CN111188057B - Preparation method of self-supporting composite electrode material - Google Patents
Preparation method of self-supporting composite electrode material Download PDFInfo
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- CN111188057B CN111188057B CN202010024352.6A CN202010024352A CN111188057B CN 111188057 B CN111188057 B CN 111188057B CN 202010024352 A CN202010024352 A CN 202010024352A CN 111188057 B CN111188057 B CN 111188057B
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- 239000002131 composite material Substances 0.000 title claims abstract description 77
- 239000007772 electrode material Substances 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 107
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 107
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 105
- 239000010941 cobalt Substances 0.000 claims abstract description 105
- 239000004744 fabric Substances 0.000 claims abstract description 101
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 99
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 34
- 238000004140 cleaning Methods 0.000 claims abstract description 22
- 238000004070 electrodeposition Methods 0.000 claims abstract description 19
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 43
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 36
- 239000013118 MOF-74-type framework Substances 0.000 claims description 33
- 239000011259 mixed solution Substances 0.000 claims description 30
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 28
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 27
- 239000008367 deionised water Substances 0.000 claims description 27
- 229910021641 deionized water Inorganic materials 0.000 claims description 27
- OYFRNYNHAZOYNF-UHFFFAOYSA-N 2,5-dihydroxyterephthalic acid Chemical compound OC(=O)C1=CC(O)=C(C(O)=O)C=C1O OYFRNYNHAZOYNF-UHFFFAOYSA-N 0.000 claims description 22
- 239000000243 solution Substances 0.000 claims description 21
- 239000012621 metal-organic framework Substances 0.000 claims description 20
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 18
- 239000012046 mixed solvent Substances 0.000 claims description 12
- -1 4,4'-biphenyl dicarboxylate cobalt Chemical compound 0.000 claims description 9
- GFHNAMRJFCEERV-UHFFFAOYSA-L cobalt chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Co+2] GFHNAMRJFCEERV-UHFFFAOYSA-L 0.000 claims description 9
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 9
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 9
- 229910001220 stainless steel Inorganic materials 0.000 claims description 9
- 239000010935 stainless steel Substances 0.000 claims description 9
- NEQFBGHQPUXOFH-UHFFFAOYSA-N 4-(4-carboxyphenyl)benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1C1=CC=C(C(O)=O)C=C1 NEQFBGHQPUXOFH-UHFFFAOYSA-N 0.000 claims description 4
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 claims description 4
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 3
- 239000002659 electrodeposit Substances 0.000 claims 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 13
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 13
- 239000001257 hydrogen Substances 0.000 abstract description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 12
- 229910052760 oxygen Inorganic materials 0.000 abstract description 12
- 239000001301 oxygen Substances 0.000 abstract description 12
- 239000000463 material Substances 0.000 abstract description 8
- 239000003054 catalyst Substances 0.000 abstract description 6
- 239000012921 cobalt-based metal-organic framework Substances 0.000 abstract description 5
- 238000000034 method Methods 0.000 abstract description 5
- 229910000510 noble metal Inorganic materials 0.000 abstract description 5
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 230000009977 dual effect Effects 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000001816 cooling Methods 0.000 description 6
- 238000001291 vacuum drying Methods 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 229910001429 cobalt ion Inorganic materials 0.000 description 5
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- HTXDPTMKBJXEOW-UHFFFAOYSA-N dioxoiridium Chemical compound O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 4
- 239000000835 fiber Substances 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 230000010287 polarization Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- GWZCCUDJHOGOSO-UHFFFAOYSA-N diphenic acid Chemical compound OC(=O)C1=CC=CC=C1C1=CC=CC=C1C(O)=O GWZCCUDJHOGOSO-UHFFFAOYSA-N 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 239000003344 environmental pollutant Substances 0.000 description 3
- 239000003446 ligand Substances 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- DSVGQVZAZSZEEX-UHFFFAOYSA-N [C].[Pt] Chemical compound [C].[Pt] DSVGQVZAZSZEEX-UHFFFAOYSA-N 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 229940044631 ferric chloride hexahydrate Drugs 0.000 description 2
- 229910001448 ferrous ion Inorganic materials 0.000 description 2
- 238000010348 incorporation Methods 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- XGJRLCKXYBBKAI-UHFFFAOYSA-L C1(=C(C(=CC=C1)C(=O)[O-])C(=O)[O-])C1=CC=CC=C1.[Co+2] Chemical compound C1(=C(C(=CC=C1)C(=O)[O-])C(=O)[O-])C1=CC=CC=C1.[Co+2] XGJRLCKXYBBKAI-UHFFFAOYSA-L 0.000 description 1
- NVQNFRJFCJRNJC-UHFFFAOYSA-N C=1(C(C(=O)O)=CC=CC1)C=1C(C(=O)O)=CC=CC1.[Co] Chemical compound C=1(C(C(=O)O)=CC=CC1)C=1C(C(=O)O)=CC=CC1.[Co] NVQNFRJFCJRNJC-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- QVYYOKWPCQYKEY-UHFFFAOYSA-N [Fe].[Co] Chemical compound [Fe].[Co] QVYYOKWPCQYKEY-UHFFFAOYSA-N 0.000 description 1
- 239000013246 bimetallic metal–organic framework Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000000970 chrono-amperometry Methods 0.000 description 1
- 238000004769 chrono-potentiometry Methods 0.000 description 1
- FQMNUIZEFUVPNU-UHFFFAOYSA-N cobalt iron Chemical compound [Fe].[Co].[Co] FQMNUIZEFUVPNU-UHFFFAOYSA-N 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000000724 energy-dispersive X-ray spectrum Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000004502 linear sweep voltammetry Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000010792 warming Methods 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
- 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
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
-
- 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
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/12—Electroplating: Baths therefor from solutions of nickel or cobalt
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/54—Electroplating of non-metallic surfaces
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
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Abstract
本发明公开了一种自支撑复合电极材料的制备方法：包括以下步骤：1、清洗步骤；2、电沉积步骤；3、复合材料制备步骤，本发明与现有技术相比，合成条件温和、方法简便、稳定性良好；且所得材料能作为析氢、析氧双功能的催化剂。在电流密度为20mA/cm2时，析氧过电势最低可达226mV；在电流密度为‑10mA/cm2时，析氢过电势最低可达94mV。此钴基MOF/钴/碳布分层复合自支撑电极材料在电催化水裂解方面与贵金属催化剂相同。
The invention discloses a method for preparing a self-supporting composite electrode material, which comprises the following steps: 1. a cleaning step; 2. an electrodeposition step; 3. a composite material preparation step. Compared with the prior art, the invention has mild synthesis conditions, The method is simple and stable, and the obtained material can be used as a catalyst with dual functions of hydrogen evolution and oxygen evolution. When the current density is 20mA/cm 2 , the oxygen evolution overpotential can be as low as 226mV; when the current density is ‑10mA/cm 2 , the hydrogen evolution overpotential can be as low as 94mV. This cobalt-based MOF/cobalt/carbon cloth layered composite self-supporting electrode material is the same as the noble metal catalyst in electrocatalytic water splitting.
Description
Technical Field
The invention belongs to a preparation method of an electrode material, and particularly belongs to the technical field of preparation methods of composite materials.
Background
With global warming, energy crisis and environmental pollution getting worse, there is an urgent need to find clean renewable energy sources that can replace traditional fossil energy sources. Hydrogen energy is attracting increasing research interest in the fields of chemistry, materials and energy science as an environmentally friendly, high calorific value fuel and an efficient secondary energy source. Hydrogen can be obtained by cracking and separating fossil fuel, decomposing water by light or electric catalysis, and fermenting and converting biomass.
Electrocatalytic water splitting is recognized as one of the sustainable methods to efficiently provide pollution-free and renewable energy hydrogen. Electrocatalytic water splitting consists of an anodic Oxygen Evolution Reaction (OER) and a cathodic Hydrogen Evolution Reaction (HER), in order to reduce the high energy consumption in the OER and HER processes, noble metal materials (e.g. Pt/C and IrO) are often used2) As a catalyst, the noble metal has low abundance and high price, and the commercial application of the noble metal is greatly limited.
Disclosure of Invention
The invention aims to provide a preparation method of a self-supporting composite electrode material without precious metal.
The technical scheme for solving the technical problem of the invention is as follows:
a preparation method of a self-supporting composite electrode material comprises the following steps: comprises the following steps
1. A cleaning step: ultrasonically cleaning the carbon cloth by using anhydrous acetone, anhydrous ethanol and deionized water in sequence for 10 minutes each time;
2. and (3) electrodeposition step: at room temperature, a solution containing 0.05M of cobalt chloride hexahydrate and 0.03M of citric acid was added at 30mA cm-2Electrodepositing for 1-2 hours, and respectively cleaning for 2-3 times by using deionized water and absolute ethyl alcohol to form a cobalt/carbon cloth electrode material;
3. the preparation method of the composite material comprises the following steps: preparing N, N-dimethylformamide: anhydrous ethanol: deionized water 5: 1:1, dissolving 2, 5-dihydroxyterephthalic acid in the mixed solvent, wherein the concentration of the 2, 5-dihydroxyterephthalic acid is 0.5-1.0 multiplied by 10-3M, continuously adding hydrochloric acid into the solution to ensure that the concentration of the hydrochloric acid is 0.75-1.25 multiplied by 10-2M, forming a mixed solution;
adding the mixed solution into a polytetrafluoroethylene stainless steel autoclave, and then putting a cobalt/carbon cloth electrode material into the mixed solution (the volume ratio of the area of the cobalt/carbon cloth electrode material to the mixed solution is 1:10-20 (cm)2And/ml)), preserving the heat at 120 ℃ for 18-24h, cooling to room temperature, washing with DMF (dimethyl formamide) and absolute ethyl alcohol for 2-3 times respectively, and vacuum-drying at 60 ℃ for 12-24 h to form the cobalt-MOF-74/cobalt/carbon cloth composite material.
A preparation method of a self-supporting composite electrode material comprises the following steps: comprises the following steps
1. A cleaning step: ultrasonically cleaning the carbon cloth by using acetone, absolute ethyl alcohol and deionized water in sequence for 10 minutes each time;
2. and (3) electrodeposition step: at room temperature, a solution containing 0.05M of cobalt chloride hexahydrate and 0.03M of citric acid was added at 30mA cm-2Electrodepositing for 1-2 hours, and respectively cleaning for 2-3 times by using deionized water and absolute ethyl alcohol to form a cobalt/carbon cloth electrode material;
3. the preparation method of the composite material comprises the following steps: preparing N, N-dimethylformamide: anhydrous ethanol: deionized water 5: 1:1, dissolving 2, 5-dihydroxyterephthalic acid in the mixed solvent, wherein the concentration of the 2, 5-dihydroxyterephthalic acid is 0.5-1.0 multiplied by 10-3M, continuously adding ferric trichloride hexahydrate into the solution to ensure that the concentration of the ferric trichloride is 4.0-8.0 multiplied by 10-4M, forming a mixed solution;
adding the mixed solution into a polytetrafluoroethylene stainless steel autoclave, and then putting a cobalt/carbon cloth electrode material into the mixed solution (the volume ratio of the area of the cobalt/carbon cloth electrode material to the mixed solution is 1:10-20 (cm)2And/ml)), keeping the temperature at 120 ℃ for 18-24h, cooling to room temperature, washing with DMF and absolute ethyl alcohol for 2-3 times respectively, and vacuum drying at 60 ℃ for 12-24 h to form the cobalt iron-MOF-74/cobalt/carbon cloth composite material.
A preparation method of a self-supporting composite electrode material comprises the following steps: comprises the following steps
1. A cleaning step: ultrasonically cleaning the carbon cloth by using acetone, absolute ethyl alcohol and deionized water in sequence for 10 minutes each time;
2. and (3) electrodeposition step: at room temperature, a solution containing 0.05M of cobalt chloride hexahydrate and 0.03M of citric acid was added at 30mA cm-2Electrodepositing for 1-2 hours, and respectively cleaning for 2-3 times by using deionized water and absolute ethyl alcohol to form a cobalt/carbon cloth electrode material;
3. the preparation method of the composite material comprises the following steps: preparing N, N-dimethylformamide: anhydrous ethanol: deionized water 13: 1:1, dissolving 4, 4' -biphenyldicarboxylic acid in the mixed solvent to a concentration of 0.5 to 1X 10-2M, continuously adding hydrochloric acid into the solution to ensure that the concentration of the hydrochloric acid is 0.75-1.25 multiplied by 10-2M, forming a mixed solution;
adding the mixed solution into a polytetrafluoroethylene stainless steel autoclave, and then putting a cobalt/carbon cloth electrode material into the mixed solution (the volume ratio of the area of the cobalt/carbon cloth electrode material to the mixed solution is 1:10-20 (cm)2And/ml)), keeping the temperature at 120 ℃ for 2-24h, cooling to room temperature, washing with DMF (dimethyl formamide) and absolute ethyl alcohol for 2-3 times respectively, and vacuum-drying at 60 ℃ for 12-24 h to form the 4, 4' -cobalt diphenate MOF/cobalt/carbon cloth composite material.
The cobalt simple substance deposited on the carbon cloth is dissolved by hydrochloric acid to be changed into cobalt ions, and then the cobalt ions and the ligand are subjected to coordination reaction to generate the cobalt MOF. The cobalt simple substance deposited on the carbon cloth provides a cobalt source, is partially converted into cobalt MOF, and enables the cobalt MOF to grow on the cobalt/carbon cloth fiber in situ, so that the three-layer composite self-supporting electrode material of the cobalt MOF/cobalt/carbon cloth can be obtained.
The added ferric trichloride can oxidize the cobalt simple substance to change the cobalt simple substance into cobalt ions and reduce the cobalt ions into ferrous ions at the same time, and the cobalt ions and the ferrous ions simultaneously perform coordination reaction with the ligand to obtain the bimetallic MOF.
2, 5-dihydroxy terephthalic acid or 4, 4' -biphenyl dicarboxylic acid is added as a ligand.
Compared with the prior art, the synthesis condition is mild, the method is simple and convenient, and the stability is good; and the obtained material can be used as a catalyst with double functions of hydrogen evolution and oxygen evolution. At a current density of 20mA/cm2When the oxygen evolution overpotential is high, the minimum oxygen evolution overpotential can reach 226 mV; at a current density of-10 mA/cm2When the electrode material is used, the minimum hydrogen evolution overpotential can reach 94mV, and the performance of the cobalt-based MOF/cobalt/carbon cloth layered composite self-supporting electrode material in the aspect of electrocatalysis water cracking is equivalent to that of a noble metal catalyst.
Description of the drawings:
FIG. 1 is an XRD pattern of a cobalt (iron) -MOF-74/cobalt/carbon cloth material obtained in example 1-2;
FIG. 2 is a scanning electron microscope top view of the cobalt-MOF-74/cobalt/carbon cloth composite obtained in example 1;
FIG. 3 is a side view of a scanning electron microscope of the cobalt-MOF-74/cobalt/carbon cloth composite obtained in example 1;
FIG. 4 is a scanning electron microscope top view of the CoFeMOF-74/Co/carbon cloth composite obtained in example 2;
FIG. 5 is a side view of a scanning electron microscope of the resulting CoFeMOF-74/Co/carbon cloth composite of example 2;
FIG. 6 is a cross-sectional view of a scanning electron microscope of the CoFeMOF-74/Co/carbon cloth composite obtained in example 2;
FIG. 7 is an XPS plot of a CoFeFe-MOF-74/Co/carbon cloth composite obtained in example 1-2;
FIG. 8 is an XPS plot of a CoFeFe-MOF-74/Co/carbon cloth composite obtained in example 2;
FIG. 9 is an EDS diagram of a ferrocobalt-MOF-74/cobalt/carbon cloth composite obtained in example 2;
FIG. 10 is an XRD pattern of the 4, 4' cobalt biphenyldicarboxylate MOF/cobalt/carbon cloth composite obtained in example 3;
FIG. 11 is a scanning electron microscope top view of the 4, 4' cobalt diphenic acid MOF/cobalt/carbon cloth composite obtained in example 3;
FIG. 12 is a graph showing hydrogen evolution polarization curves of cobalt-based MOF/cobalt/carbon cloth composite materials obtained in examples 1 to 3; 1 is a cobalt-MOF-74/cobalt/carbon cloth composite material, 2 is a cobalt iron-MOF-74/cobalt/carbon cloth composite material, and 3 is a 4, 4' -cobalt diphenic acid MOF/cobalt/carbon cloth composite material
FIG. 13 is a graph showing the oxygen evolution polarization curves of the cobalt-based MOF/cobalt/carbon cloth composite obtained in examples 1 to 3; 1 is a cobalt-MOF-74/cobalt/carbon cloth composite material, 2 is a cobalt iron-MOF-74/cobalt/carbon cloth composite material, and 3 is a 4, 4' -cobalt diphenic acid MOF/cobalt/carbon cloth composite material
FIG. 14 is a graph showing the oxygen evolution tafel slope of the cobalt-based MOF/cobalt/carbon composite obtained in examples 1 to 3; 1 is a cobalt-MOF-74/cobalt/carbon cloth composite material, 2 is a cobalt iron-MOF-74/cobalt/carbon cloth composite material, and 3 is a 4, 4' -cobalt diphenic acid MOF/cobalt/carbon cloth composite material
FIG. 15 is a graph showing the fully hydrolyzed water polarization of the CoFeFe-MOF-74/Co/carbon cloth composite obtained in example 2; 2 is cobalt iron MOF-74/cobalt/carbon cloth composite material, and 4 is two electrodes consisting of iridium dioxide/carbon cloth and platinum carbon/carbon cloth.
FIG. 16 is a graph of the hydrogen evolution stability of the resulting coferro-MOF-74/cobalt/carbon cloth composite of example 2;
FIG. 17 is a graph of the oxygen evolution stability of the resulting coferro-MOF-74/cobalt/carbon cloth composite of example 2; 5 is the initial value and 6 is the value after 1000 volt-ampere cycles.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
Example 1
A preparation method of a self-supporting composite electrode material comprises the following steps: comprises the following steps
1. A cleaning step:
ultrasonically cleaning carbon cloth (Taiwan W0S1009) by using anhydrous acetone, anhydrous ethanol and deionized water in sequence, wherein each time is 10 minutes, so as to remove surface pollutants;
2. and (3) electrodeposition step:
at room temperature, 20 ml of a solution containing 0.05M of cobalt chloride hexahydrate and 0.03M of citric acid was used as an electrolyte at 30mA cm-2And (3) performing electrodeposition for 1 hour, and after the electrodeposition, respectively cleaning the carbon cloth electrode material by deionized water and absolute ethyl alcohol for 3 times to obtain the cobalt/carbon cloth electrode material. The cathode electrodeposition reaction is a two-electrode system, the working electrode is carbon cloth, and the counter electrode is a carbon rod.
3. Preparation step of composite Material
Preparing N, N-dimethylformamide: anhydrous ethanol: deionized water 5: 1:1, dissolving 2, 5-dihydroxyterephthalic acid in the mixed solvent to a concentration of 1X 10-3M, continuously adding hydrochloric acid into the solution to ensure that the hydrochloric acid concentration is 1 multiplied by 10-2M。
Adding 20 ml of mixed solution into a polytetrafluoroethylene stainless steel autoclave, and adding a cobalt/carbon cloth electrode material (1 multiplied by 1.5 cm)2) Putting the mixture into the mixed solution, keeping the temperature at 120 ℃ for 24h, cooling to room temperature, washing with DMF (dimethyl formamide) and absolute ethyl alcohol for 3 times respectively, and vacuum-drying at 60 ℃ for 12h to form the cobalt-MOF-74/cobalt/carbon cloth composite material.
As shown in fig. 1: the composition of the cobalt MOF/cobalt/carbon cloth composite material can be verified by showing corresponding MOF characteristic peaks in XRD peaks of the cobalt-MOF-74/cobalt/carbon cloth composite material, namely a carbon cloth peak (PDF No.41-1487) and a cobalt single mass peak (PDF No. 05-0727).
As shown in figures 2 and 3, the prepared material has the morphology that the nano-scale wedge-shaped cobalt-MOF-74 is uniformly distributed on the cobalt/carbon cloth fiber.
Example 2:
1. a cleaning step:
ultrasonically cleaning carbon cloth (Taiwan W0S1009) by using anhydrous acetone, anhydrous ethanol and deionized water in sequence, wherein each time is 10 minutes, so as to remove surface pollutants;
2. and (3) electrodeposition step:
at room temperature, 20 ml of a solution containing 0.05M of cobalt chloride hexahydrate and 0.03M of citric acid was used as an electrolyte at 30mA cm-2And (3) performing electrodeposition for 1 hour, and after the electrodeposition, respectively cleaning the carbon cloth electrode material by deionized water and absolute ethyl alcohol for 3 times to obtain the cobalt/carbon cloth electrode material. The cathode electrodeposition reaction is a two-electrode system, the working electrode is carbon cloth, and the counter electrode is a carbon rod.
3. Preparation step of composite Material
Preparing N, N-dimethylformamide: anhydrous ethanol: deionized water 5: 1:1, dissolving 2, 5-dihydroxyterephthalic acid in the mixed solvent to a concentration of 1X 10-3M, continuing to add ferric chloride hexahydrate to make the concentration of the ferric chloride hexahydrate 8X 10-4M。
Adding 20 ml of mixed solution into a polytetrafluoroethylene stainless steel autoclave, and adding a cobalt/carbon cloth electrode material (1 multiplied by 1.5 cm)2) Putting into the mixed solution, keeping the temperature at 120 ℃ for 24h, cooling to room temperature, washing with DMF and absolute ethyl alcohol for 3 times respectively, and vacuum drying at 60 ℃ for 12h to form the cobalt iron-MOF-74/cobalt/carbon cloth composite material.
As shown in fig. 1: the composition of the cobalt iron-MOF-74/cobalt/carbon cloth composite material can be confirmed by that the existing carbon cloth peak (PDF No.41-1487) and cobalt single peak (PDF No.05-0727) in the XRD peaks of the cobalt iron-MOF-74/cobalt/carbon cloth composite material also have corresponding MOF characteristic peaks.
As shown in figures 4 and 5, the morphology of the prepared material is that the cobalt iron-MOF-74 with the nanometer level wedge shape is uniformly distributed on the cobalt/carbon cloth fiber.
As shown in fig. 6, which is a cross-sectional view of the resulting broken cofe-MOF-74/cobalt/carbon cloth composite, it can be clearly seen that the composite is composed of three layers of carbon fibers, elemental cobalt nanosheets and wedged nanoscale MOF-74.
As shown in fig. 7: in the XPS plot of Fe 2p, the peaks at 711.2 and 724.4eV and the satellite peaks at 716.1 and 730.1eV correspond to Fe2+. The peak of Co 2p can be seen to shift to 781.11eV at 781.46eV after Fe ion incorporation.
As shown in fig. 8: the element characteristic peak of Fe appears in the EDS spectrum, and further confirms the successful incorporation of Fe.
As shown in fig. 15: and the comparison graph of the total hydrolysis overpotential of the cobalt iron-MOF-74/cobalt/carbon cloth composite material and two electrodes consisting of iridium dioxide/carbon cloth and platinum carbon/carbon cloth. The overpotential of the cofe-MOF-74/cobalt/carbon cloth composite was lower after the current density was greater than 186 milliamps/cm.
As shown in fig. 16: the chronopotentiometric graph of the cobalt iron-MOF-74/cobalt/carbon cloth composite material at the current density of-10 milliampere/square centimeter is subjected to hydrogen evolution catalysis for 35 hours, and the potential rises by about 35 millivolts.
As shown in fig. 17: the chronopotentiometric graph of the cobalt iron-MOF-74/cobalt/carbon cloth composite material at the current density of 20 milliampere/square centimeter is subjected to oxygen evolution catalysis for 70 hours, and the potential rises by about 50 millivolts.
Example 3
A preparation method of a self-supporting composite electrode material comprises the following steps: comprises the following steps
1. A cleaning step:
ultrasonically cleaning carbon cloth (Taiwan W0S1009) by using anhydrous acetone, anhydrous ethanol and deionized water in sequence, wherein each time is 10 minutes, so as to remove surface pollutants;
2. and (3) electrodeposition step:
at room temperature, 20 ml of a solution containing 0.05M of cobalt chloride hexahydrate and 0.03M of citric acid was used as an electrolyte at 30mA cm-2And (3) performing electrodeposition for 1 hour, and after the electrodeposition, respectively cleaning the carbon cloth electrode material by deionized water and absolute ethyl alcohol for 3 times to obtain the cobalt/carbon cloth electrode material. The cathode electrodeposition reaction is a two-electrode system, the working electrode is carbon cloth, and the counter electrode is a carbon rod.
3. Preparation step of composite Material
Preparing N, N-dimethylformamide: anhydrous ethanol: deionized water 13: 1:1, dissolving 4, 4' -biphenyldicarboxylic acid in the mixed solvent to a concentration of 1X 10-2M, continuously adding hydrochloric acid into the solution to make the hydrochloric acid concentration of the solution be 1 x 10-2M。
Adding 20 ml of mixed solution into a polytetrafluoroethylene stainless steel autoclave, and adding a cobalt/carbon cloth electrode material (1 multiplied by 1.5 cm)2) And putting the mixture into the mixed solution, preserving heat at 120 ℃ for 24h, cooling to room temperature, washing with DMF (dimethyl formamide) and absolute ethyl alcohol for 3 times respectively, and performing vacuum drying at 60 ℃ for 12h to form the 4, 4' -biphenyl dicarboxylic acid cobalt MOF/cobalt/carbon cloth composite material.
As shown in fig. 10: the morphology of the 4, 4' -biphenyldicarboxylic acid cobalt MOF/cobalt/carbon cloth composite material shows that the flaky MOF material is uniformly distributed on the cobalt/carbon cloth fiber.
As shown in fig. 11: the existing carbon distribution peak (PDF No.41-1487) and cobalt single mass peak (PDF No.05-0727) in the XRD peaks of the 4, 4 '-cobalt diphenic dicarboxylate MOF/cobalt/carbon cloth composite material also have corresponding MOF characteristic peaks, so that the composition of the 4, 4' -cobalt diphenic dicarboxylate MOF/cobalt/carbon cloth composite material can be verified.
In order to evaluate the catalytic electrolysis water performance of the obtained material, the hydrogen evolution performance and the oxygen evolution performance of the self-supporting composite material are measured, wherein the hydrogen evolution performance and the oxygen evolution performance comprise overpotential, Tafel slope and stability.
Preparing 1mol L of-150mL of KOH solution. The electrochemical performance of the catalyst was tested on the CHI660E electrochemical workstation using a three-electrode system with an Hg/HgO electrode as a reference electrode, a carbon rod as a counter electrode, and a self-supporting composite as a working electrode.
The polarization curve reflecting the overpotential was obtained by linear sweep voltammetry on an electrochemical workstation.
The tafel slope is a parameter of the dynamic property of the self-supporting composite material, and is calculated by using the formula eta ═ b log (j) + a, wherein j is the current density and b is the tafel slope.
The stability was judged by a chronoamperometry or chronopotentiometry for a long time.
The results are shown in table 1:
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