CN110343257B - Polychlorinated cobalt-based composite material, preparation method and application thereof - Google Patents
Polychlorinated cobalt-based composite material, preparation method and application thereof Download PDFInfo
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- 150000001868 cobalt Chemical class 0.000 title claims abstract description 47
- 239000002131 composite material Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000006230 acetylene black Substances 0.000 claims abstract description 37
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 32
- 239000001257 hydrogen Substances 0.000 claims abstract description 32
- 239000012621 metal-organic framework Substances 0.000 claims abstract description 31
- 239000013256 coordination polymer Substances 0.000 claims abstract description 28
- 229920001795 coordination polymer Polymers 0.000 claims abstract description 28
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- 239000000463 material Substances 0.000 claims abstract description 16
- WZHHYIOUKQNLQM-UHFFFAOYSA-N 3,4,5,6-tetrachlorophthalic acid Chemical compound OC(=O)C1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1C(O)=O WZHHYIOUKQNLQM-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000013110 organic ligand Substances 0.000 claims abstract description 11
- MWVTWFVJZLCBMC-UHFFFAOYSA-N 4,4'-bipyridine Chemical group C1=NC=CC(C=2C=CN=CC=2)=C1 MWVTWFVJZLCBMC-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000012917 MOF crystal Substances 0.000 claims abstract description 9
- 239000003054 catalyst Substances 0.000 claims abstract description 9
- 238000000227 grinding Methods 0.000 claims abstract description 9
- 239000000126 substance Substances 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 31
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 20
- 239000008367 deionised water Substances 0.000 claims description 18
- 229910021641 deionized water Inorganic materials 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 229910001868 water Inorganic materials 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 10
- 239000003446 ligand Substances 0.000 claims description 7
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 6
- 239000004570 mortar (masonry) Substances 0.000 claims description 5
- 229910001220 stainless steel Inorganic materials 0.000 claims description 5
- 239000010935 stainless steel Substances 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 4
- -1 polytetrafluoroethylene Polymers 0.000 claims description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- 238000000034 method Methods 0.000 abstract description 9
- 239000010941 cobalt Substances 0.000 abstract description 8
- 229910017052 cobalt Inorganic materials 0.000 abstract description 8
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 abstract description 7
- 238000001338 self-assembly Methods 0.000 abstract description 4
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 238000010189 synthetic method Methods 0.000 abstract 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 6
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 239000013078 crystal Substances 0.000 description 4
- 238000001027 hydrothermal synthesis Methods 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 238000005868 electrolysis reaction Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 2
- 238000012937 correction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000010411 electrocatalyst Substances 0.000 description 2
- 229910021397 glassy carbon Inorganic materials 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 229910016523 CuKa Inorganic materials 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- CWSCMEBPTGNWML-UHFFFAOYSA-M [Co]Cl Chemical compound [Co]Cl CWSCMEBPTGNWML-UHFFFAOYSA-M 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 238000002447 crystallographic data Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 150000001990 dicarboxylic acid derivatives Polymers 0.000 description 1
- 150000001991 dicarboxylic acids Polymers 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 125000006575 electron-withdrawing group Chemical group 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 150000003021 phthalic acid derivatives Polymers 0.000 description 1
- 150000003022 phthalic acids Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 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
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
- B01J31/223—At least two oxygen atoms present in one at least bidentate or bridging ligand
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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
- B01J35/30—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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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
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- C—CHEMISTRY; METALLURGY
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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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- 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
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Abstract
The invention discloses a polychlorinated cobalt-based composite material, a preparation method and application thereof. The specific synthetic method is to use tetrachlorophthalic acid organic ligand, cobalt salt and 4, 4' -bipyridyl in deionized waterThe polychlorinated cobalt-based coordination polymer is obtained by self-assembly, and the chemical molecular formula of the material is [ Co (Cl)4‑bdc)(bpy)(H2O)2]n. Acetylene Black (AB) is used as a conductive substance to obtain the polychlorinated cobalt-based composite material through self-assembly by a grinding and ultra-grinding method. Pure Co-Cl-MOF crystals at a current density of 10mA/cm2The time hydrogen evolution potential is 424mV, the Tafel slope is 125mV dec‑1Polychloro cobalt-based composite material AB compounded with acetylene black&Co-Cl-MOF (3:4) at a current density of 10mA/cm2The time-evolution hydrogen potential is 115mV, and the Tafel slope is 66mV dec‑1The catalyst exhibits superior catalytic activity in electrocatalytic Hydrogen Evolution Reaction (HER).
Description
Technical Field
The invention belongs to the technical field of crystalline materials, and particularly relates to a polychlorinated cobalt-based composite material with high-efficiency hydrogen production performance and a preparation method thereof.
Background
In order to meet the increasing energy and environmental demands, various methods have been developed to produce new energy, and hydrogen is considered to be one of the most important clean energy sources in the future. Therefore, extensive research has been conducted on a highly efficient and environmentally friendly method of producing hydrogen. Electrolysis of water is one of the simplest and most advanced hydrogen evolution processes currently in commercial use. Currently, platinum is still the most effective electrocatalyst for electrocatalytic hydrogen evolution, however, reducing the use of platinum and finding alternative materials is always the ultimate goal of electrocatalyst design to improve its efficiency and achieve cost-effective hydrogen production at low cost.
At present, the research bottleneck of electrocatalytic hydrogen evolution is that the overpotential is too high, and therefore, the development of low-cost, highly stable materials with the highest possible energy efficiency by reducing the overpotential required to drive the reaction is urgently required. Among the many new catalysts, one of the best choices is based on earth-abundant metals, such as iron, cobalt, nickel, etc., which are abundant in production and relatively low in price. Recently, some studies have also shown that their sulfides, carbides, phosphides and nitrides are effective catalyst substitutes. In recent years, the application of metal organic framework materials as catalysts for hydrogen production by water electrolysis has been greatly developed. The metal organic framework material is considered to be a precursor or a template with great potential when different functionalized materials are constructed due to the characteristics of high specific surface area, adjustable pore size and volume, metal ion selection diversity, designable organic ligands and the like.
The cobalt-based metal framework material is a hotspot of hydrogen evolution research at present, particularly, a polymer coordinated with polyhalogenated phthalic acid has strong hydrogen evolution research potential, the cobalt-based material has a special electronic structure, and under the influence of some electron-withdrawing atoms, the hybrid material can enhance the affinity of reactants and an intermediate, so that the overpotential of water dissociation is reduced. On the other hand, halogen atoms exhibit both an electronegative electron-withdrawing effect and a resonance-donating effect in which lone pair electrons exist, and to some extent, introduction of halogen elements in the catalyst is also an important factor that affects selection. In addition, the conductivity of the cobalt-based metal framework material can be improved by doping substances such as graphene, acetylene black and the like, and the method is another way for improving the electrocatalytic hydrogen evolution performance of the composite material.
Therefore, the development of a cobalt-based hydrogen production catalyst with abundant earth reserves and low price to replace a noble metal catalyst is very important for realizing the large-scale electrolysis of hydrogen production.
Disclosure of Invention
Based on the preparation method, the invention provides the preparation method of the polychlorinated cobalt-based composite material, and the material is applied to electrocatalytic hydrogen evolution, and the preparation method is reasonable and simple and has excellent performance.
The polychlorinated bi-carboxylic acid based coordination polymer is prepared by self-assembly of a polyhalogenated dicarboxylic acid organic ligand, a rigid nitrogen-containing auxiliary ligand and cobalt salt by adopting a hydrothermal method, contains a large amount of chlorinated electron-withdrawing groups, and is doped and compounded on a metal organic framework material obtained by self-assembly by using Acetylene Black (AB) as a conductive substance through a grinding and ultra-grinding method to obtain the polychlorinated bi-carboxylic acid based composite material. The composite material exhibits superior catalytic activity in electrocatalytic Hydrogen Evolution Reaction (HER).
In order to achieve the purpose, the invention adopts the technical scheme that:
the polychlorinated cobalt-based coordination polymer has a chemical formula of [ Co (Cl)4-bdc)(bpy)(H2O)2]n；(Cl4-bdc denotes the removal of two protons from tetrachlorophthalic acid, Cl4-H2bdc-tetrachlorophthalic acid, bpy-4, 4' -bipyridine), the basic unit of the polychlorinated cobalt-based coordination polymer comprises a Co (II) ion and a Cl4-bdc2-Ions, one 4, 4' -bipyridine and two coordinated water molecules. n represents infinity.
The organic rigid ligand tetrachlorophthalic acid used by the polychlorinated cobalt-based coordination polymer has a chemical molecular formula of C8H2Cl4O4。
The polychlorinated cobalt-based coordination polymer belongs to an orthorhombic system, a space group Pccn space group, unit cell parameters of alpha-90 degrees, beta-90 degrees and gamma-90 degrees,
the preparation method of the polychlorinated cobalt-based coordination polymer comprises the following steps:
adding organic ligands of tetrachlorophthalic acid, 4' -bipyridine and cobalt salt into a deionized water solution, adding a proper amount of potassium hydroxide solution into the deionized water solution, and carrying out hydrothermal reaction to obtain a metal organic framework material with a crystal structure, namely [ Co (Cl)4-bdc)(bpy)(H2O)2]nThe polychlorinated cobalt-based coordination polymer is called Co-Cl-MOF for short.
The preparation method of the cobalt-polychloride-based composite material comprises the following steps:
(1) Adding organic ligands of tetrachlorophthalic acid, 4' -bipyridine and cobalt salt into a deionized water solution, adding a proper amount of potassium hydroxide solution into the deionized water solution, and carrying out hydrothermal reaction to obtain a metal organic framework material with a crystal structure, namely [ Co (Cl)4-bdc)(bpy)(H2O)2]nThe polychlorinated cobalt-based coordination polymer is called Co-Cl-MOF for short.
(2) And (2) adding Acetylene Black (AB) and the Co-Cl-MOF polychlorinated cobalt-based coordination polymer in the step (1) into a mortar for mechanical grinding for 5-10 minutes, adding the ground sample into ethanol, ultrasonically dispersing for 20-30 minutes, and drying in a vacuum drying oven at 50-60 ℃ to obtain the polychlorinated cobalt-based composite material AB & Co-Cl-MOF.
The cobalt salt is Co (ClO)4)2·6H2O、Co(CH3COO)2·4H2O、Co(NO3)2·6H2Any one of O, preferably Co (ClO)4)2·6H2O。
The mole ratio of tetrachlorophthalic acid, auxiliary nitrogen-containing ligand 4, 4' -bipyridine, cobalt salt and potassium hydroxide is 1: 1-2: 1-4: 1-4; said [ Co (Cl) ]4-bdc)(bpy)(H2O)2]nThe mass ratio of the polychlorinated cobalt-based coordination polymer to the acetylene black is 1: 0.25-1.
Every 0.01mmol of organic ligand tetrachlorophthalic acid corresponds to 1-2mL of deionized water, the hydrothermal reaction temperature is 80-140 ℃, the reaction time is 60-90 hours, then the mixture is naturally cooled to room temperature for 24 hours, and the mixture is washed by deionized water for 3 times to obtain Co-Cl-MOF crystals.
Further, the preparation method of the cobalt-polychlorinated composite material is preferably tetrachlorophthalic acid: co (ClO)4)2·6H2O: 4, 4' -bipyridine: the molar ratio of potassium hydroxide is 1:4:1:2, each 0.01mmol of organic ligand tetrachlorophthalic acid corresponds to 2mL of deionized water, the mixture is put into a stainless steel reaction kettle with a polytetrafluoroethylene lining for 120 ℃ autogenous pressure reaction for 72 hours, the mixture is naturally cooled to room temperature for 24 hours, and the product is washed by deionized water for 3 times to obtain peach-red Co-Cl-MOF crystals. The mass ratio of the Co-Cl-MOF to the Acetylene Black (AB) is 1: 0.75.
said [ Co (Cl) ]4-bdc)(bpy)(H2O)2]nThe application of the polychlorinated cobalt-based coordination polymer and the chloro-cobalt-based composite material in electrocatalysis.
The application is particularly the application of the polychlorinated cobalt-based composite material in the electrocatalytic hydrogen evolution.
The specific method for electrolyzing water and evolving hydrogen by using the polychlorinated cobalt-based composite material comprises the following steps:
electrolyzing water to separate hydrogen: the obtained polychlorinated cobalt-based composite material AB&Weighing 4mg of Co-Cl-MOF, adding 0.5ml of ethanol and 1.5ml of deionized water, and carrying out ultrasonic mixing for 30min to prepare an electrode solution for later use; then 4 mu L of the electrode solution is coated on a glassy carbon electrode to be used as a working electrode, a graphite rod is used as a counter electrode, a saturated Ag/AgCl is used as a reference electrode to form a three-electrode system, and the three-electrode system is inserted into 0.5mol/LH2SO4The hydrogen evolution reaction was carried out in the solution. For comparison, commercial Pt/C was also run as the working electrode for subsequent electrocatalytic performance testing.
The precursor polychlorinated cobalt-based coordination polymer obtained by the invention is used for carrying out structure measurement on crystals by using a micro-focal spot X-ray diffractometer of Rigaku corporation in Japan, a graphite monochromator is utilized, CuKa rays with the wavelength of lambda being 1.54184nm are used, data such as diffraction intensity, unit cell parameters and the like are measured under 293K, empirical absorption correction is carried out on collected data by using a scanning technology, the obtained result is directly analyzed by using a Shelxtl-97 program, and the correction is carried out by using a full matrix least square method. The obtained crystallographic data are shown below.
TABLE 1 Crystal science parameter table
Drawings
FIG. 1: is a minimum asymmetric structure diagram of the polychlorocobalt-based coordination polymer synthesized in example 1.
FIG. 2: the X-ray diffraction pattern of the polychlorocobalt-based coordination polymer synthesized in example 1 is compared with a simulated X-ray diffraction pattern.
FIG. 3: is a thermogravimetric analysis chart of the polychlorocobalt-based coordination polymer synthesized in example 1.
FIG. 4: is a hydrogen evolution overpotential experimental graph of the polychlorinated cobalt-based composite material synthesized in example 1.
FIG. 5: a hydrogen evolution tafel experimental diagram of the polychlorinated cobalt-based composite material synthesized in example 1 is shown.
Detailed Description
The invention is further illustrated by the following examples, but the scope of the invention as claimed is not limited to the scope of the examples.
Example 1
Taking 0.04mmol of organic ligand tetrachlorophthalic acid and Co (ClO)4)2·6H20.16mmol of O, 0.04mmol of auxiliary nitrogen-containing ligand 4, 4' -bipyridine, 0.08mmol of potassium hydroxide and 8ml of deionized water, placing the mixture into a stainless steel reaction kettle with a polytetrafluoroethylene lining for an autogenous pressure reaction at 120 ℃ for 72 hours, then naturally cooling the reaction kettle to room temperature for 24 hours, and washing the reaction kettle for 3 times by using the deionized water to obtain a peach-red Co-Cl-MOF crystal (namely the polychlorinated cobalt-based coordination polymer). Acetylene Black (AB) and a Co-Cl-MOF polychlorinated cobalt-based coordination polymer (the weighed amounts of the Acetylene Black (AB) and the Co-Cl-MOF polychlorinated cobalt-based coordination polymer are respectively 1mg and 4 mg; 2mg and 4 mg; 3mg and 4 mg; 4mg and 4mg for tests) are added into a mortar for mechanical grinding for 10 minutes, the ground sample is added into ethanol for ultrasonic dispersion for 30 minutes, and the mixture is dried in a vacuum drying oven at 60 ℃ to obtain the polychlorinated cobalt-based composite material AB&Co-Cl-MOF, 4mg of which was weighed out in the above-mentioned amount of acetylene black and Co-Cl-MOF polychlorinated cobalt-based coordination polymer, was subjected to an electrocatalytic test.
Example 2
Taking organic ligand tetrachlorophthalic acid 0.04mmol, Co (CH)3COO)2·4H20.08mmol of O, 0.06mmol of auxiliary nitrogen-containing ligand 4, 4' -bipyridine, 0.04mmol of potassium hydroxide and 8ml of deionized water are filled into polytetrafluoroethyleneThe stainless steel reactor with the lining is subjected to autogenous pressure reaction for 90 hours at 100 ℃, then is naturally cooled to room temperature for 24 hours, and is washed by deionized water for 3 times to obtain peach-red Co-Cl-MOF crystals (namely the polychlorinated cobalt-based coordination polymer). Adding 1mg of Acetylene Black (AB) and 4mg of Co-Cl-MOF precursor polychlorinated cobalt-based coordination polymer into a mortar for mechanical grinding for 10 minutes, adding the ground sample into ethanol, ultrasonically dispersing for 30 minutes, and drying in a vacuum drying oven at 60 ℃ to obtain the polychlorinated cobalt-based composite material AB&Co-Cl-MOF。
Example 3
Taking organic ligand tetrachlorophthalic acid 0.04mmol, Co (NO)3)2·6H20.04mmol of O, 0.08mmol of auxiliary nitrogen-containing ligand 4, 4' -bipyridine, 0.16mmol of potassium hydroxide and 8ml of deionized water, placing the mixture into a stainless steel reaction kettle with a polytetrafluoroethylene lining, carrying out a 120 ℃ autogenous pressure reaction for 90 hours, then naturally cooling the reaction kettle to room temperature for 24 hours, and washing the reaction kettle for 3 times by using the deionized water to obtain a peach-red Co-Cl-MOF crystal (namely the polychlorinated cobalt-based coordination polymer). Adding 4mg of Acetylene Black (AB) and 4mg of Co-Cl-MOF precursor polychlorinated cobalt-based coordination polymer into a mortar for mechanical grinding for 10 minutes, adding the ground sample into ethanol, ultrasonically dispersing for 30 minutes, and drying in a vacuum drying oven at 60 ℃ to obtain the polychlorinated cobalt-based composite material AB&Co-Cl-MOF。
The materials prepared in the examples were subjected to an electrolytic water hydrogen evolution test:
the polychlorocobalt-based coordination polymer Co-Cl-MOF and the polychlorocobalt-based composite material AB obtained in example 1 were mixed&Co-Cl-MOF [1mg, 4mg, i.e. representing AB in FIGS. 4 and 5&Co-Cl-MOF(1:4)]、AB&Co-Cl-MOF [2mg, 4mg, i.e. representing AB in FIGS. 4 and 5&Co-Cl-MOF(2:4)]、AB&Co-Cl-MOF [3mg, 4mg, i.e. representing AB in FIGS. 4 and 5&Co-Cl-MOF(3:4)]、AB&Co-Cl-MOF [4mg, i.e. representing AB in FIGS. 4 and 5&Co-Cl-MOF(4:4)]Mixing the two, respectively weighing 4mg of each mixture, adding 0.5ml of ethanol and 1.5ml of deionized water, and carrying out ultrasonic treatment for 30min to uniformly mix to prepare an electrode solution for later use; then 4 microliter of the electrode solution is coated on a glassy carbon electrode to be used as a working electrode, a platinum wire is used as a counter electrode, a saturated calomel electrode is used as a reference electrode to form a three-electrode system, and the three-electrode system is inserted into 0.5mol/LH2SO4The hydrogen evolution reaction was carried out in the solution. For comparison, commercial Pt/C was also run as the working electrode for subsequent electrocatalytic performance testing.
It can be seen from FIGS. 4 and 5 that the polychloro-cobalt-based composite material prepared in example 1 had a low hydrogen evolution overpotential and a low Tafel slope, wherein pure Co-Cl-MOF crystals had a current density of 10mA/cm2The time hydrogen evolution potential is 424mV, the Tafel slope is 125mV dec-1Polychloro cobalt-based composite material AB compounded with acetylene black&Co-Cl-MOF (3:4) at a current density of 10mA/cm2The time-evolution hydrogen potential is 115mV, and the Tafel slope is 66mV dec-1The polychlorinated cobalt-based composite material prepared by the method has good application potential of electrocatalytic hydrogen evolution.
Claims (2)
1. An application of a polychlorinated cobalt-based composite material as a catalyst for electrocatalytic hydrogen evolution is characterized in that the composite material is prepared by respectively weighing 3mg and 4mg of acetylene black AB and Co-Cl-MOF polychlorinated cobalt-based coordination polymer, adding the weighed materials into a mortar for mechanical grinding for 10 minutes, adding a ground sample into ethanol, ultrasonically dispersing for 30 minutes, and drying in a vacuum drying oven at 60 ℃ to obtain the polychlorinated cobalt-based composite material AB&The preparation method of the polychlorinated cobalt-based coordination polymer comprises the following steps: taking 0.04mmol of organic ligand tetrachlorophthalic acid and Co (ClO)4)2·6H20.16mmol of O, 0.04mmol of auxiliary nitrogen-containing ligand 4, 4' -bipyridine, 0.08mmol of potassium hydroxide and 8ml of deionized water, placing the mixture into a stainless steel reaction kettle with a polytetrafluoroethylene lining for an autogenous pressure reaction at 120 ℃ for 72 hours, then naturally cooling the reaction kettle to room temperature for 24 hours, and washing the reaction kettle for 3 times by using deionized water to obtain a pink Co-Cl-MOF crystal.
2. The use of a polychlorinated cobalt-based composite material as a catalyst for electrocatalytic hydrogen evolution according to claim 1, wherein the peach-colored Co-Cl-MOF crystal has a chemical formula of [ Co (Cl)4-bdc) (bpy) (H2O)2 ]n(ii) a Wherein Cl is4Bdc denotes the removal of tetrachlorophthalic acidTwo protons, the chemical formula of the tetrachlorophthalic acid is C8H2Cl4O4Bpy is expressed as 4, 4' -bipyridine, n is infinite, the polychlorocobalt-based coordination polymer belongs to an orthorhombic system, the space group Pccn space group has unit cell parameters α =90 °, β =90 °, γ =90 °, a =23.1710(3) a, b =11.96450(10) a, c =23.1710 (3).
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