CN111389466A - Cobalt (II) metal organic framework material and application thereof in electrocatalytic hydrogen evolution - Google Patents
Cobalt (II) metal organic framework material and application thereof in electrocatalytic hydrogen evolution Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 58
- 239000001257 hydrogen Substances 0.000 title claims abstract description 37
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 37
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 27
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 title claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910001868 water Inorganic materials 0.000 claims abstract description 25
- GFHNAMRJFCEERV-UHFFFAOYSA-L cobalt chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Co+2] GFHNAMRJFCEERV-UHFFFAOYSA-L 0.000 claims abstract description 8
- NLKPHVPDYJGDES-UHFFFAOYSA-N 2,4,6-trimethyl-6-phenylcyclohexa-1,3-diene-1,3,5-tricarboxylic acid Chemical compound CC1(C(C(=C(C(=C1C(=O)O)C)C(=O)O)C)C(=O)O)C1=CC=CC=C1 NLKPHVPDYJGDES-UHFFFAOYSA-N 0.000 claims abstract description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 32
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 239000011259 mixed solution Substances 0.000 claims description 17
- 239000013078 crystal Substances 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 4
- 238000009210 therapy by ultrasound Methods 0.000 claims description 4
- RILZRCJGXSFXNE-UHFFFAOYSA-N 2-[4-(trifluoromethoxy)phenyl]ethanol Chemical compound OCCC1=CC=C(OC(F)(F)F)C=C1 RILZRCJGXSFXNE-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 claims description 2
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- 230000035484 reaction time Effects 0.000 claims description 2
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- 230000002194 synthesizing effect Effects 0.000 claims 3
- 238000006356 dehydrogenation reaction Methods 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 15
- 238000002360 preparation method Methods 0.000 abstract description 7
- 229920000557 Nafion® Polymers 0.000 abstract description 3
- 239000002178 crystalline material Substances 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 238000004729 solvothermal method Methods 0.000 abstract description 2
- 238000005868 electrolysis reaction Methods 0.000 abstract 1
- 238000011056 performance test Methods 0.000 abstract 1
- 239000012921 cobalt-based metal-organic framework Substances 0.000 description 24
- -1 hydrogen ions Chemical class 0.000 description 9
- 239000000725 suspension Substances 0.000 description 5
- PBPZGWJKXHZWFE-UHFFFAOYSA-N 4-[3,5-bis(4-carboxyphenyl)-2,4,6-trimethylphenyl]benzoic acid Chemical compound CC1=C(C=2C=CC(=CC=2)C(O)=O)C(C)=C(C=2C=CC(=CC=2)C(O)=O)C(C)=C1C1=CC=C(C(O)=O)C=C1 PBPZGWJKXHZWFE-UHFFFAOYSA-N 0.000 description 4
- 229910004039 HBF4 Inorganic materials 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 229910021397 glassy carbon Inorganic materials 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229910021645 metal ion Inorganic materials 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical group [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
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- 230000008859 change Effects 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- 229910001429 cobalt ion Inorganic materials 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000010411 electrocatalyst Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
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- 230000008569 process Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- ORFSSYGWXNGVFB-UHFFFAOYSA-N sodium 4-amino-6-[[4-[4-[(8-amino-1-hydroxy-5,7-disulfonaphthalen-2-yl)diazenyl]-3-methoxyphenyl]-2-methoxyphenyl]diazenyl]-5-hydroxynaphthalene-1,3-disulfonic acid Chemical compound COC1=C(C=CC(=C1)C2=CC(=C(C=C2)N=NC3=C(C4=C(C=C3)C(=CC(=C4N)S(=O)(=O)O)S(=O)(=O)O)O)OC)N=NC5=C(C6=C(C=C5)C(=CC(=C6N)S(=O)(=O)O)S(=O)(=O)O)O.[Na+] ORFSSYGWXNGVFB-UHFFFAOYSA-N 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
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- 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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- C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
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Abstract
The invention relates to a cobalt (II) metal organic framework material with electrocatalytic hydrogen evolution performance and a performance test preparation of the cobalt (II) metal organic framework material as an electrocatalytic hydrogen evolution catalyst. The invention mainly utilizes cobalt chloride hexahydrate and 1,3, 5-trimethyl-2, 4, 6-tricarboxyphenyl benzene (H)3TMTA) as main synthetic raw material, obtaining blue block-shaped crystalline product by solvothermal method, wherein the molecular formula of the product can be expressed as [ Co ]2(TMTA)(DMF)(H2O)3]Cl. The blue crystalline material is washed, dried, ground and ultrasonically homogenized with Nafion, and then the electro-catalytic hydrogen evolution material can be prepared. The preparation method of the material is relatively simple, the yield of the material is high, the obtained catalyst has good capability of hydrogen evolution by water electrolysis, the tafel slope is 125mV/decade, and the current density is 10 mA/cm2Under the condition, the hydrogen evolution potential is 283mV, which shows good electrocatalysis performance and has certain reference value for developing the field of novel electrocatalysis hydrogen evolution catalysts.
Description
Technical Field
The invention belongs to the technical field of synthesis and application of novel catalyst materials, and particularly relates to a preparation method of a metal organic framework material and application of the metal organic framework material in the aspect of electrocatalytic decomposition of water for hydrogen evolution.
Background
With the continuous development of society and the use of fossil fuels since the industrial revolution, the productivity of human society is greatly improved, but a series of serious problems such as global warming are caused, and the problem of resource and energy shortage in the world concerned by countries around the world is gradually caused to appear in most countries and even in the world. Hydrogen energy becomes a secondary energy which plays a significant role in the world energy stage. It is a new energy source with high combustion heat value and the combustion product is only water, which is the cleanest energy source in the world.
How to conveniently and rapidly prepare hydrogen becomes a leading topic that scientists of all countries in the world continuously search for. At present, in the aspect of industrial application, hydrogen production by electrocatalysis decomposition of water is a relatively simple and efficient method. The preparation process goes through the process from water to hydrogen to water, so that the method perfectly deduces the classic example of the cyclic utilization and continuous development of natural substances.
Theoretically, the voltage for hydrogen evolution of the cathode of the electrolyzed water is 0V, however, the actual minimum hydrogen evolution voltage is far away from the theoretical voltage in consideration of the situations that certain overpotential, ohmic resistance and the like are required for hydrogen evolution. Thermodynamically, the electrolytic water evolution hydrogen reaction is expected to occur, and a relatively high activation energy is required, so that energy consumption is reduced by seeking different catalyst materials to lower the activation energy of the reaction. The traditional electrocatalytic hydrogen evolution material has the defects of high overpotential, overlarge tafel slope and the like, so that a novel catalyst material needs to be searched for in order to improve the hydrogen production efficiency. In recent years, Metal-Organic Frameworks (Metal-Organic Frameworks) are a class of crystalline porous materials with a periodic network structure formed by connecting inorganic Metal centers (Metal ions or Metal clusters) and bridged Organic ligands with each other through self-assembly. The size, shape, composition and the like of the MOFs cavities can be adjusted by selecting different ligands and metal ions or changing the synthesis strategy. The hydrogen ions are discharged to become hydrogen gas by virtue of the valence change characteristic of the central metal ions, thereby transferring electrons of an external circuit to the hydrogen ions in the water. There is an increasing interest in research surrounding the development of the synthesis of new metal organic framework materials and their use for electrocatalytic hydrogen evolution. For the above reasons, the present patent discloses a cobalt (ii) metal organic framework material and its application in electrocatalytic hydrogen evolution.
Disclosure of Invention
The invention aims to provide a preparation method of a cobalt (II) metal organic framework material, and the application of the cobalt (II) metal organic framework material in electrocatalytic hydrogen evolution is realized by utilizing the catalytic performance of the metal organic framework material.
In order to achieve the purpose, the invention adopts the technical scheme that: a1, 3, 5-trimethyl-2, 4, 6-tricarboxyphenylcobalt metal organic framework material, a synthetic method and an application thereof are disclosed, wherein the chemical general formula is as follows: [ Co ] A2(TMTA)( DMF)(H2O)3]Cl, abbreviated to Co-MOF, H3TMTA represents 1,3, 5-trimethyl-2, 4, 6-tricarboxyphenyl benzene, and the chemical formula of the organic rigid ligand used in the material is C30H24O6. The crystalline material being mono-crystallineOrthorhombic system, space group ofP21/cThe unit cell parameters are:a= 10.0067(11)Å，b= 28.284(4) Å，c=15.6049(18)Å，α= 90°，β=101.891(11)，γ= 90°。
the purpose of the invention is realized by the following technical scheme that the material has good stability in a sulfuric acid solution, especially in a 0.5M sulfuric acid solution, the preparation process of the material is prepared by a solvothermal method, and the material is specifically synthesized by the following steps:
(1) taking cobalt chloride, 1,3, 5-trimethyl-2, 4, 6-tricarboxyphenyl benzene, DMF (dimethyl formamide), fluoroboric acid and water, and carrying out ultrasonic treatment and dispersion on the obtained mixed solution to obtain a mixed solution;
(2) putting the mixed solution into a constant-temperature oven for constant-temperature reaction, and then slowly cooling to room temperature to obtain blue blocky crystals, namely, metal organic framework materials (Co-MOF);
(3) and washing the obtained blue blocky crystals with water, and drying at 50-80 ℃ to obtain a pure blue metal organic framework material (Co-MOF).
The molar ratio of the cobalt chloride hexahydrate to the 1,3, 5-trimethyl-2, 4, 6-tricarboxyphenyl benzene is 1: 2.
The volume ratio of DMF to water is 3:1, and the pH value of the solution is adjusted to 4-5 after the fluoboric acid is added, so that the mineralization degree of crystals can be increased while the pH value is adjusted, and the crystallization performance of the crystals is better.
The reaction temperature in the step (2) is 80-120 ℃, and the reaction time is 24-30 h.
The other technical scheme of the invention is to use the prepared cobalt (II) -based metal organic framework material as an electrocatalyst, in particular to a catalyst for electrocatalytic hydrogen evolution.
Weighing the Co-MOF prepared by the invention, putting the Co-MOF into a weighing tube, adding water, absolute ethyl alcohol and Nafion, performing ultrasonic treatment for 30 min, completely dispersing the Co-MOF to obtain a suspension, dripping 5 mu L of the suspension onto a glassy carbon electrode, drying the glassy carbon electrode at room temperature, and performing electro-catalytic hydrogen evolution on the glassy carbon electrode at 0.5M H2SO4Solutions ofTo perform the test. For comparison, a commercial electrocatalytic hydrogen evolution catalyst with 20% Pt/C was also run in the same manner.
The room temperature referred to in the invention refers to the ambient temperature under normal pressure.
The invention has the following advantages:
(1) the product prepared by the invention has the structural formula of [ Co2(TMTA)(DMF)(H2O)3]Cl, the preparation method is relatively simple and has strong controllability;
(2) the catalyst material prepared by the invention is a blocky crystal, good crystallinity can accurately obtain internal structure information through an X-ray single crystal diffraction technology, and the catalyst material is easy to separate and clean;
(3) the catalyst material prepared by the invention has better capability of electrocatalytic decomposition of water and hydrogen evolution;
(4) the raw materials used in the invention are relatively cheap and easily available, the cost of the catalyst can be effectively reduced, and the method is beneficial to large-scale production;
(5) the structure of the Co-MOF electrocatalytic hydrogen evolution material is a framework structure formed by alternately connecting metal cobalt atoms and organic ligands, and more surface hydrogen evolution reaction active sites are exposed compared with the traditional inorganic cobalt metal salt, so that the electrocatalytic hydrogen evolution performance of the material is improved. In the electro-catalysis hydrogen evolution test of the Co-MOF catalyst synthesized by the scheme, the Tafel slope is 125mV/decade, and the current density is 10 mA/cm2Under the condition, the hydrogen evolution potential is 283mV, which shows good electrocatalysis performance and provides a new method for developing electrocatalysis hydrogen evolution catalyst with low price and high efficiency.
Drawings
FIG. 1 is a diagram of coordination environment of metal ions inside the structure of the Co-MOF material prepared in example 1.
FIG. 2 is a two-dimensional layer diagram of the Co-MOF material prepared in example 1.
FIG. 3 is a thermogravimetric plot of the Co-MOF material prepared in example 1.
FIG. 4 is an X-ray diffraction pattern and a simulated X-ray diffraction pattern of a 1,3, 5-trimethyl-2, 4, 6-tricarboxyphenylbenzene transition metal cobalt-based metal organic framework material prepared in example 1.
FIG. 5 is a graph comparing the L SV of 1,3, 5-trimethyl-2, 4, 6-tricarboxyphenylbenzene transition metal cobalt-based metal organic framework material prepared in example 5 and commercial Pt/C.
FIG. 6 is a comparison of Tafel slopes for 1,3, 5-trimethyl-2, 4, 6-tricarboxyphenylbenzene transition metal cobalt-based metal organic framework material prepared in example 5 and commercial Pt/C.
Detailed Description
Example 1
9.6 mg of 1,3, 5-trimethyl-2, 4, 6-tris (4-carboxyphenyl) benzene, 4.7 mg of cobalt chloride hexahydrate, N, N-dimethylformamide (3 m L) and deionized water (1 m L) were mixed together in a beaker, and then 50 μ L of HBF was added dropwise to the mixed solution4Aqueous solution (A), (B) and (C)V HBF4:V H2O= 1: 3), continuing to ultrasonically treat the mixed solution for 30 minutes, and finally transferring the mixed solution to a stainless steel reaction kettle with a polytetrafluoroethylene lining. And placing the reaction kettle in an oven at 80 ℃ for constant-temperature reaction for 24 hours, and then cooling the oven to room temperature for 10 hours to obtain blue transparent blocky crystals, namely the Co-MOF material. As can be seen from FIGS. 1-2, the metallic cobalt ions adopt two coordination configurations of four coordination and six coordination in the material, and the whole structure belongs to a two-dimensional plane structure. As shown in the thermogravimetric diagram of FIG. 3, the material can be stabilized to 380 in airoAnd C is about. As can be seen from FIG. 4, the powder diffraction peak of the prepared sample is matched with the diffraction peak of Co-MOF simulated by single crystal data, and the obtained sample is the Co-MOF material with higher purity.
Example 2
9.6 mg of 1,3, 5-trimethyl-2, 4, 6-tris (4-carboxyphenyl) benzene, 4.7 mg of cobalt chloride hexahydrate, N, N-dimethylformamide (3 m L) and deionized water (1 m L) were mixed together in a beaker, and then 50 μ L of HBF was added dropwise to the mixed solution4Aqueous solution (A), (B) and (C)V HBF4:V H2O= 1: 3), continuing to ultrasonically treat the mixed solution for 30 minutes, and finally transferring the mixed solution to a stainless steel reaction kettle with a polytetrafluoroethylene lining. Placing the reaction kettleReacting for 24 hours in an oven with the constant temperature of 100 ℃, and then cooling the oven to the room temperature for 10 hours to obtain blue transparent blocky crystals, namely the Co-MOF material. The powder diffraction peak of the sample prepared in the embodiment is consistent with the XRD diffraction peak of the embodiment 1, and the obtained sample is the Co-MOF material with higher purity.
Example 3
9.6 mg of 1,3, 5-trimethyl-2, 4, 6-tris (4-carboxyphenyl) benzene, 4.7 mg of cobalt chloride hexahydrate, N, N-dimethylformamide (3 m L) and deionized water (1 m L) were mixed together in a beaker, and then 50 μ L of HBF was added dropwise to the mixed solution4Aqueous solution (A), (B) and (C)V HBF4:V H2O= 1: 3), continuing to ultrasonically treat the mixed solution for 30 minutes, and finally transferring the mixed solution to a stainless steel reaction kettle with a polytetrafluoroethylene lining. And placing the reaction kettle in an oven at 120 ℃ for constant-temperature reaction for 24 hours, and then cooling the oven to room temperature for 10 hours to obtain blue transparent blocky crystals, namely the Co-MOF material. The powder diffraction peak of the sample prepared in the embodiment is consistent with the XRD diffraction peak of the embodiment 1, and the obtained sample is the Co-MOF material with higher purity.
Example 4
9.6 mg of 1,3, 5-trimethyl-2, 4, 6-tris (4-carboxyphenyl) benzene, 4.7 mg of cobalt chloride hexahydrate, N, N-dimethylformamide (3 m L) and deionized water (1 m L) were mixed together in a beaker, and then 50 μ L of HBF was added dropwise to the mixed solution4Aqueous solution (A), (B) and (C)V HBF4:V H2O= 1: 3), continuing to ultrasonically treat the mixed solution for 30 minutes, and finally transferring the mixed solution to a stainless steel reaction kettle with a polytetrafluoroethylene lining. And placing the reaction kettle in an oven at 120 ℃ for constant-temperature reaction for 30 hours, and then cooling the oven to room temperature for 12 hours to obtain blue transparent blocky crystals, namely the Co-MOF material. The powder diffraction peak of the sample prepared in the embodiment is consistent with the XRD diffraction peak of the embodiment 1, and the obtained sample is the Co-MOF material with higher purity.
Example 5
Taking 4 mg of the Co-MOF catalyst material prepared in example 1, adding 0.7 m L water, 0.2m L absolute ethyl alcohol and 0.2m L Nafion, carrying out ultrasonic treatment for 30 min to completely disperse the mixture to obtain a suspension, then using a liquid-moving gun to remove 5 mu L of the suspension, dripping the suspension to a glassy carbon electrode, and drying at room temperature to obtain the cobalt (II) -based metal organic framework material modified electrode, wherein for comparison, commercial Pt/C is also carried out in the same way, as can be seen from FIGS. 5-6, in an electrocatalytic hydrogen evolution test, the gradient of Tafel is 125mV/decade, and the hydrogen evolution potential is 283mV under the condition that the current density is 10 mA/cm2, thus showing good electrocatalytic performance.
The above-mentioned embodiments are merely preferred technical solutions of the present invention, and should not be construed as limiting the present invention, and the embodiments and features of the embodiments in the present application can be arbitrarily combined with each other without conflict, and any changes, substitutions and improvements, which can be easily conceived by those skilled in the art within the spirit and principle of the present invention, should be covered within the protection scope of the present invention.
Claims (8)
1. A cobalt (II) metal organic framework material is characterized in that the molecular formula is [ Co ]2(TMTA)(DMF)(H2O)3]Cl, TMTA is the product of dehydrogenation of 1,3, 5-trimethyl-2, 4, 6-tricarboxyphenylbenzene and DMF is N, N-dimethylformamide.
2. The cobalt (II) metal organic framework material as claimed in claim 1, wherein the single crystal structure of the material belongs to the monoclinic system and the space group isP21/cThe unit cell parameters are:a= 10.0067(11)Å，b= 28.284(4) Å，c=15.6049(18)Å，α= 90°，β= 101.891(11)，γand the Co adopts four coordination and six coordination modes, has unsaturated catalytic active sites, and is a two-dimensional metal organic framework material.
3. The method for synthesizing cobalt (II) metal organic framework material as claimed in claim 1 or 2, characterized by comprising the following steps:
(1) mixing cobalt chloride hexahydrate, 1,3, 5-trimethyl-2, 4, 6-tricarboxyphenylbenzene, N-dimethylformamide, fluoroboric acid and water, and then carrying out ultrasonic treatment and dispersion to obtain a mixed solution;
(2) and (3) putting the mixed solution into a constant-temperature oven, reacting at a constant temperature, slowly cooling to room temperature to obtain blue blocky crystals, and washing and drying to obtain the cobalt (II) metal organic framework material.
4. The method of claim 3, wherein the molar ratio of cobalt chloride hexahydrate to 1,3, 5-trimethyl-2, 4, 6-tricarboxyphenylbenzene is 1: 2.
5. The method of claim 3, wherein the volume ratio of DMF to water is 3-5: 1.
6. The method for synthesizing cobalt (II) metal organic framework material as claimed in claim 3, wherein the pH of the solution is adjusted to 4-5 after adding fluoboric acid.
7. The method for synthesizing cobalt (II) metal organic framework material according to claim 3, wherein the reaction temperature in the step (2) is 80-120 ℃ and the reaction time is 24-30 h.
8. Use of a cobalt (ii) metal organic framework material according to claim 1 or 2 for electrocatalytic hydrogen evolution.
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| CN111871463A (en) * | 2020-07-14 | 2020-11-03 | 南昌航空大学 | Preparation method of electrocatalytic full-decomposition water material based on ZIF-67 and UiO-66 double MOFs |
| CN114395138A (en) * | 2022-02-17 | 2022-04-26 | 浙江大学 | Preparation method of microporous aluminum-based metal organic framework material with high specific surface area and water stability |
| CN114426671A (en) * | 2020-10-29 | 2022-05-03 | 中国石油天然气股份有限公司 | Metal organic framework material, preparation method and application |
| CN116082649A (en) * | 2022-12-24 | 2023-05-09 | 三峡大学 | Cobalt-based metal organic framework material and application thereof in glucose electrochemical sensing |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111871463A (en) * | 2020-07-14 | 2020-11-03 | 南昌航空大学 | Preparation method of electrocatalytic full-decomposition water material based on ZIF-67 and UiO-66 double MOFs |
| CN111871463B (en) * | 2020-07-14 | 2022-02-01 | 南昌航空大学 | Preparation method of electrocatalytic full-decomposition water material based on ZIF-67 and UiO-66 double MOFs |
| CN114426671A (en) * | 2020-10-29 | 2022-05-03 | 中国石油天然气股份有限公司 | Metal organic framework material, preparation method and application |
| CN114426671B (en) * | 2020-10-29 | 2023-10-31 | 中国石油天然气股份有限公司 | Metal organic framework material and preparation method and application thereof |
| CN114395138A (en) * | 2022-02-17 | 2022-04-26 | 浙江大学 | Preparation method of microporous aluminum-based metal organic framework material with high specific surface area and water stability |
| CN116082649A (en) * | 2022-12-24 | 2023-05-09 | 三峡大学 | Cobalt-based metal organic framework material and application thereof in glucose electrochemical sensing |
| CN116082649B (en) * | 2022-12-24 | 2024-03-22 | 三峡大学 | Cobalt-based metal organic framework material and application thereof in glucose electrochemical sensing |
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