WO2022205491A1 - Metal-organic framework composite material and preparation method therefor - Google Patents
Metal-organic framework composite material and preparation method therefor Download PDFInfo
- Publication number
- WO2022205491A1 WO2022205491A1 PCT/CN2021/085760 CN2021085760W WO2022205491A1 WO 2022205491 A1 WO2022205491 A1 WO 2022205491A1 CN 2021085760 W CN2021085760 W CN 2021085760W WO 2022205491 A1 WO2022205491 A1 WO 2022205491A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- cubtc
- composite material
- metal
- cubht
- organic framework
- Prior art date
Links
- 238000002360 preparation method Methods 0.000 title claims abstract description 45
- 239000000463 material Substances 0.000 title claims abstract description 32
- 239000012924 metal-organic framework composite Substances 0.000 title claims abstract description 24
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims abstract description 46
- 239000000243 solution Substances 0.000 claims abstract description 42
- 239000000843 powder Substances 0.000 claims abstract description 39
- 239000006185 dispersion Substances 0.000 claims abstract description 37
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims abstract description 29
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 29
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 29
- 239000002244 precipitate Substances 0.000 claims abstract description 28
- 238000003756 stirring Methods 0.000 claims abstract description 28
- NVGVNJDFTHQFQR-UHFFFAOYSA-N benzene-1,2,3,4,5,6-hexathiol Chemical compound SC1=C(S)C(S)=C(S)C(S)=C1S NVGVNJDFTHQFQR-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- SXTLQDJHRPXDSB-UHFFFAOYSA-N copper;dinitrate;trihydrate Chemical compound O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SXTLQDJHRPXDSB-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000002904 solvent Substances 0.000 claims abstract description 19
- 239000011259 mixed solution Substances 0.000 claims abstract description 16
- 239000011258 core-shell material Substances 0.000 claims abstract description 15
- 238000001035 drying Methods 0.000 claims abstract description 12
- 238000011065 in-situ storage Methods 0.000 claims abstract description 12
- 238000005406 washing Methods 0.000 claims abstract description 10
- 238000001556 precipitation Methods 0.000 claims abstract description 7
- 238000000926 separation method Methods 0.000 claims abstract description 4
- 238000000227 grinding Methods 0.000 claims abstract description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 63
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 43
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 30
- 229910052757 nitrogen Inorganic materials 0.000 claims description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 12
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 8
- 150000001879 copper Chemical class 0.000 claims description 8
- 239000011261 inert gas Substances 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000002131 composite material Substances 0.000 abstract description 13
- QPGJEXWQNJCCSN-UHFFFAOYSA-K [Cu+3].[O-]C(=O)C1=CC(C([O-])=O)=CC(C([O-])=O)=C1 Chemical compound [Cu+3].[O-]C(=O)C1=CC(C([O-])=O)=CC(C([O-])=O)=C1 QPGJEXWQNJCCSN-UHFFFAOYSA-K 0.000 abstract description 12
- 238000001132 ultrasonic dispersion Methods 0.000 abstract 1
- 238000005303 weighing Methods 0.000 abstract 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 21
- 239000000047 product Substances 0.000 description 9
- 239000012621 metal-organic framework Substances 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 238000005119 centrifugation Methods 0.000 description 6
- 239000004570 mortar (masonry) Substances 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 238000007664 blowing Methods 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 230000001476 alcoholic effect Effects 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 229910000365 copper sulfate Inorganic materials 0.000 description 3
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical group Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 3
- 230000005518 electrochemistry Effects 0.000 description 3
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical compound SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 description 3
- 150000003623 transition metal compounds Chemical class 0.000 description 3
- -1 transition metal salts Chemical class 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000005587 bubbling Effects 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000012983 electrochemical energy storage Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 229910001428 transition metal ion Inorganic materials 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000013256 coordination polymer Substances 0.000 description 1
- 229920001795 coordination polymer Polymers 0.000 description 1
- 239000013084 copper-based metal-organic framework Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000010411 electrocatalyst Substances 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000002149 hierarchical pore Substances 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 1
- 239000013384 organic framework Substances 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- 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
Definitions
- the invention relates to an organic framework material and a preparation method thereof, in particular to a metal-organic framework composite material and a preparation method thereof.
- Metal-organic frameworks with hierarchical pore structures, controllable structures, and abundant active centers have received great attention from researchers since their introduction in the 1990s, and have been widely used in gas storage and separation, molecular recognition, pollutant enrichment and adsorption, photocatalysis and other fields.
- the application of metal-organic framework materials in the field of electrochemistry has been gradually carried out, and it is one of the hottest materials in the field of electrochemical energy storage devices and electrocatalysts.
- the transfer efficiency of charges has a significant impact on the kinetics of chemical reactions, which in turn affects the overall performance of active materials.
- Metal-organic frameworks usually have extremely low electronic conductivity due to their special valence bond structure, so their charge transfer efficiency is low when used as active materials, which hinders their application in the field of electrochemistry.
- the common metal-organic framework material copper trimesate as an example, its electrical conductivity is usually 10 -9 S/cm, which is much lower than 10 0 S/cm of common semiconductor material single crystal silicon.
- the purpose of the present invention is to provide a metal-organic framework composite material with significantly improved electrical conductivity
- another purpose of the present invention is to provide a mild reaction, easy to operate and control, The preparation method of metal-organic framework composite material which can significantly improve the electrical conductivity.
- the metal-organic framework composite material of the present invention forms a core-shell structure CuBHT@CuBTC from CuBHT and CuBTC.
- CuBHT is the shell
- CuBTC is the core
- the preparation method of the above-mentioned metal-organic framework composite material comprises the following steps:
- Step 1 preparation of copper trimesate (CuBTC): under stirring, slowly drop the trimesic acid solution into the mixed solution of copper nitrate trihydrate and polyvinylpyrrolidone at a rate of 10mL/min, and then dropwise add the solution. After the end, the obtained mixed solution was allowed to stand at room temperature to obtain a blue precipitate, the precipitate was centrifuged, washed with methanol for several times and then dried to obtain CuBTC powder;
- CuBTC copper trimesate
- Step 2 preparation of copper trimesate (CuBTC) dispersion: Weigh the CuBTC powder obtained in step 1, add a solvent after grinding, and ultrasonically disperse to obtain a CuBTC dispersion;
- Step 3 preparation of CuBHT@CuBTC composite material: adding hexamercaptobenzene into CuBTC dispersion under the protection of inert gas for in-situ reaction, centrifuging, washing the precipitate and drying in an oven to obtain the core-shell structure CuBHT@CuBTC .
- This method has good universality and can be extended to the synthesis of other core-shell structure metal-organic framework composites containing copper, iron, nickel, cobalt, manganese, palladium and other transition metals, and its electrical conductivity has been improved to varying degrees.
- This method has the greatest improvement in the electrical conductivity of copper-based metal-organic frameworks.
- step 1 the concentration of copper nitrate trihydrate is 10-20 mg/mL, and the concentration of polyvinylpyrrolidone is 5-8 mg/mL.
- the molar ratio of copper nitrate trihydrate and trimesic acid was 3:2.
- the solvent is any one of N,N-dimethylformamide, N-methylpyrrolidone and dichloromethane.
- concentration of the CuBTC dispersion liquid is 1 to 10 mg/mL.
- the preparation method of CuBHT is as follows: dissolving the copper salt in ethanol, N,N-dimethylformamide or N-methylpyrrolidone to form a solution of 1-50 mg/mL, blowing nitrogen gas for 30 minutes, Then add hexamercaptobenzene powder under nitrogen protection and stir rapidly.
- the molar ratio of hexamercaptobenzene powder and copper salt is 1:3.
- the copper salt is copper chloride, copper sulfate or copper nitrate.
- the mass ratio of hexamercaptobenzene to CuBTC is 1-10:30.
- the in-situ reaction temperature is 5-35°C
- the reaction time is 2-120 minutes
- the powder drying temperature is 40-90°C.
- hexamercaptobenzene has a very high coordination ability, and can directly extract transition metal ions from the surface of transition metal salts, hydroxides, oxides, and other coordination polymers, and generate transition metal-hexanol at an extremely fast speed.
- the mercaptobenzene complex covers the surface of the original transition metal compound to form a core-shell structure. This is a one-step kinetically controlled process, and the determining step of the reaction is the diffusion rate of hexamercaptobenzene, so the morphology of the original transition metal compound is preserved.
- transition metal-hexamercaptobenzene complexes usually have higher electrical conductivity, so they can be used to improve the electrical conductivity of transition metal compounds.
- a CuBHT@CuBTC composite material with a core-shell structure was successfully synthesized.
- the electrical conductivity of the powder tablet of this material is more than 1 S/cm, which is higher than that of pure copper trimesate (10 -9 S/cm). ) increased by 9 orders of magnitude;
- the preparation method is simple and convenient, the reactions are all carried out in solution, the process is easier to control, the product purification is easier, and the application prospect in the field of electrochemistry is broad;
- transition metal ions such as copper, iron, nickel, cobalt, manganese, and palladium.
- Fig. 1 is the scanning electron microscope picture of the present invention, a is CuBHT@CuBTC composite material, b is pure CuBTC;
- Fig. 2 is the element distribution diagram of CuBHT@CuBTC composite material of the present invention.
- Fig. 3 is the X-ray powder diffraction pattern of the present invention, a is CuBHT@CuBTC composite material, b is pure CuBTC.
- the preparation method of CuBHT is as follows: dissolving copper chloride in ethanol to form a solution of 1 mg/mL, bubbling nitrogen for 30 minutes to remove oxygen, and then adding hexamercaptobenzene powder (molar ratio to copper salt is 1:3) under nitrogen protection And rapid stirring, black solid precipitation appeared immediately in the blue solution, after stirring for 30 minutes, the precipitation was filtered, washed three times with solvent, and then dried in a vacuum oven at 80°C.
- a preparation method of CuBHT@CuBTC metal-organic framework composite material comprising the following steps:
- the molar ratio of copper nitrate and trimesic acid was 3:2.
- the obtained mixed solution was allowed to stand at room temperature for 24 hours to obtain a blue precipitate. After washing three times, drying at 80°C to obtain CuBTC powder;
- the preparation method of CuBHT is as follows: dissolving copper sulfate in N,N-dimethylformamide to form a solution of 50 mg/mL, blowing nitrogen for 30 minutes to remove oxygen, then adding hexamercaptobenzene powder (with copper salt) under nitrogen protection Molar ratio of 1:3) and rapid stirring, black solid precipitate appeared in the blue solution immediately, after stirring for 30 minutes, the precipitate was filtered, washed with solvent 3 times, and then dried in a vacuum oven at 80°C.
- a preparation method of CuBHT@CuBTC metal-organic framework composite material comprising the following steps:
- the molar ratio of copper nitrate and trimesic acid was 3:2.
- the obtained mixed solution was allowed to stand at room temperature for 24 hours to obtain a blue precipitate. After washing three times, drying at 80°C to obtain CuBTC powder;
- the preparation method of CuBHT is as follows: dissolving copper nitrate in N-methylpyrrolidone to form a solution of 25 mg/mL, blowing nitrogen for 30 minutes to remove oxygen, and then adding hexamercaptobenzene powder (molar ratio to copper salt is 1) under nitrogen protection : 3) and stirred rapidly, a black solid precipitate appeared in the blue solution immediately, and after stirring for 30 minutes, the precipitate was filtered, washed with solvent 3 times, and then dried in a vacuum oven at 80°C.
- a preparation method of CuBHT@CuBTC metal-organic framework composite material comprising the following steps:
- the molar ratio of copper nitrate and trimesic acid was 3:2.
- the obtained mixed solution was allowed to stand at room temperature for 24 hours to obtain a blue precipitate. After washing three times, drying at 80°C to obtain CuBTC powder;
- the preparation method of CuBHT is as follows: dissolving copper chloride in ethanol to form a solution of 10 mg/mL, bubbling nitrogen for 30 minutes to remove oxygen, and then adding hexamercaptobenzene powder (molar ratio to copper salt is 1:3) under nitrogen protection And rapid stirring, black solid precipitation appeared immediately in the blue solution, after stirring for 30 minutes, the precipitation was filtered, washed three times with solvent, and then dried in a vacuum oven at 80°C.
- a preparation method of CuBHT@CuBTC metal-organic framework composite material comprising the following steps:
- the molar ratio of copper nitrate and trimesic acid is 3:2.
- the resulting mixed solution is allowed to stand at room temperature for 24 hours to obtain a blue precipitate.
- the precipitate is centrifuged and washed three times with methanol. After drying at 80°C, CuBTC powder was obtained;
- the preparation method of CuBHT is as follows: dissolving copper sulfate in N-methylpyrrolidone to form a solution of 40 mg/mL, blowing nitrogen for 30 minutes to remove oxygen, then adding hexamercaptobenzene powder (molar ratio to copper salt is 1) under nitrogen protection : 3) and stirred rapidly, a black solid precipitate appeared in the blue solution immediately, and after stirring for 30 minutes, the precipitate was filtered, washed with solvent 3 times, and then dried in a vacuum oven at 80°C.
- a preparation method of CuBHT@CuBTC metal-organic framework composite material comprising the following steps:
- the molar ratio of copper nitrate and trimesic acid was 3:2.
- the obtained mixed solution was allowed to stand at room temperature for 24 hours to obtain a blue precipitate. After washing three times, drying at 50 °C to obtain CuBTC powder;
- the preparation method of CuBHT is as follows: dissolving copper nitrate in N,N-dimethylformamide to form a solution of 30 mg/mL, blowing nitrogen for 30 minutes to remove oxygen, then adding hexamercaptobenzene powder (with copper salt) under nitrogen protection Molar ratio of 1:3) and rapid stirring, black solid precipitate appeared in the blue solution immediately, after stirring for 30 minutes, the precipitate was filtered, washed with solvent 3 times, and then dried in a vacuum oven at 80°C.
- a preparation method of CuBHT@CuBTC metal-organic framework composite material comprising the following steps:
- the molar ratio of copper nitrate and trimesic acid was 3:2.
- the obtained mixed solution was allowed to stand at room temperature for 24 hours to obtain a blue precipitate. After washing three times, drying at 80°C to obtain CuBTC powder;
Abstract
Disclosed are a metal-organic framework composite material and a preparation method therefor. The composite material is CuBHT@CuBTC with a core-shell structure formed by CuBHT and CuBTC. The preparation method comprises the following steps: step 1, dropwise adding a solution of trimesic acid to a mixed solution of copper nitrate trihydrate and polyvinylpyrrolidone while stirring, leaving same to stand for precipitation, then carrying out centrifugal separation on same, washing same and drying same to obtain a CuBTC powder; step 2, weighing the obtained CuBTC powder, grinding same and then adding a solvent, followed by carrying out ultrasonic dispersion to obtain a CuBTC dispersion; and step 3, adding hexamercaptobenzene to the CuBTC dispersion for in-situ reaction, followed by carrying out centrifugal separation on same, washing a precipitate and then drying same to obtain the CuBHT@CuBTC. The CuBHT@CuBTC composite material with a core-shell structure is successfully synthesized in the present invention, and the electrical conductivity thereof reaches 1 S/cm or more, which is 9 orders of magnitude higher than the electrical conductivity of pure copper trimesate.
Description
本发明涉及有机骨架材料及其制法，具体为一种金属有机骨架复合材料及其制备方法。The invention relates to an organic framework material and a preparation method thereof, in particular to a metal-organic framework composite material and a preparation method thereof.
具有多级孔道结构、结构可控且活性中心丰富的金属有机骨架材料自1990s年面世以来便受到科研工作者的极大关注，已广泛应用于气体存储和分离、分子识别、污染物富集和吸附、光催化等领域。近年，将金属有机骨架材料应用于电化学领域的研究也逐渐开展，其在电化学储能器件和电催化剂中大显身手，是研究的热点材料之一。然而，在电化学器件中，电荷的传递效率对化学反应的动力学具有重要影响，进而影响活性材料的总体性能。金属有机骨架材料由于其特殊的价键结构，通常具有极低的电子导电率，因此其作为活性物质时电荷传递效率较低，阻碍了其在电化学领域的应用扩展。以常见的具有广泛用途的金属有机骨架材料均苯三酸铜为例，其电导率通常为10
-9S/cm，远低于常见半导体材料单晶硅10
0S/cm。通过改善金属有机骨架材料的电导率以提高其综合性能，扩展其在电化学储能和电催化领域的应用，对丰富基础知识，发展和设计新材料具有极其重要的意义。
Metal-organic frameworks with hierarchical pore structures, controllable structures, and abundant active centers have received great attention from researchers since their introduction in the 1990s, and have been widely used in gas storage and separation, molecular recognition, pollutant enrichment and adsorption, photocatalysis and other fields. In recent years, the application of metal-organic framework materials in the field of electrochemistry has been gradually carried out, and it is one of the hottest materials in the field of electrochemical energy storage devices and electrocatalysts. However, in electrochemical devices, the transfer efficiency of charges has a significant impact on the kinetics of chemical reactions, which in turn affects the overall performance of active materials. Metal-organic frameworks usually have extremely low electronic conductivity due to their special valence bond structure, so their charge transfer efficiency is low when used as active materials, which hinders their application in the field of electrochemistry. Taking the common metal-organic framework material copper trimesate as an example, its electrical conductivity is usually 10 -9 S/cm, which is much lower than 10 0 S/cm of common semiconductor material single crystal silicon. By improving the electrical conductivity of metal-organic frameworks to enhance their comprehensive properties and expand their applications in electrochemical energy storage and electrocatalysis, it is of great significance to enrich basic knowledge and develop and design new materials.
目前，已有研究报道在金属有机骨架材料的孔道结构中引入具有氧化还原活性的客体、变价金属离子等方法来提高材料的电荷传递能力，然而这些方法不仅制备过程较繁琐，破坏金属有机骨架的多孔结构，对电导率的改善程度也有限。At present, it has been reported that the introduction of redox-active guests and variable valence metal ions into the pore structure of metal-organic frameworks can improve the charge transfer ability of materials. Porous structure, the degree of improvement in conductivity is also limited.
因此，如何在温和的条件下大幅度提高金属有机骨架材料的导电性性能亟待解决。Therefore, how to greatly improve the electrical conductivity of metal-organic frameworks under mild conditions needs to be solved urgently.
发明内容SUMMARY OF THE INVENTION
发明目的：为了克服现有技术中存在的不足，本发明的目的是提供一种电导率显著提高的金属有机骨架复合材料，本发明的另一目的是提供一种反应温和、易于操作和控制、能显著提高导电性能的金属有机骨架复合材料的制备方法。Purpose of the invention: In order to overcome the deficiencies in the prior art, the purpose of the present invention is to provide a metal-organic framework composite material with significantly improved electrical conductivity, and another purpose of the present invention is to provide a mild reaction, easy to operate and control, The preparation method of metal-organic framework composite material which can significantly improve the electrical conductivity.
技术方案：本发明所述的一种金属有机骨架复合材料，由CuBHT和CuBTC形成核壳结构CuBHT@CuBTC。Technical solution: The metal-organic framework composite material of the present invention forms a core-shell structure CuBHT@CuBTC from CuBHT and CuBTC.
进一步地，CuBHT为壳层，CuBTC为核。Further, CuBHT is the shell, and CuBTC is the core.
上述金属有机骨架复合材料的制备方法，包括以下步骤：The preparation method of the above-mentioned metal-organic framework composite material comprises the following steps:
步骤一，均苯三酸铜(CuBTC)的制备：在搅拌下，将均苯三酸溶液以10mL/min 的速率缓慢滴加到三水合硝酸铜与聚乙烯吡咯烷酮的混合溶液中，待滴加结束后，将所得混合溶液在室温下静置，得到蓝色沉淀，将沉淀离心分离，用甲醇洗涤多次后干燥得到CuBTC粉末；Step 1, preparation of copper trimesate (CuBTC): under stirring, slowly drop the trimesic acid solution into the mixed solution of copper nitrate trihydrate and polyvinylpyrrolidone at a rate of 10mL/min, and then dropwise add the solution. After the end, the obtained mixed solution was allowed to stand at room temperature to obtain a blue precipitate, the precipitate was centrifuged, washed with methanol for several times and then dried to obtain CuBTC powder;
步骤二，均苯三酸铜(CuBTC)分散液的制备：称取步骤一所得CuBTC粉末，研磨后加入溶剂，超声分散，得到CuBTC分散液；Step 2, preparation of copper trimesate (CuBTC) dispersion: Weigh the CuBTC powder obtained in step 1, add a solvent after grinding, and ultrasonically disperse to obtain a CuBTC dispersion;
步骤三，CuBHT@CuBTC复合材料的制备：在惰性气体保护下将六巯基苯加入到CuBTC分散液中进行原位反应，离心分离，将沉淀洗涤后放入烘箱干燥，得到核壳结构CuBHT@CuBTC。Step 3, preparation of CuBHT@CuBTC composite material: adding hexamercaptobenzene into CuBTC dispersion under the protection of inert gas for in-situ reaction, centrifuging, washing the precipitate and drying in an oven to obtain the core-shell structure CuBHT@CuBTC .
此方法有较好的普适性，可推广至合成其他含有铜、铁、镍、钴、锰、钯等过渡金属的核壳结构金属有机骨架复合材料，并且其电导率有不同程度的提升。此方法对铜基金属有机骨架材料的电导性能提升最大。This method has good universality and can be extended to the synthesis of other core-shell structure metal-organic framework composites containing copper, iron, nickel, cobalt, manganese, palladium and other transition metals, and its electrical conductivity has been improved to varying degrees. This method has the greatest improvement in the electrical conductivity of copper-based metal-organic frameworks.
进一步地，步骤一中，三水合硝酸铜的浓度为10～20mg/mL，聚乙烯吡咯烷酮的浓度为5～8mg/mL。三水合硝酸铜和均苯三酸的摩尔比为3:2。Further, in step 1, the concentration of copper nitrate trihydrate is 10-20 mg/mL, and the concentration of polyvinylpyrrolidone is 5-8 mg/mL. The molar ratio of copper nitrate trihydrate and trimesic acid was 3:2.
进一步地，步骤二中，溶剂为N，N-二甲基甲酰胺、N-甲基吡咯烷酮和二氯甲烷中的任意一种。CuBTC分散液的浓度为1～10mg/mL。Further, in step 2, the solvent is any one of N,N-dimethylformamide, N-methylpyrrolidone and dichloromethane. The concentration of the CuBTC dispersion liquid is 1 to 10 mg/mL.
进一步地，步骤三中，CuBHT的制备方法为：将铜盐溶解在乙醇、N，N-二甲基甲酰胺或N-甲基吡咯烷酮中形成1～50mg/mL的溶液，鼓氮气30分钟，然后在氮气保护下加入六巯基苯粉末并快速搅拌，六巯基苯粉末与铜盐摩尔比为1：3，搅拌30～40分钟反应结束后将沉淀过滤，用溶剂洗涤3次，然后用真空烘箱在80℃烘干。铜盐为氯化铜、硫酸铜或硝酸铜。六巯基苯与CuBTC的质量比为1～10:30。原位反应的温度为5～35℃，反应时间为2～120分钟，粉末干燥温度为40～90℃。Further, in step 3, the preparation method of CuBHT is as follows: dissolving the copper salt in ethanol, N,N-dimethylformamide or N-methylpyrrolidone to form a solution of 1-50 mg/mL, blowing nitrogen gas for 30 minutes, Then add hexamercaptobenzene powder under nitrogen protection and stir rapidly. The molar ratio of hexamercaptobenzene powder and copper salt is 1:3. After stirring for 30 to 40 minutes, after the reaction is over, filter the precipitate, wash it with solvent 3 times, and then use a vacuum oven Dry at 80°C. The copper salt is copper chloride, copper sulfate or copper nitrate. The mass ratio of hexamercaptobenzene to CuBTC is 1-10:30. The in-situ reaction temperature is 5-35°C, the reaction time is 2-120 minutes, and the powder drying temperature is 40-90°C.
制备原理：六巯基苯具有极高的配位能力，可从过渡金属盐、氢氧化物、氧化物、以及其他配位聚合物表面直接夺取过渡金属离子，以极快的速度生成过渡金属-六巯基苯配合物，覆盖在原过渡金属化合物表面，形成核壳结构。这是一步动力学控制的过程，反应的决定步骤为六巯基苯的扩散速率，所以原过渡金属化合物的形貌得以保留。同时，过渡金属-六巯基苯配合物通常具有较高的电导率，因此可以用来改善过渡金属化合物的电导率。Preparation principle: hexamercaptobenzene has a very high coordination ability, and can directly extract transition metal ions from the surface of transition metal salts, hydroxides, oxides, and other coordination polymers, and generate transition metal-hexanol at an extremely fast speed. The mercaptobenzene complex covers the surface of the original transition metal compound to form a core-shell structure. This is a one-step kinetically controlled process, and the determining step of the reaction is the diffusion rate of hexamercaptobenzene, so the morphology of the original transition metal compound is preserved. Meanwhile, transition metal-hexamercaptobenzene complexes usually have higher electrical conductivity, so they can be used to improve the electrical conductivity of transition metal compounds.
有益效果：本发明和现有技术相比，具有如下显著性特点：Beneficial effect: Compared with the prior art, the present invention has the following remarkable features:
1、成功的合成出了一种具有核壳结构的CuBHT@CuBTC复合材料，这种材料粉末压片的电导率达1S/cm以上，相比纯均苯三酸铜(10
-9S/cm)的电导率提升了9个 数量级；
1. A CuBHT@CuBTC composite material with a core-shell structure was successfully synthesized. The electrical conductivity of the powder tablet of this material is more than 1 S/cm, which is higher than that of pure copper trimesate (10 -9 S/cm). ) increased by 9 orders of magnitude;
2、制备方法简单便捷，反应均在溶液中进行，进程更加容易控制，产物提纯更加容易，在电化学领域应用前景广阔；2. The preparation method is simple and convenient, the reactions are all carried out in solution, the process is easier to control, the product purification is easier, and the application prospect in the field of electrochemistry is broad;
3、可推广至其他含铜、铁、镍、钴、锰、钯等过渡金属离子的金属有机骨架材料。3. It can be extended to other metal-organic framework materials containing transition metal ions such as copper, iron, nickel, cobalt, manganese, and palladium.
图1是本发明的扫描电镜图，a为CuBHT@CuBTC复合材料，b为纯CuBTC；Fig. 1 is the scanning electron microscope picture of the present invention, a is CuBHT@CuBTC composite material, b is pure CuBTC;
图2是本发明CuBHT@CuBTC复合材料的元素分布图；Fig. 2 is the element distribution diagram of CuBHT@CuBTC composite material of the present invention;
图3是本发明的X射线粉末衍射图，a为CuBHT@CuBTC复合材料，b为纯CuBTC。Fig. 3 is the X-ray powder diffraction pattern of the present invention, a is CuBHT@CuBTC composite material, b is pure CuBTC.
以下各实施例中所使用的原料均为购买直接使用。The raw materials used in the following examples are purchased and used directly.
实施例1Example 1
CuBHT的制备方法为：将氯化铜溶解在乙醇中形成1mg/mL的溶液，鼓氮气30分钟以除去氧气，然后在氮气保护下加入六巯基苯粉末(与铜盐摩尔比为1：3)并快速搅拌，蓝色溶液中立即出现黑色固体沉淀，搅拌30分钟后将沉淀过滤，用溶剂洗涤3次，然后用真空烘箱80℃烘干。The preparation method of CuBHT is as follows: dissolving copper chloride in ethanol to form a solution of 1 mg/mL, bubbling nitrogen for 30 minutes to remove oxygen, and then adding hexamercaptobenzene powder (molar ratio to copper salt is 1:3) under nitrogen protection And rapid stirring, black solid precipitation appeared immediately in the blue solution, after stirring for 30 minutes, the precipitation was filtered, washed three times with solvent, and then dried in a vacuum oven at 80°C.
一种CuBHT@CuBTC金属有机骨架复合材料的制备方法，包括以下步骤：A preparation method of CuBHT@CuBTC metal-organic framework composite material, comprising the following steps:
(1)均苯三酸铜的制备：(1) preparation of copper trimesate:
将3.9g三水合硝酸铜与2g聚乙烯吡咯烷酮溶解于250mL无水甲醇溶剂中，得到硝酸铜与聚乙烯吡咯烷酮的混合甲醇溶液，三水合硝酸铜的浓度为15.6mg/mL，聚乙烯吡咯烷酮的浓度为8mg/mL，另称取2.26g均苯三酸溶解于250mL无水甲醇溶液，在搅拌下将均苯三酸的醇溶液以10mL/min的速率缓慢滴加到上述硝酸铜与聚乙烯吡咯烷酮的混合溶液中，硝酸铜和均苯三酸的摩尔比为3:2，待滴加结束后，将所得混合溶液在室温下静置24小时，得到蓝色沉淀，将沉淀离心分离，用甲醇洗涤三次后80℃干燥，得到CuBTC粉末；Dissolve 3.9g of copper nitrate trihydrate and 2g of polyvinylpyrrolidone in 250mL of anhydrous methanol solvent to obtain a mixed methanol solution of copper nitrate and polyvinylpyrrolidone, the concentration of copper nitrate trihydrate is 15.6mg/mL, the concentration of polyvinylpyrrolidone It is 8mg/mL, and 2.26g of trimesic acid is taken and dissolved in 250mL of anhydrous methanol solution, and the alcoholic solution of trimesic acid is slowly added dropwise to the above-mentioned copper nitrate and polyvinylpyrrolidone at a rate of 10mL/min under stirring. In the mixed solution, the molar ratio of copper nitrate and trimesic acid was 3:2. After the dropwise addition, the obtained mixed solution was allowed to stand at room temperature for 24 hours to obtain a blue precipitate. After washing three times, drying at 80°C to obtain CuBTC powder;
(2)CuBTC分散液的制备：(2) Preparation of CuBTC dispersion:
称取20mg的CuBTC粉末，置于研钵中充分研磨后加入二氯甲烷20mL，超声至分散液为均匀的蓝色，得到浓度为1mg/mL的CuBTC分散液。Weigh 20 mg of CuBTC powder, place it in a mortar and fully grind it, add 20 mL of dichloromethane, and sonicate until the dispersion is uniform blue to obtain a CuBTC dispersion with a concentration of 1 mg/mL.
(3)CuBHT@CuBTC复合材料的制备：(3) Preparation of CuBHT@CuBTC composites:
在氮气保护和搅拌下将含1mg六巯基苯的5mL二氯甲烷溶液加入到CuBTC分散液 中。5℃原位反应60分钟后离心分离，将沉淀用二氯甲烷洗涤后放入烘箱40℃干燥，得到核壳结构CuBHT@CuBTC。产物外观为蓝绿色粉末，电导率为1.1S/cm。A solution of 1 mg of hexamercaptobenzene in 5 mL of dichloromethane was added to the CuBTC dispersion under nitrogen blanketing with stirring. After in-situ reaction at 5°C for 60 minutes, centrifugation was performed, and the precipitate was washed with dichloromethane and then dried in an oven at 40°C to obtain the core-shell structure CuBHT@CuBTC. The appearance of the product is blue-green powder, and the conductivity is 1.1 S/cm.
实施例2Example 2
CuBHT的制备方法为：将硫酸铜溶解在N，N-二甲基甲酰胺中形成50mg/mL的溶液，鼓氮气30分钟以除去氧气，然后在氮气保护下加入六巯基苯粉末(与铜盐摩尔比为1：3)并快速搅拌，蓝色溶液中立即出现黑色固体沉淀，搅拌30分钟后将沉淀过滤，用溶剂洗涤3次，然后用真空烘箱80℃烘干。The preparation method of CuBHT is as follows: dissolving copper sulfate in N,N-dimethylformamide to form a solution of 50 mg/mL, blowing nitrogen for 30 minutes to remove oxygen, then adding hexamercaptobenzene powder (with copper salt) under nitrogen protection Molar ratio of 1:3) and rapid stirring, black solid precipitate appeared in the blue solution immediately, after stirring for 30 minutes, the precipitate was filtered, washed with solvent 3 times, and then dried in a vacuum oven at 80°C.
一种CuBHT@CuBTC金属有机骨架复合材料的制备方法，包括以下步骤：A preparation method of CuBHT@CuBTC metal-organic framework composite material, comprising the following steps:
(1)均苯三酸铜的制备：(1) preparation of copper trimesate:
将2.59g三水合硝酸铜与1.25g聚乙烯吡咯烷酮溶解于250mL无水甲醇溶剂中，得到硝酸铜与聚乙烯吡咯烷酮的混合甲醇溶液，三水合硝酸铜的浓度为10mg/mL，聚乙烯吡咯烷酮的浓度为5mg/mL，另称取1.5g均苯三酸溶解于250mL无水甲醇溶液，在搅拌下将均苯三酸的醇溶液以10mL/min的速率缓慢滴加到上述硝酸铜与聚乙烯吡咯烷酮的混合溶液中，硝酸铜和均苯三酸的摩尔比为3:2，待滴加结束后，将所得混合溶液在室温下静置24小时，得到蓝色沉淀，将沉淀离心分离，用甲醇洗涤三次后80℃干燥，得到CuBTC粉末；Dissolve 2.59g of copper nitrate trihydrate and 1.25g of polyvinylpyrrolidone in 250mL of anhydrous methanol solvent to obtain a mixed methanol solution of copper nitrate and polyvinylpyrrolidone, the concentration of copper nitrate trihydrate is 10mg/mL, the concentration of polyvinylpyrrolidone It is 5mg/mL, and 1.5g of trimesic acid is taken and dissolved in 250mL of anhydrous methanol solution, and the alcohol solution of trimesic acid is slowly added dropwise to the above-mentioned copper nitrate and polyvinylpyrrolidone at a rate of 10mL/min under stirring. In the mixed solution, the molar ratio of copper nitrate and trimesic acid was 3:2. After the dropwise addition, the obtained mixed solution was allowed to stand at room temperature for 24 hours to obtain a blue precipitate. After washing three times, drying at 80°C to obtain CuBTC powder;
(2)CuBTC分散液的制备：(2) Preparation of CuBTC dispersion:
称取50mg的CuBTC粉末，置于研钵中充分研磨后加入N-甲基吡咯烷酮20mL，超声至分散液为均匀的蓝色，得到浓度为2.5mg/mL的CuBTC分散液。Weigh 50 mg of CuBTC powder, place it in a mortar and fully grind it, add 20 mL of N-methylpyrrolidone, and sonicate until the dispersion is uniform blue to obtain a CuBTC dispersion with a concentration of 2.5 mg/mL.
(3)CuBHT@CuBTC复合材料的制备：(3) Preparation of CuBHT@CuBTC composites:
在氩气保护和搅拌下将5mg六巯基苯粉末加入到CuBTC分散液中。35℃原位反应120分钟后离心分离，将沉淀用乙醇洗涤后放入烘箱80℃干燥，得到核壳结构CuBHT@CuBTC。产物外观为绿色粉末，其压片电导率为1.3S/cm。5 mg of hexamercaptobenzene powder was added to the CuBTC dispersion under argon protection and stirring. After in-situ reaction at 35 °C for 120 minutes, centrifugation was performed, and the precipitate was washed with ethanol and then dried in an oven at 80 °C to obtain the core-shell structure CuBHT@CuBTC. The appearance of the product is green powder, and its tablet conductivity is 1.3 S/cm.
实施例3Example 3
CuBHT的制备方法为：将硝酸铜溶解在N-甲基吡咯烷酮中形成25mg/mL的溶液，鼓氮气30分钟以除去氧气，然后在氮气保护下加入六巯基苯粉末(与铜盐摩尔比为1：3)并快速搅拌，蓝色溶液中立即出现黑色固体沉淀，搅拌30分钟后将沉淀过滤，用溶剂洗涤3次，然后用真空烘箱80℃烘干。The preparation method of CuBHT is as follows: dissolving copper nitrate in N-methylpyrrolidone to form a solution of 25 mg/mL, blowing nitrogen for 30 minutes to remove oxygen, and then adding hexamercaptobenzene powder (molar ratio to copper salt is 1) under nitrogen protection : 3) and stirred rapidly, a black solid precipitate appeared in the blue solution immediately, and after stirring for 30 minutes, the precipitate was filtered, washed with solvent 3 times, and then dried in a vacuum oven at 80°C.
一种CuBHT@CuBTC金属有机骨架复合材料的制备方法，包括以下步骤：A preparation method of CuBHT@CuBTC metal-organic framework composite material, comprising the following steps:
(1)均苯三酸铜的制备：(1) preparation of copper trimesate:
将3.9g三水合硝酸铜与2g聚乙烯吡咯烷酮溶解于250mL无水甲醇溶剂中，得到硝酸铜与聚乙烯吡咯烷酮的混合甲醇溶液，三水合硝酸铜的浓度为15.6mg/mL，聚乙烯吡咯烷酮的浓度为8mg/mL，另称取2.26g均苯三酸溶解于250mL无水甲醇溶液，在搅拌下将均苯三酸的醇溶液以10mL/min的速率缓慢滴加到上述硝酸铜与聚乙烯吡咯烷酮的混合溶液中，硝酸铜和均苯三酸的摩尔比为3:2，待滴加结束后，将所得混合溶液在室温下静置24小时，得到蓝色沉淀，将沉淀离心分离，用甲醇洗涤三次后80℃干燥，得到CuBTC粉末；Dissolve 3.9g of copper nitrate trihydrate and 2g of polyvinylpyrrolidone in 250mL of anhydrous methanol solvent to obtain a mixed methanol solution of copper nitrate and polyvinylpyrrolidone, the concentration of copper nitrate trihydrate is 15.6mg/mL, the concentration of polyvinylpyrrolidone It is 8mg/mL, and 2.26g of trimesic acid is taken and dissolved in 250mL of anhydrous methanol solution, and the alcoholic solution of trimesic acid is slowly added dropwise to the above-mentioned copper nitrate and polyvinylpyrrolidone at a rate of 10mL/min under stirring. In the mixed solution, the molar ratio of copper nitrate and trimesic acid was 3:2. After the dropwise addition, the obtained mixed solution was allowed to stand at room temperature for 24 hours to obtain a blue precipitate. After washing three times, drying at 80°C to obtain CuBTC powder;
(2)CuBTC分散液的制备：(2) Preparation of CuBTC dispersion:
称取0.15g的CuBTC粉末，置于研钵中充分研磨后加入N,N-二甲基甲酰胺20mL，超声至分散液为均匀的蓝色，得到浓度为7.5mg/mL的CuBTC分散液。Weigh 0.15 g of CuBTC powder, place it in a mortar and grind it fully, add 20 mL of N,N-dimethylformamide, and sonicate until the dispersion is uniform blue to obtain a CuBTC dispersion with a concentration of 7.5 mg/mL.
(3)CuBHT@CuBTC复合材料的制备：(3) Preparation of CuBHT@CuBTC composites:
在氮气保护和搅拌下将10mg六巯基苯粉末加入到CuBTC分散液中，分散液立即变为黑色。20℃原位反应2分钟后离心分离，将沉淀用乙醇洗涤后放入烘箱80℃干燥，得到核壳结构CuBHT@CuBTC。产物外观为墨绿色粉末，电导率为4.6S/cm。10 mg of hexamercaptobenzene powder was added to the CuBTC dispersion under nitrogen protection and stirring, and the dispersion turned black immediately. After in-situ reaction at 20 °C for 2 minutes, centrifugation was performed, and the precipitate was washed with ethanol and then dried in an oven at 80 °C to obtain the core-shell structure CuBHT@CuBTC. The appearance of the product is dark green powder, and the conductivity is 4.6S/cm.
本实施例所得产物的扫描电镜结果如图1所示，反应前的CuBTC表面较光滑，反应后生成的CuBHT@CuBTC表面***糙，但八面体结构没有改变。The scanning electron microscope results of the product obtained in this example are shown in Figure 1. The surface of the CuBTC before the reaction is relatively smooth, and the surface of the CuBHT@CuBTC generated after the reaction becomes rough, but the octahedral structure does not change.
实施例4Example 4
CuBHT的制备方法为：将氯化铜溶解在乙醇中形成10mg/mL的溶液，鼓氮气30分钟以除去氧气，然后在氮气保护下加入六巯基苯粉末(与铜盐摩尔比为1：3)并快速搅拌，蓝色溶液中立即出现黑色固体沉淀，搅拌30分钟后将沉淀过滤，用溶剂洗涤3次，然后用真空烘箱80℃烘干。The preparation method of CuBHT is as follows: dissolving copper chloride in ethanol to form a solution of 10 mg/mL, bubbling nitrogen for 30 minutes to remove oxygen, and then adding hexamercaptobenzene powder (molar ratio to copper salt is 1:3) under nitrogen protection And rapid stirring, black solid precipitation appeared immediately in the blue solution, after stirring for 30 minutes, the precipitation was filtered, washed three times with solvent, and then dried in a vacuum oven at 80°C.
一种CuBHT@CuBTC金属有机骨架复合材料的制备方法，包括以下步骤：A preparation method of CuBHT@CuBTC metal-organic framework composite material, comprising the following steps:
(1)均苯三酸铜的制备：(1) preparation of copper trimesate:
将5g三水合硝酸铜与2g聚乙烯吡咯烷酮溶解于250mL无水甲醇溶剂中，得到硝酸铜与聚乙烯吡咯烷酮的混合甲醇溶液，三水合硝酸铜的浓度为20mg/mL，聚乙烯吡咯烷酮的浓度为8mg/mL，另称取2.9g均苯三酸溶解于250mL无水甲醇溶液，在搅拌下将均苯三酸的醇溶液以10mL/min的速率缓慢滴加到上述硝酸铜与聚乙烯吡咯烷酮的混合溶液中，硝酸铜和均苯三酸的摩尔比为3:2，待滴加结束后，将所得混合溶液在室温下静置24小时，得到蓝色沉淀，将沉淀离心分离，用甲醇洗涤三次后80℃干燥，得到CuBTC粉末；Dissolve 5g of copper nitrate trihydrate and 2g of polyvinylpyrrolidone in 250mL of anhydrous methanol solvent to obtain a mixed methanol solution of copper nitrate and polyvinylpyrrolidone, the concentration of copper nitrate trihydrate is 20mg/mL, and the concentration of polyvinylpyrrolidone is 8mg /mL, take 2.9g of trimesic acid and dissolve it in 250mL of anhydrous methanol solution. Under stirring, the alcohol solution of trimesic acid is slowly added dropwise to the mixture of the above copper nitrate and polyvinylpyrrolidone at a rate of 10mL/min. In the solution, the molar ratio of copper nitrate and trimesic acid is 3:2. After the dropwise addition, the resulting mixed solution is allowed to stand at room temperature for 24 hours to obtain a blue precipitate. The precipitate is centrifuged and washed three times with methanol. After drying at 80°C, CuBTC powder was obtained;
(2)CuBTC分散液的制备：(2) Preparation of CuBTC dispersion:
称取0.15g的CuBTC粉末，置于研钵中充分研磨后加入N,N-二甲基甲酰胺20mL，超声至分散液为均匀的蓝色，得到浓度为7.5mg/mL的CuBTC分散液。Weigh 0.15 g of CuBTC powder, place it in a mortar and grind it fully, add 20 mL of N,N-dimethylformamide, and sonicate until the dispersion is uniform blue to obtain a CuBTC dispersion with a concentration of 7.5 mg/mL.
(3)CuBHT@CuBTC复合材料的制备：(3) Preparation of CuBHT@CuBTC composites:
在氮气保护和搅拌下将50mg六巯基苯粉末加入到CuBTC分散液中，蓝色分散液立即变为黑色。10℃原位反应120分钟后离心分离，将沉淀用乙醇洗涤后放入烘箱90℃干燥，得到核壳结构CuBHT@CuBTC。产物外观为黑色，电导率为13.4S/cm。50 mg of hexamercaptobenzene powder was added to the CuBTC dispersion under nitrogen protection and stirring, and the blue dispersion immediately turned black. After in-situ reaction at 10 °C for 120 minutes, centrifugation was performed, and the precipitate was washed with ethanol and then dried in an oven at 90 °C to obtain the core-shell structure CuBHT@CuBTC. The appearance of the product is black, and the conductivity is 13.4 S/cm.
实施例5Example 5
CuBHT的制备方法为：将硫酸铜溶解在N-甲基吡咯烷酮中形成40mg/mL的溶液，鼓氮气30分钟以除去氧气，然后在氮气保护下加入六巯基苯粉末(与铜盐摩尔比为1：3)并快速搅拌，蓝色溶液中立即出现黑色固体沉淀，搅拌30分钟后将沉淀过滤，用溶剂洗涤3次，然后用真空烘箱80℃烘干。The preparation method of CuBHT is as follows: dissolving copper sulfate in N-methylpyrrolidone to form a solution of 40 mg/mL, blowing nitrogen for 30 minutes to remove oxygen, then adding hexamercaptobenzene powder (molar ratio to copper salt is 1) under nitrogen protection : 3) and stirred rapidly, a black solid precipitate appeared in the blue solution immediately, and after stirring for 30 minutes, the precipitate was filtered, washed with solvent 3 times, and then dried in a vacuum oven at 80°C.
一种CuBHT@CuBTC金属有机骨架复合材料的制备方法，包括以下步骤：A preparation method of CuBHT@CuBTC metal-organic framework composite material, comprising the following steps:
(1)均苯三酸铜的制备：(1) preparation of copper trimesate:
将3.9g三水合硝酸铜与2g聚乙烯吡咯烷酮溶解于250mL无水甲醇溶剂中，得到硝酸铜与聚乙烯吡咯烷酮的混合甲醇溶液，三水合硝酸铜的浓度为15.6mg/mL，聚乙烯吡咯烷酮的浓度为8mg/mL，另称取2.26g均苯三酸溶解于250mL无水甲醇溶液，在搅拌下将均苯三酸的醇溶液以10mL/min的速率缓慢滴加到上述硝酸铜与聚乙烯吡咯烷酮的混合溶液中，硝酸铜和均苯三酸的摩尔比为3:2，待滴加结束后，将所得混合溶液在室温下静置24小时，得到蓝色沉淀，将沉淀离心分离，用甲醇洗涤三次后50℃干燥，得到CuBTC粉末；Dissolve 3.9g of copper nitrate trihydrate and 2g of polyvinylpyrrolidone in 250mL of anhydrous methanol solvent to obtain a mixed methanol solution of copper nitrate and polyvinylpyrrolidone, the concentration of copper nitrate trihydrate is 15.6mg/mL, the concentration of polyvinylpyrrolidone It is 8mg/mL, and 2.26g of trimesic acid is taken and dissolved in 250mL of anhydrous methanol solution, and the alcoholic solution of trimesic acid is slowly added dropwise to the above-mentioned copper nitrate and polyvinylpyrrolidone at a rate of 10mL/min under stirring. In the mixed solution, the molar ratio of copper nitrate and trimesic acid was 3:2. After the dropwise addition, the obtained mixed solution was allowed to stand at room temperature for 24 hours to obtain a blue precipitate. After washing three times, drying at 50 °C to obtain CuBTC powder;
(2)CuBTC分散液的制备：(2) Preparation of CuBTC dispersion:
称取0.21g的CuBTC粉末，置于研钵中充分研磨后加入N-甲基吡咯烷酮20mL，超声至分散液为均匀的蓝色，得到浓度为10.5mg/mL的CuBTC分散液。Weigh 0.21 g of CuBTC powder, place it in a mortar and fully grind it, add 20 mL of N-methylpyrrolidone, and sonicate until the dispersion is uniform blue to obtain a CuBTC dispersion with a concentration of 10.5 mg/mL.
(3)CuBHT@CuBTC复合材料的制备：(3) Preparation of CuBHT@CuBTC composites:
在氮气保护和搅拌下将50mg六巯基苯溶解在10mL的N,N-二甲基甲酰胺中制得浓度为5mg/mL的溶液。在氮气保护下吸取6mL六巯基苯溶液滴加到CuBTC分散液中，分散液立即变为黑色。30℃原位反应30分钟后离心分离，将沉淀用乙醇洗涤后放入烘箱90℃干燥，得到核壳结构CuBHT@CuBTC。产物外观为墨绿色粉末，压片电导率8.3S/cm。Under nitrogen protection and stirring, 50 mg of hexamercaptobenzene was dissolved in 10 mL of N,N-dimethylformamide to prepare a solution with a concentration of 5 mg/mL. Under nitrogen protection, 6 mL of hexamercaptobenzene solution was added dropwise to the CuBTC dispersion, and the dispersion turned black immediately. After in-situ reaction at 30 °C for 30 minutes, centrifugation was performed, and the precipitate was washed with ethanol and then dried in an oven at 90 °C to obtain the core-shell structure CuBHT@CuBTC. The appearance of the product is dark green powder, and the tablet conductivity is 8.3S/cm.
实施例6Example 6
CuBHT的制备方法为：将硝酸铜溶解在N，N-二甲基甲酰胺中形成30mg/mL的溶液，鼓氮气30分钟以除去氧气，然后在氮气保护下加入六巯基苯粉末(与铜盐摩尔比为1：3)并快速搅拌，蓝色溶液中立即出现黑色固体沉淀，搅拌30分钟后将沉淀过滤，用溶剂洗涤3次，然后用真空烘箱80℃烘干。The preparation method of CuBHT is as follows: dissolving copper nitrate in N,N-dimethylformamide to form a solution of 30 mg/mL, blowing nitrogen for 30 minutes to remove oxygen, then adding hexamercaptobenzene powder (with copper salt) under nitrogen protection Molar ratio of 1:3) and rapid stirring, black solid precipitate appeared in the blue solution immediately, after stirring for 30 minutes, the precipitate was filtered, washed with solvent 3 times, and then dried in a vacuum oven at 80°C.
一种CuBHT@CuBTC金属有机骨架复合材料的制备方法，包括以下步骤：A preparation method of CuBHT@CuBTC metal-organic framework composite material, comprising the following steps:
(1)均苯三酸铜的制备：(1) preparation of copper trimesate:
将3.9g三水合硝酸铜与2g聚乙烯吡咯烷酮溶解于250mL无水甲醇溶剂中，得到硝酸铜与聚乙烯吡咯烷酮的混合甲醇溶液，三水合硝酸铜的浓度为15.6mg/mL，聚乙烯吡咯烷酮的浓度为8mg/mL，另称取2.26g均苯三酸溶解于250mL无水甲醇溶液，在搅拌下将均苯三酸的醇溶液以10mL/min的速率缓慢滴加到上述硝酸铜与聚乙烯吡咯烷酮的混合溶液中，硝酸铜和均苯三酸的摩尔比为3:2，待滴加结束后，将所得混合溶液在室温下静置24小时，得到蓝色沉淀，将沉淀离心分离，用甲醇洗涤三次后80℃干燥，得到CuBTC粉末；Dissolve 3.9g of copper nitrate trihydrate and 2g of polyvinylpyrrolidone in 250mL of anhydrous methanol solvent to obtain a mixed methanol solution of copper nitrate and polyvinylpyrrolidone, the concentration of copper nitrate trihydrate is 15.6mg/mL, the concentration of polyvinylpyrrolidone It is 8mg/mL, and 2.26g of trimesic acid is taken and dissolved in 250mL of anhydrous methanol solution, and the alcoholic solution of trimesic acid is slowly added dropwise to the above-mentioned copper nitrate and polyvinylpyrrolidone at a rate of 10mL/min under stirring. In the mixed solution, the molar ratio of copper nitrate and trimesic acid was 3:2. After the dropwise addition, the obtained mixed solution was allowed to stand at room temperature for 24 hours to obtain a blue precipitate. After washing three times, drying at 80°C to obtain CuBTC powder;
(2)CuBTC分散液的制备：(2) Preparation of CuBTC dispersion:
称取0.15g的CuBTC粉末，置于研钵中充分研磨后加入N,N-二甲基甲酰胺20mL，超声至分散液为均匀的蓝色，得到浓度为7.5mg/mL的CuBTC分散液。Weigh 0.15 g of CuBTC powder, place it in a mortar and grind it fully, add 20 mL of N,N-dimethylformamide, and sonicate until the dispersion is uniform blue to obtain a CuBTC dispersion with a concentration of 7.5 mg/mL.
(3)CuBHT@CuBTC复合材料的制备：(3) Preparation of CuBHT@CuBTC composites:
在氮气保护和搅拌下将30mg六巯基苯粉末加入到CuBTC分散液中，分散液立即变为黑色。15℃原位反应60分钟后离心分离，将沉淀用乙醇洗涤后放入烘箱80℃干燥，得到核壳结构CuBHT@CuBTC。产物外观为墨绿色粉末，压片电导率为6.7S/cm。30 mg of hexamercaptobenzene powder was added to the CuBTC dispersion under nitrogen protection and stirring, and the dispersion turned black immediately. After in-situ reaction at 15 °C for 60 minutes, centrifugation was performed, and the precipitate was washed with ethanol and then dried in an oven at 80 °C to obtain the core-shell structure CuBHT@CuBTC. The appearance of the product is dark green powder, and the tablet conductivity is 6.7S/cm.
对比例Comparative ratio
纯均苯三酸铜(CuBTC)，具体合成见实施例6的步骤(1)。Pure copper trimesate (CuBTC), see step (1) of Example 6 for the specific synthesis.
如图2，由实施例6所得产物的元素分布图，可以看出，硫元素仅分布在八面体壳层，说明六巯基苯与CuBTC表面的铜反应后原位生成了CuBHT包裹在CuBTC表面，CuBTC核不受影响。实施例6所得CuBHT@CuBTC与纯CuBTC的X射线粉末衍射图如图3所示，反应后的产物中CuBTC的量仍占据绝对优势，CuBHT信号不明显。As shown in Figure 2, from the element distribution diagram of the product obtained in Example 6, it can be seen that the sulfur element is only distributed in the octahedral shell layer, indicating that after the reaction between hexamercaptobenzene and the copper on the surface of CuBTC, CuBHT was formed in situ and wrapped on the surface of CuBTC, CuBTC cores are not affected. The X-ray powder diffraction patterns of CuBHT@CuBTC and pure CuBTC obtained in Example 6 are shown in Figure 3. The amount of CuBTC in the reaction product still dominates, and the CuBHT signal is not obvious.
Claims (10)
- 一种金属有机骨架复合材料，其特征在于：由CuBHT和CuBTC形成核壳结构CuBHT@CuBTC。A metal-organic framework composite material is characterized in that: a core-shell structure CuBHT@CuBTC is formed by CuBHT and CuBTC.
- 根据权利要求1所述的一种金属有机骨架复合材料，其特征在于：所述CuBHT为壳层，所述CuBTC为核。The metal-organic framework composite material according to claim 1, wherein the CuBHT is a shell, and the CuBTC is a core.
- 根据权利要求1所述的一种金属有机骨架复合材料的制备方法，其特征在于，包括以下步骤：A kind of preparation method of metal-organic framework composite material according to claim 1, is characterized in that, comprises the following steps:步骤一，在搅拌下，将均苯三酸溶液滴加到三水合硝酸铜与聚乙烯吡咯烷酮的混合溶液中，待滴加结束后，将所得混合溶液在室温下静置，得到沉淀，将沉淀离心分离，用甲醇洗涤多次后干燥得到CuBTC粉末；Step 1, under stirring, add the trimesic acid solution dropwise to the mixed solution of copper nitrate trihydrate and polyvinylpyrrolidone, after the dropwise addition is completed, the obtained mixed solution is allowed to stand at room temperature to obtain precipitation, and the precipitation is Centrifugal separation, washing with methanol for several times and drying to obtain CuBTC powder;步骤二，称取步骤一所得CuBTC粉末，研磨后加入溶剂，超声分散，得到CuBTC分散液；Step 2, weigh the CuBTC powder obtained in step 1, add a solvent after grinding, and ultrasonically disperse to obtain a CuBTC dispersion;步骤三，在惰性气体保护下将六巯基苯加入到CuBTC分散液中进行原位反应，离心分离，将沉淀洗涤后放入烘箱干燥，得到核壳结构CuBHT@CuBTC。Step 3, adding hexamercaptobenzene into the CuBTC dispersion under the protection of inert gas for in-situ reaction, centrifuging, washing the precipitate, and then placing it in an oven to dry to obtain the core-shell structure CuBHT@CuBTC.
- 根据权利要求3所述的一种金属有机骨架复合材料的制备方法，其特征在于：所述步骤一中，三水合硝酸铜的浓度为10～20mg/mL，聚乙烯吡咯烷酮的浓度为5～8mg/mL。The method for preparing a metal-organic framework composite material according to claim 3, wherein in the step 1, the concentration of copper nitrate trihydrate is 10-20 mg/mL, and the concentration of polyvinylpyrrolidone is 5-8 mg /mL.
- 根据权利要求3所述的一种金属有机骨架复合材料的制备方法，其特征在于：所述步骤一中，三水合硝酸铜和均苯三酸的摩尔比为3:2。The method for preparing a metal-organic framework composite material according to claim 3, wherein in the step 1, the molar ratio of copper nitrate trihydrate and trimesic acid is 3:2.
- 根据权利要求3所述的一种金属有机骨架复合材料的制备方法，其特征在于：所述步骤二中，溶剂为N，N-二甲基甲酰胺、N-甲基吡咯烷酮和二氯甲烷中的任意一种。The method for preparing a metal-organic framework composite material according to claim 3, wherein in the second step, the solvent is N,N-dimethylformamide, N-methylpyrrolidone and dichloromethane any of the .
- 根据权利要求3所述的一种金属有机骨架复合材料的制备方法，其特征在于：所述步骤二中，CuBTC分散液的浓度为1～10mg/mL。The method for preparing a metal-organic framework composite material according to claim 3, wherein in the second step, the concentration of the CuBTC dispersion liquid is 1-10 mg/mL.
- 根据权利要求3所述的一种金属有机骨架复合材料的制备方法，其特征在于：所述步骤三中，CuBHT的制备方法为：将铜盐溶解在乙醇、N，N-二甲基甲酰胺或N-甲基吡咯烷酮中形成1～50mg/mL的溶液，鼓氮气，然后在氮气保护下加入六巯基苯粉末并搅拌，反应结束后将沉淀过滤，用溶剂洗涤，然后真空烘干。The method for preparing a metal-organic framework composite material according to claim 3, wherein in the step 3, the preparation method of CuBHT is: dissolving copper salt in ethanol, N,N-dimethylformamide or N-methylpyrrolidone to form a solution of 1-50 mg/mL, blow nitrogen, then add hexamercaptobenzene powder and stir under nitrogen protection, filter the precipitate after the reaction, wash with solvent, and then vacuum dry.
- 根据权利要求3所述的一种金属有机骨架复合材料的制备方法，其特征在于：所述步骤三中，六巯基苯与CuBTC的质量比为1～10:30。The method for preparing a metal-organic framework composite material according to claim 3, wherein in the step 3, the mass ratio of hexamercaptobenzene to CuBTC is 1-10:30.
- 根据权利要求3所述的一种金属有机骨架复合材料的制备方法，其特征在于：所述步骤三中，原位反应的温度为5～35℃，反应时间为2～120分钟，粉末干燥温度为 40～90℃。The method for preparing a metal-organic framework composite material according to claim 3, wherein in the third step, the temperature of the in-situ reaction is 5-35°C, the reaction time is 2-120 minutes, and the powder drying temperature is 5-35°C. It is 40～90 ℃.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110337158.8 | 2021-03-29 | ||
| CN202110337158.8A CN113087920B (en) | 2021-03-29 | 2021-03-29 | Preparation method of metal organic framework composite material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2022205491A1 true WO2022205491A1 (en) | 2022-10-06 |
Family
ID=76670901
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/CN2021/085760 WO2022205491A1 (en) | 2021-03-29 | 2021-04-07 | Metal-organic framework composite material and preparation method therefor |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN113087920B (en) |
| WO (1) | WO2022205491A1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115926189A (en) * | 2023-01-12 | 2023-04-07 | 台州学院 | Novel composite material HKUST-1@ PQ and preparation method thereof |
| CN116632219A (en) * | 2023-07-19 | 2023-08-22 | 兰溪博观循环科技有限公司 | Metal phosphate composite material with core-shell structure, and preparation method and application thereof |
| CN116818850A (en) * | 2023-07-03 | 2023-09-29 | 张博 | Novel gas sensor and preparation method thereof |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114628162B (en) * | 2022-03-22 | 2023-11-28 | 中国科学院化学研究所 | High-performance supercapacitor based on nonporous conductive coordination polymer |
| CN115198532B (en) * | 2022-08-17 | 2023-05-26 | 中国科学院兰州化学物理研究所 | Solid-liquid composite lubrication blend fiber fabric and preparation method and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109759063A (en) * | 2018-12-12 | 2019-05-17 | 浙江工业大学 | A kind of hud typed CO oxidation catalyst and the preparation method and application thereof |
| KR20190105465A (en) * | 2018-03-05 | 2019-09-17 | 국방과학연구소 | Composition for removal of toxic gases containing multi-functional metal-organic composite |
| CN112225914A (en) * | 2020-10-14 | 2021-01-15 | 江苏科技大学 | CuTCNQ @ CuBTC core-shell material and preparation method thereof |
| CN112394095A (en) * | 2020-11-30 | 2021-02-23 | 江西农业大学 | Electrochemical sensor for selectively detecting nitrite ions and preparation method and application thereof |
| CN112490441A (en) * | 2020-10-30 | 2021-03-12 | 江苏科技大学 | Graphene-hexa-mercapto-benzene-copper electrode material and preparation method and application thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108654696A (en) * | 2018-03-22 | 2018-10-16 | 中国科学院上海高等研究院 | Cobaltosic oxide@HKUST-1 types composite material of core-shell structure and preparation method |
-
2021
- 2021-03-29 CN CN202110337158.8A patent/CN113087920B/en active Active
- 2021-04-07 WO PCT/CN2021/085760 patent/WO2022205491A1/en active Application Filing
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20190105465A (en) * | 2018-03-05 | 2019-09-17 | 국방과학연구소 | Composition for removal of toxic gases containing multi-functional metal-organic composite |
| CN109759063A (en) * | 2018-12-12 | 2019-05-17 | 浙江工业大学 | A kind of hud typed CO oxidation catalyst and the preparation method and application thereof |
| CN112225914A (en) * | 2020-10-14 | 2021-01-15 | 江苏科技大学 | CuTCNQ @ CuBTC core-shell material and preparation method thereof |
| CN112490441A (en) * | 2020-10-30 | 2021-03-12 | 江苏科技大学 | Graphene-hexa-mercapto-benzene-copper electrode material and preparation method and application thereof |
| CN112394095A (en) * | 2020-11-30 | 2021-02-23 | 江西农业大学 | Electrochemical sensor for selectively detecting nitrite ions and preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| WU ZHENZHEN, ADEKOYA DAVID, HUANG XING, KIEFEL MILTON J., XIE JIAN, XU WEI, ZHANG QICHUN, ZHU DAOBEN, ZHANG SHANQING: "Highly Conductive Two-Dimensional Metal–Organic Frameworks for Resilient Lithium Storage with Superb Rate Capability", ACS NANO, AMERICAN CHEMICAL SOCIETY, US, vol. 14, no. 9, 22 September 2020 (2020-09-22), US , pages 12016 - 12026, XP055925071, ISSN: 1936-0851, DOI: 10.1021/acsnano.0c05200 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115926189A (en) * | 2023-01-12 | 2023-04-07 | 台州学院 | Novel composite material HKUST-1@ PQ and preparation method thereof |
| CN115926189B (en) * | 2023-01-12 | 2023-11-10 | 台州学院 | Composite material HKUST-1@PQ and preparation method thereof |
| CN116818850A (en) * | 2023-07-03 | 2023-09-29 | 张博 | Novel gas sensor and preparation method thereof |
| CN116632219A (en) * | 2023-07-19 | 2023-08-22 | 兰溪博观循环科技有限公司 | Metal phosphate composite material with core-shell structure, and preparation method and application thereof |
| CN116632219B (en) * | 2023-07-19 | 2023-10-24 | 兰溪博观循环科技有限公司 | Metal phosphate composite material with core-shell structure, and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113087920B (en) | 2021-11-16 |
| CN113087920A (en) | 2021-07-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| WO2022205491A1 (en) | Metal-organic framework composite material and preparation method therefor | |
| CN101421034B (en) | Adsorbent for water adsorption and desorption | |
| CN103964412B (en) | A kind of preparation method of N doping loose structure material with carbon element | |
| Ataee-Esfahani et al. | Rational synthesis of Pt spheres with hollow interior and nanosponge shell using silica particles as template | |
| CN110563992B (en) | Preparation method of cationic metal organic framework membrane material | |
| CN108806998B (en) | Synthesis of ZIF-8-based ternary composite ZnO/ZnCo by solvothermal method2O4Method for producing NiO and use thereof | |
| Wang et al. | Facile synthesis of nanorod-type graphitic carbon nitride/Fe2O3 composite with enhanced photocatalytic performance | |
| Li et al. | Thermo-enhanced photocatalytic oxidation of amines to imines over MIL-125-NH 2@ Ag@ COF hybrids under visible light | |
| WO2021068570A1 (en) | Composite photocatalyst for degrading tetracycline, preparation method therefor and use thereof | |
| Shen et al. | Bottom-up synthesis of cerium–citric acid coordination polymers hollow microspheres with tunable shell thickness and their corresponding porous CeO 2 hollow spheres for Pt-based electrocatalysts | |
| CN109449415B (en) | Preparation method of MOF-derived manganese dioxide/trimanganese tetroxide layered composite material | |
| CN110760074B (en) | Preparation method of hierarchical porous metal organic framework material in ionic liquid system | |
| WO2018046930A1 (en) | Process for the preparation of zirconium based mofs. | |
| CN105289749B (en) | Amorphous Fe2O3@Cd MOF and magnetic Fe3O4@Cd MOF nano composite materials and preparation method thereof | |
| CN111215032B (en) | Rapid preparation method of MOF material | |
| Liu et al. | Controllable fabrication of 3D porous carbon nitride with ultra-thin nanosheets templated by ionic liquid for highly efficient water splitting | |
| Liang et al. | Tetrazole-functionalized two-dimensional covalent organic frameworks coordinated with metal ions for electrocatalytic oxygen evolution reaction | |
| CN113337063A (en) | Organic-inorganic nano composite particle, preparation method and application | |
| CN114481202B (en) | Ultra-thin heterogeneous interface Ti 3 C 2 T x LDH and preparation method thereof | |
| Zhang et al. | Atomically dispersed metal catalysts confined by covalent organic frameworks and their derivatives for electrochemical energy conversion and storage | |
| Zhou et al. | Oriented assembled prussian blue analogue framework for confined catalytic decomposition of ammonium perchlorate | |
| CN114130396A (en) | Preparation method of monatomic catalyst with ultrahigh norfloxacin degradation performance | |
| Jing et al. | Cyano‐Rich g‐C3N4 in Photochemistry: Design, Applications, and Prospects | |
| CN111690148B (en) | Green preparation method of two-dimensional metal-organic framework material | |
| Saran et al. | Synthesis of coordination polymers of cobalt meso-pyridylporphyrins and its oxygen reduction properties |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| 121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 21934145 Country of ref document: EP Kind code of ref document: A1 |
|
| NENP | Non-entry into the national phase |
Ref country code: DE |
|
| 122 | Ep: pct application non-entry in european phase |
Ref document number: 21934145 Country of ref document: EP Kind code of ref document: A1 |