salt is selected from one or more of cobalt sulfate, cobalt nitrate and cobalt chloride; the nickel ion salt is selected from one or more of nickel sulfate, nickel nitrate and nickel chloride.
In order to test the practical applicability of the obtained material, phenol which is difficult to degrade and remove in industrial wastewater is used as a pollution additive to simulate a complex electrolysis environment, the electrocatalytic performance and the stable practicability of the composite material obtained by the method are further researched, and important technical and material support is provided for realizing the practical operation of large-scale water electrolysis.
The invention provides the application of the cobalt-nickel hydroxide sleeve-type modified carbon fiber composite material in electrocatalytic oxygen evolution in neutral media and environments with pollutants, preferably, the neutral condition is 0.1mol/L Phosphate Buffer Solution (PBS), and the pH value is kept stable in the electrolytic process; phenol is used as a pollutant to be added into the electrolyte, and the oxygen evolution performance of the electrocatalyst in a complex electrolysis environment is further verified.
The electrochemical oxygen evolution performance of the composite material provided by the invention is tested according to the following method:
a three-electrode system is adopted, the working electrode is the electrocatalyst provided by the invention, the reference electrode is a silver/silver chloride electrode (Ag/AgCl), and the counter electrode is a platinum electrode (Pt). The test is carried out on a Princeton electrochemical workstation, electrolyte is respectively 0.1mol/L phosphate buffer solution and phosphate buffer solution added with 100ppm phenol, the temperature of the electrolyte is controlled by water bath, the electrocatalysis process is ensured to be stably carried out at 25 ℃, and the influence of the temperature on the electrocatalysis performance is eliminated;
electrochemical oxygen evolution test: linear Sweep Voltammogram (LSV): sweeping at 5mV/s and 1600 rpm, and exploring the electrochemical kinetics of the composite material OER; cyclic Voltammogram (CV): and (3) taking a glassy carbon electrode as a working electrode, sweeping at a speed of 10mV/s, and testing the influence of the environmental change of the electrolyte on the material performance. The electrode potential is converted to the electrode potential relative to the Reversible Hydrogen Electrode (RHE) using the formula: e (rhe) = E (Ag/AgCl) +0.059 × pH + 0.197;
and (3) stability testing: and (3) respectively fixing applied bias voltages in the environment of neutral electrolyte, neutral dielectric medium and phenol in a constant voltage mode to prepare the electrocatalyst which is directly used as a working electrode, and detecting the change of current density along with time.
The invention has the beneficial effects that:
1) the one-step method for synthesizing the cobalt-nickel hydroxide sleeve type modified carbon fiber composite material has the advantages of definite active components, high electrocatalytic efficiency, cheap and easily-obtained substrate material and easiness in processing, improves the electrocatalytic conductivity and active sites under the synergistic effect of the active components and the substrate material, and fully exerts the excellent performances of hydroxide and carbon fiber felt in the aspect of electrocatalysis.
2) The catalyst prepared by the invention is a non-noble metal composite material, and the used material resources are rich, the operation is easy, and the large-scale production is convenient; the electrocatalyst prepared by the invention can be directly used for electrolyzing water, and avoids using a binder. Not only is beneficial to the exertion of the intrinsic catalytic performance of the catalyst, but also simplifies the process and reduces the complexity of the system.
3) The test condition of the catalyst obtained by the invention relates to neutral electrolyte and an electrolysis environment containing pollutant phenol, the catalyst has better OER activity, a constant potential is applied in 0.1mol/L phosphate buffer solution, and after 15 hours, the influence of the addition of the phenol on the oxygen evolution current density can be observed, and the catalyst has more practical reference significance and value compared with the oxygen evolution electrocatalyst researched and reported at present.
Drawings
FIG. 1 is an SEM image of a Co/Ni PAN-120 composite prepared in example 2 of the invention.
FIG. 2 shows the Co/Ni 6/4-PAN composite prepared in example 4 of the invention, the Co-PAN of comparative example 2,
XPS plots of Ni-PAN composites.
FIG. 3 is an XRD pattern of PAN prepared in comparative example 1, Co-PAN and Ni-PAN prepared in comparative example 2 according to the present invention.
FIG. 4 is an OER linear voltammogram and corresponding Tafel plot for the Co/Ni PAN-90 composite prepared in example 1 of the invention, the Co/Ni PAN-120 composite prepared in example 2, the Co/Ni PAN-180 composite prepared in example 3, and the acidified PAN-modified glassy carbon electrode of comparative example 1.
FIG. 5 is the OER linear voltammogram of the Co/Ni PAN-120 composite prepared in example 2, the Co/Ni 6/4-PAN composite prepared in example 4, and the Co/Ni 4/6-PAN composite modified glassy carbon electrode prepared in example 5.
FIG. 6 is the OER cyclic voltammetry curve of the Co/Ni PAN-120 composite material prepared in example 2 of the invention and the Co/Ni-120 powder material modified glassy carbon electrode prepared in comparative example 1.
FIG. 7 is the OER cyclic voltammogram of the Co/Ni PAN-120 composite modified glassy carbon electrode prepared in example 2 of the invention.
FIG. 8 is an OER chronoamperometric graph of the Co/Ni PAN-120 composite material prepared in example 2 of the invention directly as the working electrode.
Detailed Description
The present invention is further illustrated by, but is not limited to, the following examples.
Example 1:
putting a polyacrylonitrile carbon felt (PAN) acidified by concentrated acid into the inner liner of the reaction kettle; deionized water is used as a solvent, 0.46mol/L urea is dissolved to be used as a hydrolytic agent, 0.01 mol/L ammonium fluoride is added to be used as a growth guiding agent, and cobalt ion salt and nickel ion salt are added under magnetic stirring, so that the ratio of cobalt to nickel elements is 9/1. Uniformly mixing, transferring the mixture to a reaction kettle, immersing a carbon felt in the lining, and keeping the mixture at 90 ℃ for hydrothermal reaction for 7 hours; and after cooling, washing the polyacrylonitrile carbon felt with deionized water, and drying at 7 ℃ overnight to obtain the layered cobalt-nickel hydroxide/polyacrylonitrile carbon felt composite material which is marked as Co/Ni PAN-90.
Example 2:
putting a polyacrylonitrile carbon felt (PAN) acidified by concentrated acid into the inner liner of the reaction kettle; deionized water is used as a solvent, 0.46mol/L urea is dissolved to be used as a hydrolytic agent, 0.01 mol/L ammonium fluoride is added to be used as a growth guiding agent, and cobalt ion salt and nickel ion salt are added under magnetic stirring, so that the ratio of cobalt to nickel elements is 9/1. Uniformly mixing, transferring the mixture to a reaction kettle, immersing a carbon felt in the lining, and keeping the mixture at the temperature of 120 ℃ for hydrothermal reaction for 7 hours; and after cooling, washing the polyacrylonitrile carbon felt with deionized water, and drying at 70 ℃ overnight to obtain the layered cobalt-nickel hydroxide/polyacrylonitrile carbon felt composite material which is marked as Co/Ni PAN-120.
Example 3:
putting a polyacrylonitrile carbon felt (PAN) acidified by concentrated acid into the inner liner of the reaction kettle; deionized water is used as a solvent, 0.46mol/L urea is dissolved to be used as a hydrolytic agent, 0.01 mol/L ammonium fluoride is added to be used as a growth guiding agent, and cobalt ion salt and nickel ion salt are added under magnetic stirring, so that the ratio of cobalt to nickel elements is 9/1. Uniformly mixing, transferring the mixture to a reaction kettle, immersing a carbon felt in the lining, and keeping the mixture at 180 ℃ for hydrothermal reaction for 7 hours; and after cooling, washing the polyacrylonitrile carbon felt with deionized water, and drying at 70 ℃ overnight to obtain the layered cobalt-nickel hydroxide/polyacrylonitrile carbon felt composite material which is marked as Co/Ni PAN-180.
Example 4:
putting a polyacrylonitrile carbon felt (PAN) acidified by concentrated acid into the inner liner of the reaction kettle; deionized water is used as a solvent, 0.46mol/L urea is dissolved to be used as a hydrolytic agent, 0.01 mol/L ammonium fluoride is added to be used as a growth guiding agent, and cobalt ion salt and nickel ion salt are added under magnetic stirring, so that the ratio of cobalt to nickel elements is 6/4. Uniformly mixing, transferring the mixture to a reaction kettle, immersing a carbon felt in the lining, and keeping the mixture at the temperature of 120 ℃ for hydrothermal reaction for 7 hours; and after cooling, washing the polyacrylonitrile carbon felt with deionized water, and drying at 70 ℃ overnight to obtain the layered cobalt-nickel hydroxide/polyacrylonitrile carbon felt composite material which is marked as Co/Ni 6/4-PAN.
Example 5:
putting a polyacrylonitrile carbon felt (PAN) acidified by concentrated acid into the inner liner of the reaction kettle; deionized water is used as a solvent, 0.46mol/L urea is dissolved to be used as a hydrolytic agent, 0.01 mol/L ammonium fluoride is added to be used as a growth guiding agent, and cobalt ion salt and nickel ion salt are added under magnetic stirring, so that the ratio of cobalt to nickel elements is 4/6. Uniformly mixing, transferring the mixture to a reaction kettle, immersing a carbon felt in the lining, and keeping the mixture at the temperature of 120 ℃ for hydrothermal reaction for 7 hours; and after cooling, washing the polyacrylonitrile carbon felt with deionized water, and drying at 70 ℃ overnight to obtain the layered cobalt-nickel hydroxide/polyacrylonitrile carbon felt composite material which is marked as Co/Ni 4/6-PAN.
Comparative example 1:
deionized water is used as a solvent, 0.46mol/L urea is dissolved to be used as a hydrolytic agent, 0.01 mol/L ammonium fluoride is added to be used as a growth guiding agent, and cobalt ion salt and nickel ion salt are added under magnetic stirring, so that the ratio of cobalt to nickel elements is 9/1. Uniformly mixing, transferring to the inner liner of a reaction kettle, and keeping the hydrothermal reaction at 120 ℃ for 7 hours; after cooling, 7000 rpm centrifugal separation of reaction liquid, washing with deionized water, and drying overnight at 70 ℃ to obtain hydroxide powder material, which is marked as Co/Ni-120; and marking the polyacrylonitrile carbon felt after concentrated acid acidification as PAN.
Comparative example 2:
putting two portions of polyacrylonitrile carbon felt (PAN) after being acidified by concentrated acid into the linings of the two reaction kettles respectively; deionized water is used as a solvent, 0.55 mol/L urea is dissolved to be used as a hydrolytic agent, 0.012 mol/L ammonium fluoride is added to be used as a growth guiding agent, cobalt ion salt and nickel ion salt are respectively added under magnetic stirring, after uniform mixing, the mixture is transferred to the linings of two reaction kettles to immerse a carbon felt, and the hydrothermal reaction is kept at 120 ℃ for 7 hours; after cooling, washing the polyacrylonitrile carbon felt with deionized water, and drying at 70 ℃ overnight to obtain a layered cobalt hydroxide/polyacrylonitrile carbon felt composite material, which is marked as Co-PAN; the layered nickel hydroxide/polyacrylonitrile carbon felt composite material is marked as Ni-PAN.
FIG. 1 is an SEM image of the Co/Ni PAN-120 composite material prepared in example 2. As shown in the figure, under a low-magnification view, it can be clearly seen that a layer of active material is tightly wrapped on the outer side of the carbon fiber, the thickness is 2 ~ 5 μm, and the loading is uniform.
FIG. 2 is an XPS plot of Co/Ni 6/4-PAN composite prepared in example 4, Co-PAN and Ni-PAN prepared in comparative example 2. As shown in the figure, through the hydrothermal reaction, cobalt and nickel elements are detected on the surface of the polyacrylonitrile carbon felt.
FIG. 3 is an XRD pattern of PAN prepared in comparative example 1, Co-PAN and Ni-PAN prepared in comparative example 2. As shown in the figure, the acidified PAN felt has distinct characteristic peaks of carbon, which are respectively designated as 003 and 101; after loading the hydroxides of cobalt and nickel in the hydrothermal reaction, the characteristic peaks of carbon disappeared from the figure, and they were compared with beta-Co (OH)2PDF #51-1731, Ni (OH)2·7H2The PDF #38-0715 of O corresponds to each other, which indicates that the active component for growth is corresponding hydroxide, the layered structure of the hydroxide determines a large specific surface area and a plurality of active sites, the low valence state of the metal ions can be oxidized into a high valence state in situ in the OER reaction process, namely, oxyhydroxide, and the oxyhydroxide serves as a real electrocatalytic active site to generate oxygen evolution reaction in the electrolyte.
Example 6:
grinding the catalyst into powder, weighing 10 mg, dispersing in 1 mL of ethanol, 1.42 mL of deionized water and 80 muL of 5% Nafion solution, ultrasonically mixing uniformly, dripping 10 muL of slurry on a glassy carbon electrode, irradiating and drying by an infrared lamp, and measuring an LSV curve on a Princeton electrochemical workstation.
The electrocatalysis performance tests all use a saturated Ag/AgCl electrode as a reference, a Pt electrode as a counter electrode, a sweeping speed of 5mV/s, 0.1mol/L PBS as an electrolyte, and water bath control is carried out at 25 ℃.
The Tafel slope is calculated from E = a + b log J, where b is the Tafel slope.
Example 7:
grinding the catalyst into powder, weighing 10 mg, dispersing in 1 mL of ethanol, 1.42 mL of deionized water and 80 muL of 5% Nafion solution, ultrasonically mixing uniformly, dripping 10 muL of slurry on a glassy carbon electrode, irradiating and drying by an infrared lamp, and measuring a CV curve on a Princeton electrochemical workstation.
The electrocatalytic performance tests all use a saturated Ag/AgCl electrode as a reference, a Pt electrode as a counter electrode, a sweeping speed of 10mV/s and 0.1mol/L PBS as electrolyte; the 0.1mol/L PBS and 100ppm phenol mixed solution simulates polluted electrolyte, and the water bath is controlled at 25 ℃.
Example 8:
the Co/Ni PAN-120 composite catalyst obtained in the example 2 is cut by 1.51.5×0.3 cm3And the stainless steel electrode clamp is fixed and directly used as a working electrode, the electrolyte is wetted for 15 min before the test, the mixture is magnetically stirred, and a timing current I-t curve is measured on a Princeton electrochemical workstation.
The electrocatalytic performance tests all use a saturated Ag/AgCl electrode as a reference, a Pt electrode as a counter electrode, a fixed oxygen evolution potential and 0.1mol/L PBS as electrolyte; the 0.1mol/L PBS and 100ppm phenol mixed solution simulates polluted electrolyte, and the water bath is controlled at 25 ℃.
FIG. 4 is an OER linear voltammogram and corresponding Tafel plot for the Co/Ni PAN-90 composite prepared in example 1, the Co/Ni PAN-120 composite prepared in example 2, the Co/Ni PAN-180 composite prepared in example 3, the PAN modified glassy carbon electrode prepared in comparative example 1. It is evident from the graph (a) that the OER starting potential of the Co/Ni PAN-120 modified electrode is 1.6V (vsRhE), and the current density at the same oxygen evolution potential is much higher than that of other materials; the Tafel slopes corresponding to the respective polarization intervals were 123.07 mV/dec, 139.16 mV/dec, 131.76 mV/dec, 456.75 mV/dec, respectively, with a low Tafel slope indicating a high electron mobility rate (panel b). The hydrothermal reaction temperature has obvious influence on the catalytic oxygen evolution performance of the material.
FIG. 5 is the OER linear voltammogram of the Co/Ni PAN-120 composite prepared in example 2, the Co/Ni 6/4-PAN composite prepared in example 4, and the Co/Ni 4/6-PAN composite modified glassy carbon electrode prepared in example 5. As shown in the figure, the initial potential is obviously reduced along with the increase of the molar ratio of the cobalt, so that the metallic cobalt has higher electrocatalytic oxygen evolution performance under neutral electrolysis conditions, because hydrated trivalent cobalt ions have strong oxidizability in solution and can even directly oxidize water, and Co has high oxidation stability2+Is easily oxidized into Co3+。
FIG. 6 is the OER cyclic voltammogram of the Co/Ni PAN-120 composite material prepared in example 2 and the Co/Ni-120 powder material modified glassy carbon electrode in comparative example 1. The comparison shows that Co/Ni-120 has oxidation reaction at 1.52V (vsRHE), the valence is increased, the Co/Ni-120 is changed into oxyhydroxide serving as an active site for electrocatalytic reaction, the initial potential is lower after the reaction is carried by PAN, the current density is increased more quickly, and the oxygen evolution efficiency is higher. The results show that the metal cobalt, nickel and carbon felt load not only reduces the cost of the metal, but also improves the conductivity and the electrocatalytic oxygen evolution performance of the metal.
FIG. 7 is the OER cyclic voltammogram of the Co/Ni PAN-120 composite modified glassy carbon electrode prepared in example 2 at 0.1mol/L PBS and 0.1mol/L PBS plus 100ppm phenol. The industrial wastewater contains a large amount of phenolic organic pollutants, phenol is used as a non-degradable pollutant and is added into the electrolyte to simulate the complicated industrial electrolysis environment, as shown in the figure, 100ppm is added, the cobalt oxidation peak potential is increased, the initial oxygen evolution potential is increased by about 0.1V, the potential window is enlarged by 0.2V, the response current is increased, and the high-activity oxygen evolution reaction is maintained.
FIG. 8 is a plot of OER timing current for the Co/Ni PAN-120 composite prepared in example 2 directly as the working electrode at 0.1 mol/LPBS and 0.1mol/L PBS plus 100ppm phenol. Selecting lower oxygen evolution potential 1.8V (vsRhE), magnetically stirring, reacting for 15 h, as shown in the figure, the composite material can be directly used as an anode for catalyzing the oxygen evolution reaction under the neutral electrolysis condition for a long time, and has guiding significance for actually developing the catalyst; after the electrolyte is added with the phenol, the current density is reduced to a certain extent, which indicates that the phenol can partially cover the active sites of the catalyst, thereby affecting the oxygen evolution efficiency, but the catalyst can still maintain certain electrocatalytic activity, and provides material support for the application field of future anode oxygen evolution.
It should be understood that the above-mentioned embodiments are only for illustrating the technical idea and features of the present invention, and are intended to enable the researchers in this direction to understand the contents and implement the present invention, and not to limit the protection scope of the present invention. Changes and modifications made according to the spirit of the present invention should fall within the scope of the present invention.
Claims (9)
1. A cobalt-nickel hydroxide sleeve type modified carbon fiber composite material is characterized in that: comprises a three-dimensional conductive matrix material and a catalytic active component compounded on the surface of the matrix; the two components form a sleeve type integrated electrode material without an adhesive.
2. The cobalt-nickel hydroxide sleeve-type modified carbon fiber composite material as claimed in claim 1, wherein the matrix material comprises one of conductive polyacrylonitrile carbon felt, activated carbon felt, viscose-based graphite felt and carbon fiber cloth, and the diameter of the carbon fiber is 5 ~ 20 μm;
the catalytic active component is layered cobalt-nickel hydroxide wrapping carbon fibers, the thickness of the layered cobalt-nickel hydroxide is 2 ~ 5 mu m, and the metal atom recombination quantity on the unit mass of the carbon materials is 1 ~ 6 mmol.
3. A method for preparing a cobalt-nickel hydroxide sleeve-modified carbon fiber composite material according to claim 1 or 2, characterized in that: divalent cobalt and nickel metal ions are subjected to in-situ growth of hydroxide on a carbon fiber substrate by a one-step hydrothermal method, and the hydroxide is directly applied to neutral environment oxygen evolution research as a composite material: the active component and the matrix are compounded to form the sleeve type integrated electrode material without the adhesive.
4. The method for preparing the cobalt-nickel hydroxide sleeve-type modified carbon fiber composite material according to claim 3, wherein the method comprises the following steps: the method comprises the following steps:
(1) cutting a carbon material with the length of 3 ~ 8 cm, the width of 2 ~ 5 cm and the thickness of 0.1 ~ 1 cm, sequentially carrying out ultrasonic cleaning in acetone, ethanol and deionized water, drying, immersing a carbon substrate in 20 ~ 40 mL of concentrated nitric acid, and carrying out hydrothermal reaction for acidification treatment, so that the hydrophilicity of the carbon material is improved, oxygen-containing groups are increased, and the loading of active components is facilitated;
(2) weighing cobalt and nickel ion salts, dissolving the cobalt and nickel ion salts in a mixed solution of 0.2 ~ 0.6.6 mol/L urea and 0.005 ~ 0.05.05 mol/L ammonium fluoride under magnetic stirring, wherein the molar ratio of cobalt to nickel elements is (10 ~ 0.1.1)/1, the molar ratio of the total of metal ion salts to urea to ammonium fluoride is 1-3: 2-6: 0.1-0.5, immersing an acidified carbon felt in a precursor metal salt solution, reacting at the hydrothermal temperature of 70 ~ 180 ℃ for 4 ~ 24 hours, and cleaning and drying the composite material by deionized water to obtain the cobalt-nickel hydroxide sleeve type modified carbon fiber composite material.
5. The method for preparing the cobalt-nickel hydroxide sleeve-type modified carbon fiber composite material according to claim 4, wherein the method comprises the following steps: the carbon material is one of polyacrylonitrile carbon felt, activated carbon felt, viscose-based graphite felt and carbon fiber cloth, and the carbon felt material is mainly formed, provides a carrier with an irregular shape and has conductivity.
6. The method for preparing the cobalt-nickel hydroxide sleeve-type modified carbon fiber composite material according to claim 4, wherein the method comprises the following steps: the cobalt ion salt is selected from one or more of cobalt sulfate, cobalt nitrate and cobalt chloride; the nickel ion salt is selected from one or more of nickel sulfate, nickel nitrate and nickel chloride.
7. An application of the cobalt-nickel hydroxide sleeve-type modified carbon fiber composite material as claimed in claim 1 or 2 in electrocatalytic oxygen evolution in neutral medium and pollutant-added environment.
8. Use according to claim 7, characterized in that: the neutral condition is 0.1mol/L phosphate buffer solution PBS, and the pH value is kept stable in the electrolytic process; phenol is used as a pollutant to be added into the electrolyte, and the oxygen evolution performance of the electrocatalyst in a complex electrolysis environment is further verified.
9. Use according to claim 7, characterized in that: a three-electrode system is adopted, the working electrode is the cobalt-nickel hydroxide sleeve type modified carbon fiber composite material, the reference electrode is a silver/silver chloride electrode, and the counter electrode is a platinum electrode; the test is carried out on a Princeton electrochemical workstation, electrolyte is respectively 0.1mol/L phosphate buffer solution and phosphate buffer solution added with 100ppm phenol, the temperature of the electrolyte is controlled by water bath, the electrocatalysis process is ensured to be stably carried out at 25 ℃, and the influence of the temperature on the electrocatalysis performance is eliminated;
electrochemical oxygen evolution test: linear sweep voltammogram: sweeping at 5mV/s and 1600 rpm, and exploring the electrochemical kinetics of the composite material OER; cyclic voltammogram: taking a glassy carbon electrode as a working electrode, sweeping at a speed of 10mV/s, and testing the influence of the environmental change of the electrolyte on the material performance; the electrode potential is converted to the electrode potential relative to the reversible hydrogen electrode using the formula: e (rhe) = E (Ag/AgCl) +0.059 × pH + 0.197;
and (3) stability testing: and (3) respectively fixing applied bias voltages in the environment of neutral electrolyte, neutral dielectric medium and phenol in a constant voltage mode to prepare the electrocatalyst which is directly used as a working electrode, and detecting the change of current density along with time.
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