CN111135866A - Preparation method of multi-level structure electrocatalyst based on combination of MOFs and LDH - Google Patents
Preparation method of multi-level structure electrocatalyst based on combination of MOFs and LDH Download PDFInfo
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- CN111135866A CN111135866A CN201911167907.6A CN201911167907A CN111135866A CN 111135866 A CN111135866 A CN 111135866A CN 201911167907 A CN201911167907 A CN 201911167907A CN 111135866 A CN111135866 A CN 111135866A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 34
- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 26
- 239000010411 electrocatalyst Substances 0.000 title claims abstract description 23
- 239000000463 material Substances 0.000 claims abstract description 93
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 84
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 24
- 239000004744 fabric Substances 0.000 claims abstract description 24
- 239000012046 mixed solvent Substances 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims abstract description 14
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims abstract description 14
- 239000008367 deionised water Substances 0.000 claims abstract description 14
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 14
- 150000001868 cobalt Chemical class 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 12
- 230000008569 process Effects 0.000 claims abstract description 11
- 150000002815 nickel Chemical class 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims abstract description 4
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 4
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical group [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 4
- 229940078494 nickel acetate Drugs 0.000 claims description 4
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 4
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 4
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 4
- 229940011182 cobalt acetate Drugs 0.000 claims description 3
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 3
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 3
- 229940044175 cobalt sulfate Drugs 0.000 claims description 3
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 3
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 23
- 230000008901 benefit Effects 0.000 abstract description 9
- 238000009827 uniform distribution Methods 0.000 abstract description 4
- 238000006243 chemical reaction Methods 0.000 description 23
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 description 17
- 238000006555 catalytic reaction Methods 0.000 description 12
- 241000446313 Lamella Species 0.000 description 9
- 238000001027 hydrothermal synthesis Methods 0.000 description 9
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(II) nitrate Inorganic materials [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 8
- 229910000510 noble metal Inorganic materials 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 7
- 239000007769 metal material Substances 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 230000002195 synergetic effect Effects 0.000 description 3
- 230000004888 barrier function Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- HTXDPTMKBJXEOW-UHFFFAOYSA-N iridium(IV) oxide Inorganic materials O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(IV) oxide Inorganic materials O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/845—Cobalt
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Abstract
The invention discloses a preparation method of a multi-level structure electrocatalyst based on MOFs and LDH combination, which comprises the following steps: 1) mixing methanol and deionized water to obtain a mixed solvent; 2) dissolving cobalt salt, nickel salt and N, N, N-trimethyl-1-hexadecyl ammonium bromide in a mixed solvent, and uniformly stirring to obtain a solution A; 3) adding hydrophilic carbon cloth into the solution A, and reacting to obtain CoNi-LDH-CF; 4) dissolving cobalt salt and 2-methylimidazole in a methanol solution to form a solution B; 5) adding a CoNi-LDH-CF material into the solution B, and reacting to obtain the CoNi-LDH/ZIF-67-CF material. The preparation method is simple, the cost is low, the catalytic performance is excellent, the prepared electrocatalyst has the characteristics of large specific surface area, regular structure, uniform doping and uniform distribution, the LDH and the MOFs materials are combined to form the electrocatalyst with a multilevel structure, the advantages of the LDH and the MOFs materials can be combined in the catalytic process, and the advantages of the multilevel structure materials are shown, so that the catalytic performance of the material is greatly improved.
Description
Technical Field
The invention belongs to the field of material chemistry, and particularly relates to a preparation method of a multi-level structure electrocatalyst based on MOFs and LDH combination.
Background
Double metal hydroxides (LDHs) are host-guest compounds with special structures and functions, and have received wide attention due to their high surface area caused by their layered structures and various properties brought by different metal ions. LDH materials and derivatives thereof generally have very excellent catalytic properties and have very important development potential in the electrochemical field. Transition metal based oxygen electrocatalysts are a recent focus of research, particularly on nickel-based materials. The cobalt element is doped in the electrocatalysis process, so that the performance of the nickel-based catalyst can be improved, and the development of LDHs is concerned. The catalytic performance of LDHs in ORR and OER is equivalent to that of a noble metal oxide catalyst, so that the LDHs has wider application in the field of oxygen electrocatalysis and is expected to replace the traditional catalyst.
As a novel porous organic-inorganic hybrid material, a metal-organic framework (MOFs) material has the characteristics of various types, multiple functions, adjustable structure and the like. Similar to inorganic materials, MOFs containing redox active metal centers also have certain electrochemical activity. The MOFs have metal sites coordinated by organic molecules and easily-adjusted pore structures, and thus, a structural basis is provided for optimizing and improving the performance of the MOFs.
Oxygen Evolution (OER) is a very slow kinetic four-electron process that often occurs through multiple reactions with single electron transfer in each individual step. Thus, the accumulation of energy barriers at each individual step eventually makes the OER kinetics become particularly slow, leading to large overpotentials. To overcome the energy barrier during OER, and to achieve a smaller overpotential, electrocatalyst materials must be designed for high stability and low cost. In recent years, non-noble metal-based materials have been reported in the literature for use in OER electrocatalytic testing studies. And IrO2And RuO2Compared with noble metal-based materials, non-noble metal-based materials are low in price and easily available in raw materials. However, reports on non-noble metal-based materials as OER catalysts are still very limited, and the excessive overpotential still enables the OER catalysts to be applied to the OER reaction processThe research is limited. The LDH and the MOFs are combined to form the electrocatalyst with a multilevel structure, the advantages of the LDH and the MOFs can be combined in the catalysis process, and the catalysis advantages of the multilevel structure material are shown, so that the material catalysis performance is greatly improved, and the material catalysis activity can be optimized by forming a non-noble metal-based material through the synergistic effect of different metal atoms in the reaction process.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides a preparation method of a multi-level structure electrocatalyst based on MOFs and LDH combination, which has good OER electrocatalytic performance and simple preparation method.
The invention provides a preparation method of a multi-level structure electrocatalyst based on combination of MOFs and LDH, which comprises the following steps:
1) mixing methanol and deionized water to obtain a mixed solvent;
2) dissolving cobalt salt, nickel salt and N, N, N-trimethyl-1-hexadecylammonium bromide in the mixed solvent obtained in the step 1), and uniformly stirring to obtain a solution A;
3) adding hydrophilic carbon cloth into the solution A, and reacting for 10-20h at the temperature of 140-;
4) dissolving cobalt salt and 2-methylimidazole in a methanol solution to form a solution B;
5) adding the CoNi-LDH-CF material obtained in the step 3) into the solution B, and reacting at the temperature of 100-180 ℃ for 10-20h to obtain the CoNi-LDH/ZIF-67-CF material.
Preferably, the volume ratio of the methanol to the deionized water in the step 1) is 2-8: 1.
Preferably, the cobalt salt in step 2) is cobalt acetate, cobalt sulfate, cobalt chloride or a combination of two or three; the nickel salt is nickel acetate, nickel sulfate or nickel chloride, or the combination of two or three of the nickel acetate, the nickel sulfate and the nickel chloride.
Preferably, the mass ratio of the cobalt salt to the nickel salt in the step 2) is 0.01-1: 2; the mass input of the N, N, N-trimethyl-1-hexadecyl ammonium bromide is 0.2-0.6 g.
Preferably, the amount ratio of the cobalt salt to the 2-methylimidazole substance in the step 4) is 1:2-6, and the volume of the methanol is 10-30 mL.
Preferably, the hydrophilic carbon cloth in the step 3) is 1cm by 4 cm.
The invention aims to further find the electrocatalyst with a multilevel structure, which has the advantages of simple preparation method, low cost and excellent catalytic performance, and firstly synthesizes an LDH material CoNi-LDH-CF growing on carbon cloth, and then obtains the electrocatalytic material with the CoNi-LDH/ZIF-67-CF multilevel structure by hydrothermal treatment. The material has the characteristics of large specific surface area, regular structure, uniform doping and uniform distribution, the LDH and MOFs materials are combined to form the multi-level structure electrocatalyst, the advantages of the LDH and the MOFs materials can be combined in the catalysis process, and the catalysis advantage of the multi-level structure material is shown, so that the material catalysis performance is greatly improved, and the non-noble metal-based material formed by utilizing the synergistic effect of different metal atoms in the reaction process can optimize the material catalysis activity, so that the material is an electrocatalysis material with excellent performance.
The technical scheme adopted by the invention for solving the technical problems is as follows: the material has the characteristics of large specific surface area, regular structure, uniform doping and uniform distribution, the LDH and MOFs materials are combined to form the electrocatalyst with the multilevel structure, the advantages of the LDH and the MOFs materials can be combined in the catalysis process, and the catalysis advantage of the multilevel structure material is displayed, so that the material catalysis performance is greatly improved, and the non-noble metal-based material formed by utilizing the synergistic effect of different metal atoms in the reaction process can optimize the material catalysis activity, so that the electrocatalyst is the electrocatalyst material with the excellent OER performance.
Drawings
FIG. 1 is a scanning electron microscope picture of a sample CoNi-LDH-CF composite material prepared in example 1 of the present invention.
FIG. 2 is a scanning electron microscope picture of a prepared sample CoNi-LDH/ZIF-67-CF multi-level structure electrocatalytic material prepared in example 1 of the present invention.
FIG. 3 is a LSV curve diagram of a CoNi-LDH/ZIF-67-CF multi-level structure electrocatalytic material prepared in example 1 of the present invention.
FIG. 4 is Tafel diagram of CoNi-LDH/ZIF-67-CF multi-level structure electrocatalytic material prepared in example 1 of the present invention.
Detailed Description
In order to make the technical solutions of the present invention better understood, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
(1) Preparation of CoNi-LDH-CF:
(a) mixing 20mL of methanol and 10mL of deionized water to obtain a mixed solvent;
(b) 0.01mmol of CoCl2·6H2O、0.2mmol Ni(NO3)2And 0.4g CTAB is dissolved in the mixed solvent of the step (a) and is stirred uniformly to obtain a solution A;
(c) pouring the solution A into a reaction kettle, adding 1cm by 4cm of hydrophilic carbon cloth, and reacting for 15 hours in an oven at 180 ℃ to obtain CoNi-LDH-CF-1;
(2) preparation of CoNi-LDH/ZIF-67-CF:
(a) 1mmol of CoCl2·6H2Dissolving O and 4mmol of 2-methylimidazole in 20mL of methanol solution to form a solution B;
(b) and (3) pouring the solution B into a reaction kettle, adding the CoNi-LDH-CF material obtained in the step (2), and reacting for 20 hours in an oven at 180 ℃ to obtain the CoNi-LDH/ZIF-67-CF-1 material.
The CoNi-LDH-CF-1 material which grows uniformly on the carbon cloth base is obtained, LDH lamella is very uniform, and the CoNi-LDH/ZIF-67-CF-1 material multi-level structure point catalytic material is formed successfully by hydrothermal reaction again, and has higher material catalytic activity.
Example 2
(1) Preparation of CoNi-LDH-CF:
(a) mixing 20mL of methanol and 10mL of deionized water to obtain a mixed solvent;
(b) 0.1mmol of CoCl2·6H2O、0.2mmol Ni(NO3)2And 0.4g CTAB is dissolved in the mixed solvent of the step (a) and is stirred uniformly to obtain a solution A;
(c) pouring the solution A into a reaction kettle, adding 1cm by 4cm of hydrophilic carbon cloth, and reacting for 15 hours in an oven at 180 ℃ to obtain CoNi-LDH-CF-2;
(2) preparation of CoNi-LDH/ZIF-67-CF:
(a) 1mmol of CoCl2·6H2Dissolving O and 4mmol of 2-methylimidazole in 20mL of methanol solution to form a solution B;
(b) and (3) pouring the solution B into a reaction kettle, adding the CoNi-LDH-CF material obtained in the step (2), and reacting for 20 hours in an oven at 180 ℃ to obtain the CoNi-LDH/ZIF-67-CF-2 material.
As can be seen by combining the figures 1 and 2, the CoNi-LDH-CF-2 material which grows uniformly on the carbon cloth base is obtained, the LDH lamella is very uniform, and the CoNi-LDH/ZIF-67-CF-2 material multi-level structure point catalytic material is formed successfully by hydrothermal reaction again.
It can be seen from the combination of FIGS. 3 and 4 that the overpotential of the sample CoNi-LDH/ZIF-67-CF-2 is 338mV and the Tafel slope is 59mV dec at 10mA of current-1The performance of the catalyst is excellent when the catalyst is used for producing oxygen by electrolyzing water. The preparation method is characterized in that a sample prepared by the method has excellent electro-catalytic performance, and the LDH and the MOFs are combined to form the electro-catalyst with a multilevel structure mainly depending on the structural characteristics of the material, such as large specific surface area, regular structure and uniform distribution.
Example 3
(1) Preparation of CoNi-LDH-CF:
(a) mixing 40mL of methanol and 10mL of deionized water to obtain a mixed solvent;
(b) 0.1mmol of CoCl2·6H2O、0.2mmol Ni(NO3)2And 0.4g CTAB is dissolved in the mixed solvent of the step (a) and is stirred uniformly to obtain a solution A;
(c) pouring the solution A into a reaction kettle, adding 1cm by 4cm of hydrophilic carbon cloth, and reacting for 15 hours in an oven at 180 ℃ to obtain CoNi-LDH-CF-3;
(2) preparation of CoNi-LDH/ZIF-67-CF:
(a) 1mmol of CoCl2·6H2Dissolving O and 4mmol of 2-methylimidazole in 20mL of methanol solution to form a solution B;
(b) and (3) pouring the solution B into a reaction kettle, adding the CoNi-LDH-CF material obtained in the step (2), and reacting for 10 hours in an oven at 180 ℃ to obtain the CoNi-LDH/ZIF-67-CF-3 material.
The CoNi-LDH-CF-3 material which grows uniformly on the carbon cloth base is obtained, LDH lamella is very uniform, and the CoNi-LDH/ZIF-67-CF-3 material multi-level structure point catalytic material is formed successfully by hydrothermal reaction again, and has higher material catalytic activity.
Example 4
(1) Preparation of CoNi-LDH-CF:
(a) mixing 40mL of methanol and 5mL of deionized water to obtain a mixed solvent;
(b) 0.05mmol of Co (NO)3)2·6H2O、0.2mmol Ni(NO3)2And 0.2g CTAB is dissolved in the mixed solvent of the step (a) and is stirred uniformly to obtain a solution A;
(c) pouring the solution A into a reaction kettle, adding 1cm by 4cm of hydrophilic carbon cloth, and reacting in an oven at 140 ℃ for 10 hours to obtain CoNi-LDH-CF-4;
(2) preparation of CoNi-LDH/ZIF-67-CF:
(a) 1mmol of CoCl2·6H2Dissolving O and 2mmol of 2-methylimidazole in 10mL of methanol solution to form a solution B;
(b) and (3) pouring the solution B into a reaction kettle, adding the CoNi-LDH-CF material obtained in the step (2), and reacting for 10 hours in an oven at 100 ℃ to obtain the CoNi-LDH/ZIF-67-CF-4 material.
The CoNi-LDH-CF-4 material which grows uniformly on the carbon cloth base is obtained, LDH lamella is very uniform, and the CoNi-LDH/ZIF-67-CF-4 material multi-level structure point catalytic material is formed successfully by hydrothermal reaction again, and has higher material catalytic activity.
Example 5
(1) Preparation of CoNi-LDH-CF:
(a) mixing 160mL of methanol and 20mL of deionized water to obtain a mixed solvent;
(b) 0.1mmol of CoCl2·6H2O、0.2mmol Ni(NO3)2And 0.6g CTAB is dissolved in the mixed solvent of the step (a) and is stirred uniformly to obtain a solution A;
(c) pouring the solution A into a reaction kettle, adding 1cm by 4cm of hydrophilic carbon cloth, and reacting in an oven at 240 ℃ for 20 hours to obtain CoNi-LDH-CF-5;
(2) preparation of CoNi-LDH/ZIF-67-CF:
(a) 2mmol of CoCl2·6H2Dissolving O and 12mmol of 2-methylimidazole in 30mL of methanol solution to form a solution B;
(b) and (3) pouring the solution B into a reaction kettle, adding the CoNi-LDH-CF material obtained in the step (2), and reacting for 20 hours in an oven at 180 ℃ to obtain the CoNi-LDH/ZIF-67-CF-5 material.
The CoNi-LDH-CF-5 material which grows uniformly on the carbon cloth base is obtained, LDH lamella is very uniform, and the CoNi-LDH/ZIF-67-CF-5 material multi-level structure point catalytic material is formed successfully by hydrothermal reaction again, and has higher material catalytic activity.
Example 6
(1) Preparation of CoNi-LDH-CF:
(a) mixing 40mL of methanol and 10mL of deionized water to obtain a mixed solvent;
(b) 0.1mmol of CoCl2·6H2O、0.2mmol Ni(NO3)2And 0.4g CTAB is dissolved in the mixed solvent of the step (a) and is stirred uniformly to obtain a solution A;
(c) pouring the solution A into a reaction kettle, adding 1cm by 4cm of hydrophilic carbon cloth, and reacting in an oven at 180 ℃ for 20 hours to obtain CoNi-LDH-CF-6;
(2) preparation of CoNi-LDH/ZIF-67-CF:
(a) 1mmol of CoCl2·6H2Dissolving O and 3mmol of 2-methylimidazole in 20mL of methanol solution to form a solution B;
(b) and (3) pouring the solution B into a reaction kettle, adding the CoNi-LDH-CF material obtained in the step (2), and reacting for 10 hours in an oven at 150 ℃ to obtain the CoNi-LDH/ZIF-67-CF-6 material.
The CoNi-LDH-CF-6 material which grows uniformly on the carbon cloth base is obtained, LDH lamella is very uniform, and the CoNi-LDH/ZIF-67-CF-6 material multi-level structure point catalytic material is formed successfully by hydrothermal reaction again, and has higher material catalytic activity.
Example 7
(1) Preparation of CoNi-LDH-CF:
(a) mixing 80mL of methanol and 10mL of deionized water to obtain a mixed solvent;
(b) 0.1mmol of CoCl2·6H2O、0.1mmol Ni(NO3)2And 0.2g CTAB is dissolved in the mixed solvent of the step (a) and is stirred uniformly to obtain a solution A;
(c) pouring the solution A into a reaction kettle, adding 1cm by 4cm of hydrophilic carbon cloth, and reacting in an oven at 180 ℃ for 20 hours to obtain CoNi-LDH-CF-7;
(2) preparation of CoNi-LDH/ZIF-67-CF:
(a) 1mmol of CoCl2·6H2Dissolving O and 4mmol of 2-methylimidazole in 20mL of methanol solution to form a solution B;
(b) and (3) pouring the solution B into a reaction kettle, adding the CoNi-LDH-CF material obtained in the step (2), and reacting for 15h in an oven at 150 ℃ to obtain the CoNi-LDH/ZIF-67-CF-7 material.
The CoNi-LDH-CF-7 material which grows uniformly on the carbon cloth base is obtained, LDH lamella is very uniform, and the CoNi-LDH/ZIF-67-CF-7 material multi-level structure point catalytic material is formed successfully by hydrothermal reaction again, and has higher material catalytic activity.
Example 8
(1) Preparation of CoNi-LDH-CF:
(a) mixing 20mL of methanol and 10mL of deionized water to obtain a mixed solvent;
(b) 0.1mmol of CoCl2·6H2O、0.2mmol Ni(NO3)2And 0.4g CTAB is dissolved in the mixed solvent of the step (a) and is stirred uniformly to obtain a solution A;
(c) pouring the solution A into a reaction kettle, adding 1cm by 4cm of hydrophilic carbon cloth, and reacting for 15 hours in an oven at 180 ℃ to obtain CoNi-LDH-CF-8;
(2) preparation of CoNi-LDH/ZIF-67-CF:
(a) 1mmol of CoCl2·6H2Dissolving O and 3mmol of 2-methylimidazole in 20mL of methanol solution to form a solution B;
(b) and (3) pouring the solution B into a reaction kettle, adding the CoNi-LDH-CF material obtained in the step (2), and reacting for 10 hours in an oven at 120 ℃ to obtain the CoNi-LDH/ZIF-67-CF-8 material.
The CoNi-LDH-CF-8 material which grows uniformly on the carbon cloth base is obtained, LDH lamella is very uniform, and the CoNi-LDH/ZIF-67-CF-8 material multi-level structure point catalytic material is formed successfully by hydrothermal reaction again, and has higher material catalytic activity.
Example 9
(1) Preparation of CoNi-LDH-CF:
(a) mixing 100mL of methanol and 20mL of deionized water to obtain a mixed solvent;
(b) 0.1mmol of CoCl2·6H2Dissolving O and 0.4g CTAB in the mixed solvent in the step (a), and uniformly stirring to obtain a solution A;
(c) pouring the solution A into a reaction kettle, adding 1cm by 4cm of hydrophilic carbon cloth, and reacting for 15 hours in an oven at 200 ℃ to obtain CoNi-LDH-CF-9;
(2) preparation of CoNi-LDH/ZIF-67-CF:
(a) 1mmol of CoCl2·6H2Dissolving O and 4mmol of 2-methylimidazole in 20mL of methanol solution to form a solution B;
(b) and (3) pouring the solution B into a reaction kettle, adding the CoNi-LDH-CF material obtained in the step (2), and reacting for 10 hours in an oven at 180 ℃ to obtain the CoNi-LDH/ZIF-67-CF-9 material.
The CoNi-LDH-CF-9 material which grows uniformly on the carbon cloth base is obtained, LDH lamella is very uniform, and the CoNi-LDH/ZIF-67-CF-9 material multi-level structure point catalytic material is formed successfully by hydrothermal reaction again, and has higher material catalytic activity.
The foregoing detailed description is intended to illustrate and not limit the invention, which is intended to be within the spirit and scope of the appended claims, and any changes and modifications that fall within the true spirit and scope of the invention are intended to be covered by the following claims.
Claims (6)
1. A preparation method of a multi-level structure electrocatalyst based on combination of MOFs and LDH is characterized by comprising the following steps:
1) mixing methanol and deionized water to obtain a mixed solvent;
2) dissolving cobalt salt, nickel salt and N, N, N-trimethyl-1-hexadecylammonium bromide in the mixed solvent obtained in the step 1), and uniformly stirring to obtain a solution A;
3) adding hydrophilic carbon cloth into the solution A, and reacting for 10-20h at the temperature of 140-;
4) dissolving cobalt salt and 2-methylimidazole in a methanol solution to form a solution B;
5) adding the CoNi-LDH-CF material obtained in the step 3) into the solution B, and reacting at the temperature of 100-180 ℃ for 10-20h to obtain the CoNi-LDH/ZIF-67-CF material.
2. The process for the preparation of the multi-level structured electrocatalyst based on MOFs and LDHs binding according to claim 1, characterized in that: the volume ratio of the methanol to the deionized water in the step 1) is 2-8: 1.
3. The process for the preparation of the multi-level structured electrocatalyst based on MOFs and LDHs binding according to claim 1, characterized in that: the cobalt salt in the step 2) is cobalt acetate, cobalt sulfate or cobalt chloride, or a combination of two or three of the cobalt acetate, the cobalt sulfate and the cobalt chloride; the nickel salt is nickel acetate, nickel sulfate or nickel chloride, or the combination of two or three of the nickel acetate, the nickel sulfate and the nickel chloride.
4. The process for the preparation of the multi-level structured electrocatalyst based on MOFs and LDHs binding according to claim 1, characterized in that: the mass ratio of the cobalt salt to the nickel salt in the step 2) is 0.01-1: 2; the mass input of the N, N, N-trimethyl-1-hexadecyl ammonium bromide is 0.2-0.6 g.
5. The process for the preparation of the multi-level structured electrocatalyst based on MOFs and LDHs binding according to claim 1, characterized in that: the mass ratio of the cobalt salt to the 2-methylimidazole in the step 4) is 1:2-6, and the volume of the methanol is 10-30 mL.
6. The process for the preparation of the multi-level structured electrocatalyst based on MOFs and LDHs binding according to claim 1, characterized in that: the hydrophilic carbon cloth in the step 3) is 1cm by 4 cm.
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