CN111774085A - Transition metal carbide/metal organic framework compound and super-assembly preparation method thereof - Google Patents
Transition metal carbide/metal organic framework compound and super-assembly preparation method thereof Download PDFInfo
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- CN111774085A CN111774085A CN202010660548.4A CN202010660548A CN111774085A CN 111774085 A CN111774085 A CN 111774085A CN 202010660548 A CN202010660548 A CN 202010660548A CN 111774085 A CN111774085 A CN 111774085A
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- 229910052723 transition metal Inorganic materials 0.000 title claims abstract description 53
- 150000003624 transition metals Chemical class 0.000 title claims abstract description 52
- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 150000001875 compounds Chemical class 0.000 title claims abstract description 12
- 239000000203 mixture Substances 0.000 claims abstract description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 45
- 239000012924 metal-organic framework composite Substances 0.000 claims description 38
- 238000000034 method Methods 0.000 claims description 15
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 claims description 15
- 239000000243 solution Substances 0.000 claims description 14
- 239000003054 catalyst Substances 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 9
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 7
- 238000001354 calcination Methods 0.000 claims description 7
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 6
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 4
- 239000002243 precursor Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 13
- CKUAXEQHGKSLHN-UHFFFAOYSA-N [C].[N] Chemical compound [C].[N] CKUAXEQHGKSLHN-UHFFFAOYSA-N 0.000 abstract description 10
- 239000002923 metal particle Substances 0.000 abstract description 6
- 238000004806 packaging method and process Methods 0.000 abstract description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract 1
- 229910052799 carbon Inorganic materials 0.000 abstract 1
- 238000011065 in-situ storage Methods 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 8
- 238000010000 carbonizing Methods 0.000 description 7
- 238000000157 electrochemical-induced impedance spectroscopy Methods 0.000 description 6
- -1 Transition metal carbides Chemical class 0.000 description 5
- 238000001000 micrograph Methods 0.000 description 5
- 239000011148 porous material Substances 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000001965 increasing effect Effects 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- OQUOOEBLAKQCOP-UHFFFAOYSA-N nitric acid;hexahydrate Chemical compound O.O.O.O.O.O.O[N+]([O-])=O OQUOOEBLAKQCOP-UHFFFAOYSA-N 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- QNRATNLHPGXHMA-XZHTYLCXSA-N (r)-(6-ethoxyquinolin-4-yl)-[(2s,4s,5r)-5-ethyl-1-azabicyclo[2.2.2]octan-2-yl]methanol;hydrochloride Chemical compound Cl.C([C@H]([C@H](C1)CC)C2)CN1[C@@H]2[C@H](O)C1=CC=NC2=CC=C(OCC)C=C21 QNRATNLHPGXHMA-XZHTYLCXSA-N 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000010411 electrocatalyst Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000011185 multilayer composite material Substances 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
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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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B01J35/33—
-
- B01J35/396—
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The invention provides a transition metal carbide/metal organic framework compound and a super-assembly preparation method thereof, and relates to the field of metal organic framework materials. The transition metal carbide/metal organic framework compound provided by the invention is formed by super-assembling a transition metal carbide and wrapping a nitrogen-carbon framework, and a reverse packaging configuration is formed3Is mixed and ground so that the surface of ZIF-67 is coated with WO3And (6) packaging. Finally, the mixture is treated under an inert atmosphere, in the course of which WO3Reacting with carbon in a ZIF-67 framework to generate ditungsten carbide in situ, and super-assembling the material outside a nitrogen-carbon framework. The preparation method is simple and low in costThe obtained material not only strengthens the protection of metal particles in the nitrogen-carbon framework and improves the stability of the material, but also enhances the conductivity of the material.
Description
Technical Field
The invention relates to the field of metal organic framework materials, in particular to a transition metal carbide/metal organic framework compound and a super-assembly preparation method thereof.
Background
With global urgency of fossil energy, clean energy, especially emerging hydrogen energy, is more and more valued, and the electrocatalytic water cracking technology derived from the energy is considered as a potential hydrogen production method. Water splitting is divided into two half reactions: hydrogen Evolution Reactions (HER) and Oxygen Evolution Reactions (OER), driving the reaction to proceed require highly active and stable electrocatalysts. The layered porous structure is beneficial to exposing active centers and enhancing the mass transfer of electrolyte and substrate to the inner layer of the catalyst. Therefore, porous materials are expected to be advantageous materials.
In porous materials, Metal Organic Frameworks (MOFs) have inherent characteristics such as high specific surface area, large pore volume, ordered and adjustable pore active metal centers, and in recent years, porous nitrogen carbon materials derived from the MOFs have wide applications in the fields of energy storage, sensors, catalysis and the like. However, the pure porous nitrogen-carbon material has poor conductivity and few active sites, and the internal metal particles are easily corroded by electrolyte in the electrocatalytic reaction process, so that the overall stability of the catalyst is poor, and the catalyst is difficult to replace a noble metal catalyst. Transition metal carbides, particularly tungsten carbides, not only have a d-charge electron state density similar to that of noble metals, but also are excellent conductive agents, have excellent stability, and are not easily corroded by an electrolyte. Therefore, how to combine the advantages of the transition metal carbide and the metal organic framework to prepare a multilayer composite material with high catalytic activity is important for the development of clean energy.
Disclosure of Invention
The present invention has been made to solve the above problems, and an object of the present invention is to provide a transition metal carbide/metal organic framework composite having higher conductivity and better stability, and a super-assembly method thereof.
The invention provides a super-assembly preparation method of a transition metal carbide/metal organic framework compound, which is characterized by comprising the following steps: and (2) taking a metal organic framework as a precursor, wrapping the metal organic framework by tungsten trioxide, and reacting in an inert atmosphere to obtain the catalyst.
The super-assembly preparation method of the transition metal carbide/metal organic framework compound provided by the invention can also have the characteristic that the metal organic framework is ZIF-67.
The super-assembly preparation method of the transition metal carbide/metal organic framework composite provided by the invention can also have the characteristics that the preparation method of the metal organic framework comprises the following steps: step 1, adding a methanol solution of 2-methylimidazole into a methanol solution of cobalt nitrate to obtain a mixed solution; and 2, stirring the mixed solution at room temperature for reaction, after the reaction is finished, centrifugally washing, taking a solid, and drying to obtain the catalyst.
The super-assembly preparation method of the transition metal carbide/metal organic framework composite provided by the invention can also have the characteristic that the drying temperature is 50-80 ℃.
The super-assembly preparation method of the transition metal carbide/metal organic framework composite provided by the invention can also be characterized in that the concentration of the methanol solution of the cobalt nitrate is 3.33 g/L-13.33 g/L, and the concentration of the methanol solution of the 2-methylimidazole is 25 g/L-100 g/L.
The super-assembly preparation method of the transition metal carbide/metal organic framework composite provided by the invention can also be characterized in that the volume ratio of the methanol solution of the cobalt nitrate to the methanol solution of the 2-methylimidazole is 1-2: 1-2.
The method for preparing the transition metal carbide/metal organic framework composite by super assembly provided by the invention can also have the characteristics that the method for preparing the transition metal carbide/metal organic framework composite by super assembly comprises the following steps: step 1, mixing and grinding the metal organic framework and the tungsten trioxide powder to obtain a mixture; and 2, calcining the mixture in an inert atmosphere to obtain the catalyst.
The super-assembly preparation method of the transition metal carbide/metal-organic framework composite provided by the invention can also be characterized in that the mass ratio of the metal-organic framework to the tungsten trioxide powder is 0.8-1.2: 1.
The super-assembly preparation method of the transition metal carbide/metal organic framework composite provided by the invention can also have the characteristics that the calcination temperature is 600-900 ℃, and the calcination time is 2-5 h.
The invention also provides a transition metal carbide/metal organic framework composite, which is characterized by being prepared by the super-assembly preparation method of the transition metal carbide/metal organic framework composite.
Action and Effect of the invention
According to the transition metal carbide/metal organic framework compound and the super-assembly preparation method thereof, the nitrogen-carbon framework is wrapped by the carbon-tungsten metal compound in the super-assembly mode to form a reverse packaging configuration, so that the protection of metal particles in the nitrogen-carbon framework is enhanced, the stability is enhanced, and the conductivity of the material is also enhanced. The transition metal carbide/metal organic framework compound and the super-assembly strategy thereof have the characteristics of better conductivity, higher stability, simple preparation method and low price.
Drawings
FIG. 1 is a scanning electron microscope image of a metal organic framework ZIF-67 prepared in example 1 of the present invention;
FIG. 2 is a transmission electron microscope image of a metal organic framework ZIF-67 prepared in example 1 of the present invention;
FIG. 3 is a low power scanning electron micrograph of a transition metal carbide/metal organic framework composite prepared in example 1 of the present invention;
FIG. 4 is a high power scanning electron micrograph of a transition metal carbide/metal organic framework composite prepared in example 1 of the present invention;
FIG. 5 is a graph comparing X-ray diffraction patterns of a metal organic framework ZIF-67 prepared in example 1 of the present invention, a derivative Co-NC obtained by directly carbonizing the ZIF-67 prepared in comparative example 1, and a transition metal carbide/metal organic framework composite prepared in example 1.
FIG. 6 is a view showing the metal organic framework ZIF-67 prepared in example 1 of the present invention, the derivative Co-NC obtained by directly carbonizing the ZIF-67 prepared in comparative example 1, and the transition metal carbide/metal organic framework composite (Co-NC @ W) prepared in example 12C) The electrochemical impedance spectroscopy test contrast figure of (1).
Detailed Description
In order to make the technical means, the creation features, the achievement purposes and the effects of the invention easy to understand, the invention is specifically described below by combining the embodiment and the attached drawings.
< example 1>
The embodiment provides a transition metal carbide/metal organic framework composite, and the preparation method comprises the following steps:
step 1, 364mg of Co nitrate hexahydrate (NO)3)2·6H2Dissolving O in 50mL of methanol solution, mixing with 50mL of methanol solution containing 2.05g of 2-methylimidazole, stirring at room temperature for 12 hours, centrifuging, repeatedly washing the sample with methanol, removing redundant metal ions and organic ligands, and then drying the sample in an oven at 60 ℃ to obtain the dark purple metal organic framework ZIF-67.
< comparative example 1>
The comparative example provides a derivative Co-NC obtained by direct carbonization of ZIF-67, and the preparation method comprises the following steps:
taking 1g of metal organic framework ZIF-67, placing the metal organic framework ZIF-67 in an OTF-1200X type tubular furnace filled with inert atmosphere, and then raising the temperature in the furnace to 700 ℃ at the temperature rise rate of 5 ℃/min for 3 hours. And finally, waiting for the furnace body to naturally cool to room temperature, and obtaining the derivative Co-NC obtained by direct carbonization of ZIF-67.
< test example 1>
Scanning electron microscope and transmission electron microscope characterization
For the metal organic framework ZIF-67 and the transition metal carbide/metal organic framework composite (Co-NC @ W) prepared in example 12C) And (5) performing characterization by a scanning electron microscope and a transmission electron microscope, wherein the characterization results are shown in figures 1-4.
FIG. 1 is a scanning electron microscope image of a metal organic framework ZIF-67 prepared in example 1 of the present invention.
FIG. 2 is a transmission electron microscope image of the metal organic framework ZIF-67 prepared in example 1 of the present invention.
As shown in fig. 1 and 2: the surface of the metal organic framework ZIF-67 is smooth, a rhombic dodecahedron structure is formed, and the size is uniform and is about 700-900 nm.
FIG. 3 is a transition metal carbide/metal organic framework composite (Co-NC @ W) prepared in example 1 of the present invention2C) Low power scanning electron microscope image.
FIG. 4 is a transition metal carbide/metal organic framework composite (Co-NC @ W) prepared in example 1 of the present invention2C) High power scanning electron microscopy.
As shown in fig. 3 and 4: the prepared transition metal carbide/metal organic framework composite (Co-NC @ W)2C) Inherits the appearance of the precursor ZIF-67, but the surface of the precursor ZIF-67 becomes very rough, which shows that not only a large number of pores are generated in the calcining process, but also W is generated on the surface of the ZIF-672C, forming a reverse packaging structure. The structure not only strengthens the protection of metal particles in the nitrogen-carbon framework to ensure the stability of the metal particles, but also strengthens the conductivity of the material.
< test example 2>
X-ray diffraction test
The metal organic framework ZIF-67 prepared in example 1, the derivative Co-NC obtained by directly carbonizing the ZIF-67 prepared in comparative example 1, and the transition metal carbide/metal organic framework composite (Co-NC @ W) prepared in example 12C) The X-ray diffraction test was performed, and the test results are shown in fig. 5.
FIG. 5 is a graph comparing the X-ray diffraction patterns of the metal organic framework ZIF-67 obtained in example 1 of the present invention, the derivative Co-NC obtained by directly carbonizing the ZIF-67 obtained in comparative example 1, and the transition metal carbide/metal organic framework composite obtained in example 1
As shown in fig. 5: the Co-NC obtained by directly carbonizing the ZIF-67 has 3 diffraction peaks corresponding to metal Co (PDF:01-1255), and shows that a large amount of Co nanoparticles exist in the Co-NC. And a transition metal carbide/metal organic framework composite (Co-NC @ W)2C) The XRD spectrum of the alloy not only has the diffraction peak of metal Co, but also has strong W2Diffraction peaks of C (PDF:02-1134) confirmed that Co nanoparticles and W in the resulting composite2The two phases C coexist.
< test example 3>
Electrochemical Impedance Spectroscopy (EIS) testing
The metal organic framework ZIF-67 prepared in example 1, the derivative Co-NC obtained by directly carbonizing the ZIF-67 prepared in comparative example 1, and the transition metal carbide/metal organic framework composite (Co-NC @ W) prepared in example 12C) Electrochemical Impedance Spectroscopy (EIS) tests were performed and the results are shown in fig. 6.
FIG. 6 is a view showing the metal organic framework ZIF-67 prepared in example 1 of the present invention, the derivative Co-NC obtained by directly carbonizing the ZIF-67 prepared in comparative example 1, and the transition metal carbide/metal organic framework composite (Co-NC @ W) prepared in example 12C) The electrochemical impedance spectroscopy test contrast figure of (1).
As shown in fig. 6: transition metal carbide/metal organic framework composite (Co-NC @ W)2C) The resistance value of (A) was about half that of Co-NC, indicating that the surface of Co-NC was coated with a layer of W2After C, the conductivity is improved. Due to W2The excellent conductivity of C reduces the resistance of the material, and the smaller resistance is more beneficial to the catalytic reaction, thereby finally improving the transition metal carbide/metal organic framework composite (Co-NC @ W)2C) The catalytic activity of (3).
Effects and effects of the embodiments
According to the transition metal carbide/metal organic framework composite related to the embodiment 1, because the nitrogen-carbon framework is wrapped by the carbon-tungsten metal compound in a super-assembly mode, a reverse packaging configuration is formed, the protection of metal particles in the nitrogen-carbon framework is enhanced, the stability of the material is improved, the conductivity of the material is enhanced, and the electrochemical impedance test shows that the material has smaller resistance, so that the catalytic activity is favorably improved. The preparation and implementation method has the characteristics of simplicity, feasibility and low cost.
The above embodiments are preferred examples of the present invention, and are not intended to limit the scope of the present invention.
Claims (10)
1. A super-assembly preparation method of a transition metal carbide/metal organic framework compound is characterized by comprising the following steps:
and (2) taking a metal organic framework as a precursor, wrapping the metal organic framework by tungsten trioxide, and reacting in an inert atmosphere to obtain the catalyst.
2. The method of preparing a transition metal carbide/metal organic framework composite for super assembly according to claim 1, wherein:
wherein the metal organic framework is ZIF-67.
3. The method of preparing a super assembly of a transition metal carbide/metal organic framework composite according to claim 2, wherein the method of preparing the metal organic framework comprises the steps of:
step 1, adding a methanol solution of 2-methylimidazole into a methanol solution of cobalt nitrate to obtain a mixed solution;
and 2, stirring the mixed solution at room temperature for reaction, after the reaction is finished, centrifugally washing, taking a solid, and drying to obtain the catalyst.
4. The method of preparing a transition metal carbide/metal organic framework composite for super assembly according to claim 3, wherein:
wherein the drying temperature is 50-80 ℃.
5. The method of preparing a transition metal carbide/metal organic framework composite for super assembly according to claim 3, wherein:
wherein the concentration of the methanol solution of the cobalt nitrate is 3.33 g/L-13.33 g/L; the concentration of the methanol solution of the 2-methylimidazole is 25 g/L-100 g/L.
6. The method of preparing a transition metal carbide/metal organic framework composite for super assembly according to claim 3, wherein:
wherein the volume ratio of the methanol solution of the cobalt nitrate to the methanol solution of the 2-methylimidazole is 1-2: 1-2.
7. The method of preparing a transition metal carbide/metal organic framework composite for super assembly according to claim 6, comprising the steps of:
step 1, mixing and grinding the metal organic framework and the tungsten trioxide powder to obtain a mixture;
and 2, calcining the mixture in an inert atmosphere to obtain the transition metal carbide/metal organic framework compound.
8. The method of preparing a transition metal carbide/metal organic framework composite for super assembly according to claim 7, wherein:
wherein the mass ratio of the metal organic framework to the tungsten trioxide powder is 0.8-1.2: 1.
9. The method of preparing a transition metal carbide/metal organic framework composite for super assembly according to claim 7, wherein:
wherein, the calcining temperature in the step 2 is 600-900 ℃, and the calcining time is 2-5 h.
10. A transition metal carbide/metal organic framework composite prepared by the super-assembly method of preparing a transition metal carbide/metal organic framework composite according to any one of claims 1 to 9.
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Cited By (3)
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| CN113457632A (en) * | 2021-06-30 | 2021-10-01 | 烟台大学 | Two-dimensional transition metal carbide/metal organic framework composite aerogel and preparation method thereof |
| CN115025822A (en) * | 2022-05-16 | 2022-09-09 | 湖州特卓科技有限公司 | WO loaded on GO 3 @ ZIF-67 visible light catalytic composite material and preparation and application thereof |
| CN115025822B (en) * | 2022-05-16 | 2024-05-10 | 湖州特卓科技有限公司 | WO supported on GO3ZIF-67 visible light catalytic composite material and preparation and application thereof |
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