CN116120572A - Bimetal conductive metal organic framework material and preparation method and application thereof - Google Patents
Bimetal conductive metal organic framework material and preparation method and application thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 28
- 239000013299 conductive metal organic framework Substances 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000009792 diffusion process Methods 0.000 claims abstract description 20
- 229910052751 metal Inorganic materials 0.000 claims abstract description 17
- 239000002184 metal Substances 0.000 claims abstract description 17
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 12
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 12
- 239000012621 metal-organic framework Substances 0.000 claims abstract description 11
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 9
- 230000009467 reduction Effects 0.000 claims abstract description 8
- 239000003446 ligand Substances 0.000 claims abstract description 5
- 238000004729 solvothermal method Methods 0.000 claims abstract description 5
- GQDKQZAEQBGVBS-UHFFFAOYSA-N dibenzo[g,p]chrysene Chemical compound C1=CC=CC2=C3C4=CC=CC=C4C4=CC=CC=C4C3=C(C=CC=C3)C3=C21 GQDKQZAEQBGVBS-UHFFFAOYSA-N 0.000 claims abstract 2
- 239000010949 copper Substances 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 229910052802 copper Inorganic materials 0.000 claims description 11
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 229920000557 Nafion® Polymers 0.000 claims description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 8
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 230000002209 hydrophobic effect Effects 0.000 claims description 3
- 238000011068 loading method Methods 0.000 claims description 3
- 239000000376 reactant Substances 0.000 claims description 3
- 239000007921 spray Substances 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims description 2
- 229910021594 Copper(II) fluoride Inorganic materials 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 2
- GWFAVIIMQDUCRA-UHFFFAOYSA-L copper(ii) fluoride Chemical compound [F-].[F-].[Cu+2] GWFAVIIMQDUCRA-UHFFFAOYSA-L 0.000 claims description 2
- JIDMEYQIXXJQCC-UHFFFAOYSA-L copper;2,2,2-trifluoroacetate Chemical compound [Cu+2].[O-]C(=O)C(F)(F)F.[O-]C(=O)C(F)(F)F JIDMEYQIXXJQCC-UHFFFAOYSA-L 0.000 claims description 2
- ZKXWKVVCCTZOLD-UHFFFAOYSA-N copper;4-hydroxypent-3-en-2-one Chemical compound [Cu].CC(O)=CC(C)=O.CC(O)=CC(C)=O ZKXWKVVCCTZOLD-UHFFFAOYSA-N 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 3
- 230000003197 catalytic effect Effects 0.000 abstract description 10
- QRZUPJILJVGUFF-UHFFFAOYSA-N 2,8-dibenzylcyclooctan-1-one Chemical compound C1CCCCC(CC=2C=CC=CC=2)C(=O)C1CC1=CC=CC=C1 QRZUPJILJVGUFF-UHFFFAOYSA-N 0.000 abstract 1
- 239000002131 composite material Substances 0.000 abstract 1
- 238000005507 spraying Methods 0.000 abstract 1
- 239000003054 catalyst Substances 0.000 description 16
- 239000011701 zinc Substances 0.000 description 11
- 239000000243 solution Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 238000001308 synthesis method Methods 0.000 description 4
- 210000004027 cell Anatomy 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000010411 electrocatalyst Substances 0.000 description 3
- 230000010757 Reduction Activity Effects 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 239000003011 anion exchange membrane Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000004502 linear sweep voltammetry Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000013110 organic ligand Substances 0.000 description 2
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 2
- 235000015497 potassium bicarbonate Nutrition 0.000 description 2
- 239000011736 potassium bicarbonate Substances 0.000 description 2
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000004626 scanning electron microscopy Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 238000009210 therapy by ultrasound Methods 0.000 description 2
- 229910017518 Cu Zn Inorganic materials 0.000 description 1
- 229910017752 Cu-Zn Inorganic materials 0.000 description 1
- 229910017943 Cu—Zn Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000013246 bimetallic metal–organic framework Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 230000019771 cognition Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 description 1
- NWFNSTOSIVLCJA-UHFFFAOYSA-L copper;diacetate;hydrate Chemical compound O.[Cu+2].CC([O-])=O.CC([O-])=O NWFNSTOSIVLCJA-UHFFFAOYSA-L 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 210000000497 foam cell Anatomy 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- UUWCBFKLGFQDME-UHFFFAOYSA-N platinum titanium Chemical compound [Ti].[Pt] UUWCBFKLGFQDME-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001144 powder X-ray diffraction data Methods 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
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- 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
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- C25B11/031—Porous electrodes
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- C25B11/095—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds at least one of the compounds being organic
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Abstract
The invention belongs to the technical field of catalytic materials, and particularly relates to a bimetal conductive metal organic framework material, a preparation method and application thereof. 2,3,6,7,10,11,14,15-Octahydroxy Tetrabenzonaphthalene H 8 DBCO is a bridging ligand, and metal ion Cu 2+ With metal ions M 2+ Metal organic framework material with bi-metal co-coordinated two-dimensional layered structure prepared by solvothermal method, M 2+ Is Zn 2+ 、Co 2+ 、Ni 2+ 、Cd 2+ 、Fe 2+ 、Mn 2+ Any one of them; the material is represented by the formula CuM-DBCO. CuM-DBCO is manufactured into a gas diffusion electrode by a spraying method, so that the selective carbon dioxide reduction under high current is realized. The CuM-DBCO composite material combines the advantages of excellent conductivity and diatomic synergy, and can realize high selectivity and high stability under high current.
Description
Technical Field
The invention belongs to the technical field of catalytic materials, and particularly relates to a bimetal conductive metal organic framework material, a preparation method and application thereof.
Background
Monoatomic catalysts have made breakthrough progress in many areas due to their combination of selectivity advantages of homogeneous catalysts and ease of separation advantages of heterogeneous catalysts. With the development of monoatomic catalysts, diatomic catalysts having both advantages of monoatomic catalysts and interatomic synergistic catalysis have also received attention. However, the same disadvantages exist for single-and double-atom catalysts: firstly, the synthesis method is complex, which greatly limits the development of the method; secondly, the structural characterization is ambiguous and complex, seriously hampering the knowledge of the relevant catalytic mechanisms. Simple and convenient, therefore, the development of simple and convenient synthesis methods with definite structure of the diatomic catalyst can realize great breakthrough and innovation both in methodology and in cognition of catalytic mechanism.
Metal organic framework Materials (MOFs) are porous coordination compounds in which metal nodes are uniformly dispersed with organic ligands. The preparation method is mainly simple, convenient and mild, and reported solvothermal method, diffusion method, mechanochemical synthesis method, electrochemical synthesis method and the like. By combining the characteristic of uniform structure, the two defects of the traditional double-atom catalyst are perfectly overcome. However, a major obstacle to the use of MOFs in the field of electrocatalysis that they are poorly conductive, greatly limiting the transport of electrons within the framework. This results in a decrease in the catalytic activity of MOFs on the one hand and in an agglomeration of metal catalytic sites by structural disruption on the other hand, and thus in a decrease in selectivity. Therefore, developing bimetallic MOFs materials with high conductivity is one of the effective ways to synthesize highly efficient and stable diatomic electrocatalysts.
Disclosure of Invention
In order to solve the technical problems, the invention provides a double-layer structureA metal conductive metal organic frame material, a preparation method and application thereof. Metal ion Cu with carbon dioxide reduction activity by adopting organic ligand with conjugated structure and redox activity 2+ As main metal node, metal ion Zn with better water activating performance 2+ 、Co 2+ 、Ni 2+ 、Cd 2+ 、Fe 2+ 、Mn 2+ The diatomic electro-catalyst with high activity and high selectivity for reducing carbon dioxide is formed by a one-pot method of any one metal ion second metal node.
In order to achieve the above object, the technical scheme of the present invention is as follows:
one aspect of the invention provides a method for preparing a bimetal conductive metal organic framework material, which uses 2,3,6,7,10,11,14,15-octahydroxytetrabenzonaphthalene H 8 DBCO is a bridging ligand, and metal ion Cu 2+ With metal ions M 2+ Metal organic framework material with bi-metal co-coordinated two-dimensional layered structure prepared by solvothermal method, M 2+ Is Zn 2+ 、Co 2+ 、Ni 2 + 、Cd 2+ 、Fe 2+ 、Mn 2+ Any one of them; the material is represented by the formula CuM-DBCO; the synthetic route is as follows:
xCu(OAc) 2 ·H 2 O+(2-x)M(OAc) 2 ·H 2 O+H 8 DBCO→Cu x (M) 2-x (DBCO) 2
preferably, the preparation method specifically comprises the following steps:
(1) Adding 2,3,6,7,10,11,14,15-octahydroxytetrabenzonaphthalene, a copper source and an M metal source into water, uniformly dispersing by ultrasonic waves, and then adding an N-methylpyrrolidone (NMP) solvent dropwise while carrying out ultrasonic waves to obtain a solution A;
(2) Heating the solution A;
(3) And (3) naturally cooling the reactant obtained in the step (2) to room temperature, and then centrifuging, washing and drying to obtain the bimetal conductive metal organic framework material.
Preferably, in the step (1), the copper source is Cu (OAc) 2 ·H 2 O，Cu(NO 3 ) 2 ·3H 2 O、CuCl 2 ·2H 2 Any one of O, copper acetylacetonate, copper fluoride and copper trifluoroacetate;
the M metal source is any one of acetate, nitrate and chloride of M, wherein M= Zn, co, ni, cd, fe, mn;
in the solution A, the concentration of 2,3,6,7,10,11,14,15-octahydroxytetrabenzonaphthalene is 10-200mmol/L, the concentration of a copper source is 20-400mmol/L, the concentration of an M metal source is 20-400mmol/L, the molar ratio of the copper source to the M metal source is a,0< a <100%, and the volume concentration of NMP is 1-30%;
the ultrasonic dispersion time is not less than 2min.
Preferably, in the step (2), the heating temperature is 85 ℃ and the heating time is 12 hours.
Preferably, in the step (3), the washing method comprises the following steps: respectively washing with N, N-dimethylformamide and absolute methanol for not less than 3 times;
the drying temperature is 60 ℃, and the drying time is not less than 5 hours.
The invention also provides a bimetal conductive metal organic framework material prepared by the preparation method.
In a further aspect of the present invention, a method for preparing a gas diffusion electrode based on a bimetal conductive metal organic framework material is provided, wherein the bimetal conductive metal organic framework material of claim 6, namely CuM-DBCO, is ultrasonically dispersed in an ethanol solution of Nafion, and then is uniformly sprayed on hydrophobic carbon paper by a spray gun, and is naturally dried, so as to obtain the gas diffusion electrode.
Preferably, the mass content of Nafion in the Nafion ethanol solution is 0.25%; the concentration of the bimetal conductive metal organic framework material in Nafion ethanol solution is 5-10mg/ml.
Preferably, the CuM-DBCO loading in the gas diffusion electrode is 0.1-5mg/cm 2
The invention also provides an application of the gas diffusion electrode in electrocatalytic carbon dioxide reduction.
The gas diffusion electrode is arranged on a flow cell to be used as a cathode, the foam nickel is used as an anode, the cathode and the anode are separated by an anion exchange membrane, and the potassium bicarbonate aqueous solution with the concentration of 0.1-1.0M is used as electrolyte.
The MOFs type diatomic electrocatalyst with a definite structure is prepared by a simple solvothermal method. After the MOFs catalyst is dispersed by ultrasonic, the MOFs catalyst is sprayed on a gas diffusion electrode, so that high activity and high selectivity of carbon dioxide reduction under high current in a flow cell can be obtained. The conductivity of the bimetallic catalytic MOFs and the synergy of the diatomic atoms improve the electrocatalytic activity and selectivity. The CuM-DBCO-based gas diffusion electrode has excellent electrocatalytic carbon dioxide reduction activity for preparing methane.
The beneficial effects of the invention are as follows:
1. the invention adopts 2,3,6,7,10,11,14,15-octahydroxytetrabenzonaphthalene as ligand, has redox activity and conjugated group, and can provide efficient charge conduction.
2. The catalytic sites in the prepared bimetal conductive metal organic framework material CuM-DBCO are uniformly dispersed in the framework in the form of diatomic atoms, and can show high selectivity in the electrocatalytic process.
3. The CuM-DBCO can realize high selectivity and high stability under high current by combining the advantages of excellent conductivity and diatomic synergy.
Drawings
FIG. 1 is Cu in example 1 x Zn (1-x) -powder XRD pattern of DBCO;
FIG. 2 is Cu in example 1 0.97 Zn 0.03 -scanning electron microscopy and energy spectrum of DBCO;
FIG. 3 is Cu in example 3 0.97 Zn 0.03 -Linear Sweep Voltammetry (LSV) curve of DBCO gas diffusion electrode;
FIG. 4 is a plot of the carbon dioxide reduction product of the CuM-DBCO gas diffusion electrode of example 3;
FIG. 5 is Cu in example 4 0.97 Zn 0.03 Time-voltage diagram of constant current catalytic carbon dioxide reduction of DBCO gas diffusion electrode.
Detailed Description
The following describes the content of the present invention in detail with reference to examples and drawings, but the embodiments of the present invention are not limited thereto.
Example 1
2,3,6,7,10,11,14,15-octahydroxytetrabenzonaphthalene (10 mg,0.022 mmol) ligand was dispersed in 1 ml of water, then copper acetate hydrate (8 mg,0.04 mmol) and zinc acetate were added in a molar ratio of 0.97: and 0.03, uniformly mixing reactants by ultrasonic treatment, dropwise adding 100 microliters of NMP while ultrasonic treatment, transferring the mixed solution into a glass substrate, covering, placing in a blast drying box at 85 ℃ for reaction for 10 hours, naturally cooling to room temperature after the reaction is finished, centrifuging, and washing the obtained solid by using DMF and absolute methanol for three times respectively. A black powder was obtained, designated CuM-DBCO.
Cu obtained in example 1 x Zn (1-x) The XRD results of DBCO are shown in figure 1, and it can be seen from the figure that the XRD patterns of the synthesized bimetal conductive MOFs are identical to those of pure copper-based Cu-DBCO, and no redundant phases are found. As shown in fig. 2, scanning Electron Microscopy (SEM) binding spectroscopy (EDS) demonstrated that the bimetal was uniformly dispersed, and no segregation phenomenon was found. Compared with single-atom Cu-DBCO, the method has the advantages that Cu-Zn is increased in the frame by wavelet transformation technology of X-ray absorption spectrum 2+ Signals of bimetal, distance is
Successful preparation of the diatomic catalyst was demonstrated.
Example 2
Weigh 50mg Cu 0.97 Zn 0.03 The DBCO catalyst is dispersed in 0.25wt% Nafion ethanol solution, and is dispersed and prepared into 10mg/mL bimetallic conductive metal organic framework suspension by ultrasonic auxiliary means; the CuM-DBCO suspension is sprayed on separation 29BC or YLS-30T hydrophobic carbon paper by a spray gun to be used as a gas diffusion electrode, and the loading capacity of the obtained electrode is 1mg/cm respectively 2 The electrode area was 3.0cm 2 . Finally, a silica gel pad is used for supporting, and the area of an effective electrode actually participating in catalysis is 1.0cm 2 。
Example 3
Will utilize Cu 0.97 Zn 0.03 The gas diffusion electrode prepared by DBCO is used as a cathode catalyst for electrocatalytic carbon dioxide reduction in a flow cell, foam nickel or platinum titanium mesh is used as an anode, an anion exchange membrane is used for separating the anode from the cathode, an Ag/AgCl electrode is used as a reference electrode, and the electrochemical activity and the selectivity of the catalyst are tested in an electrolyte solution of 1.0M potassium bicarbonate.
Linear Sweep Voltammetry (LSV) of the test catalyst, 800mA/cm was obtained 2 Is a large current of the (c).
Analysis of the product at each current found that CuM-DBCO had higher methane selectivity, as shown in FIG. 4.
Example 4
Will utilize Cu 0.97 Zn 0.03 The gas diffusion electrode prepared from DBCO was tested for electrochemical stability of the catalyst in a flow cell. The surface structure of the catalyst is kept unchanged by combining an in-situ X-ray absorption spectrum in the electrocatalytic carbon dioxide reduction process with XRD test before and after the reaction, and the morphology contrast is not obviously changed, so that the CuM-DBCO has higher electrochemical stability in the electrocatalytic process. In addition, the electrode was at constant current of 200mA/cm 2 The electrocatalytic stability of the gas diffusion electrode was demonstrated by stable catalytic carbon dioxide reduction and 80% selectivity maintained over 12 hours (fig. 5).
The above examples are only preferred embodiments of the present invention and are not limiting of the implementation. The protection scope of the present invention shall be subject to the scope defined by the claims. Other variations or modifications may be made in the various forms based on the above description. Obvious variations or modifications of the embodiments are within the scope of the invention.
Claims (10)
1. A process for preparing the bimetal electrically conductive metal-organic frame material features that 2,3,6,7,10,11,14,15-octahydroxy tetrabenzonaphthalene H 8 DBCO is a bridging ligand, and metal ion Cu 2+ With metal ions M 2+ Metal organic framework material with bi-metal co-coordinated two-dimensional layered structure prepared by solvothermal method，M 2+ Is Zn 2+ 、Co 2+ 、Ni 2+ 、Cd 2+ 、Fe 2+ 、Mn 2+ Any one of them; the material is represented by the formula CuM-DBCO;
the synthetic route is as follows:
xCu(OAc) 2 ·H 2 O+(2-x)M(OAc) 2 ·H 2 O+H 8 DBCO→Cu x (M) 2-x (DBCO) 2
2. the preparation method according to claim 1, characterized in that it comprises in particular the following steps:
(1) Adding 2,3,6,7,10,11,14,15-octahydroxytetrabenzonaphthalene, a copper source and an M metal source into water, uniformly dispersing by ultrasonic waves, and then adding an N-methylpyrrolidone (NMP) solvent dropwise while carrying out ultrasonic waves to obtain a solution A;
(2) Heating the solution A;
(3) And (3) naturally cooling the reactant obtained in the step (2) to room temperature, and then centrifuging, washing and drying to obtain the bimetal conductive metal organic framework material.
3. The method according to claim 2, wherein in the step (1), the copper source is Cu (OAc) 2 ·H 2 O，Cu(NO 3 ) 2 ·3H 2 O、CuCl 2 ·2H 2 Any one of O, copper acetylacetonate, copper fluoride and copper trifluoroacetate;
the M metal source is any one of acetate, nitrate and chloride of M, wherein M= Zn, co, ni, cd, fe, mn;
in the solution A, the concentration of 2,3,6,7,10,11,14,15-octahydroxytetrabenzonaphthalene is 10-200mmol/L, the concentration of a copper source is 20-400mmol/L, the concentration of an M metal source is 20-400mmol/L, the molar ratio of the copper source to the M metal source is a,0< a <100%, and the volume concentration of NMP is 1-30%;
the ultrasonic dispersion time is not less than 2min.
4. The method according to claim 2, wherein in the step (2), the heating temperature is 65 to 140 ℃ and the heating time is 6 to 36 hours.
5. The method according to claim 2, wherein in the step (3), the washing method comprises: respectively washing with N, N-dimethylformamide and absolute methanol for not less than 3 times;
the drying temperature is 60 ℃, and the drying time is not less than 5 hours.
6. A bimetallic conductive metal organic framework material made by the method of any one of claims 1-5.
7. A preparation method of a gas diffusion electrode based on a bimetal conductive metal organic framework material is characterized by comprising the following steps of: the bimetal conductive metal organic framework material in claim 6 is dispersed in Nafion ethanol solution by ultrasonic, and then is sprayed on hydrophobic carbon paper by a spray gun uniformly, and is dried naturally, thus obtaining the gas diffusion electrode.
8. The method of manufacturing according to claim 7, wherein: the mass content of Nafion in the Nafion ethanol solution is 0.25%; the concentration of the bimetal conductive metal organic framework material in Nafion ethanol solution is 5-10mg/ml.
9. The method of manufacturing according to claim 7, wherein: the CuM-DBCO loading in the gas diffusion electrode is 0.1-5mg/cm 2 。
10. Use of a gas diffusion electrode made by the method of any one of claims 7-9 in electrocatalytic carbon dioxide reduction.
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| CN113699556A (en) * | 2021-08-27 | 2021-11-26 | 常州大学 | CoNiMOF-BP QDs/b-CNF composite material electrocatalyst and preparation method thereof |
| CN115172770A (en) * | 2022-08-08 | 2022-10-11 | 苏州大学 | Gas diffusion electrode and preparation method and application thereof |
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| CN109675632A (en) * | 2018-12-28 | 2019-04-26 | 西安交通大学 | A kind of carbon-based ZIF composite catalyst and preparation method thereof and the application in electro-catalysis reduction carbon dioxide reaction |
| CN110010367A (en) * | 2019-03-15 | 2019-07-12 | 天津大学 | A kind of two-dimensional metallic organic frame semiconductor material and preparation method and application |
| WO2021088196A1 (en) * | 2019-11-06 | 2021-05-14 | 中国科学院过程工程研究所 | Dual metal mofs catalyst, and preparation method therefor and use thereof |
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