Multifunctional supramolecular hybrids encompassing hierarchical self-ordering of metal-organic framework nanoparticles and method of preparing same
View Patent ↗A supramolecular metal-organic framework material is a reaction product of a copper compound, a trialkylamine represented by Chemical Formula 1, and benzene substituted with 3 or more carboxyl groups.
1. A supramolecular metal-organic framework material consisting essentially of:
a reaction product of copper nitrate (Cu(NO 3 ) 2 ), a trialkylamine represented by Chemical Formula 1, and a benzene substituted with 3 carboxyl groups in a non-aqueous solvent that is an organic solvent and does not include water,
wherein in Chemical Formula 1,
each of R 1 , R 2 , and R 3 are the same or different and are independently a C 1 to C 10 alkyl group,
wherein the copper nitrate (Cu(NO 3 ) 2 ) is in a form of a Cu(II) solution formed in the non-aqueous solvent,
wherein the supramolecular metal-organic framework material is in a gel state, and wherein a molar concentration of the trialkylamine represented by Chemical Formula 1 in the non-aqueous solvent is greater than a molar concentration of the copper nitrate in the non-aqueous solvent when forming the reaction product, and
the molar concentration of the copper nitrate in the non-aqueous solvent is greater than a molar concentration of the benzene substituted with 3 carboxyl groups in the non-aqueous solvent when forming the reaction product.
2. A supramolecular metal-organic framework material consisting essentially of:
a reaction product of copper nitrate (Cu(NO 3 ) 2 ), triethylamine (NEt 3 ), and 1,3,5-benzenetricarboxylic acid (BTC) in a non-aqueous solvent that is an organic solvent and does not include water,
wherein the non-aqueous solvent includes one of a C 1 -C 10 alkanol, dimethyl sulfoxide (DMSO), N,N-dimethyl formamide (DMF), N,N-diethylformamide (DEF), N,N-dimethylacetimide (DMAc), acetonitrile (ACN), toluene, dioxane, chlorobenzene, methylethylketone (MEK), pyridine, or a combination thereof,
wherein the supramolecular metal-organic framework material is in a gel state, and wherein a molar concentration of the NEt3 in the non-aqueous solvent is greater than a molar concentration of the copper nitrate in the non-aqueous solvent when forming the reaction product, and
the molar concentration of the copper nitrate in the non-aqueous solvent is greater than a molar concentration of the BTC in the non-aqueous solvent when forming the reaction product.
3. The supramolecular metal-organic framework material of claim 1 , wherein
the trialkylamine represented by the Chemical Formula 1 is triethylamine (NEt 3 ), and
the benzene substituted with 3 carboxyl groups is 1,3,5-benzenetricarboxylic acid (BTC).
4. The supramolecular metal-organic framework material of claim 1 , wherein the non-aqueous solvent includes one of a C 1 -C 10 alkanol, dimethyl sulfoxide (DMSO), N,N-dimethyl formamide (DMF), N,N-diethylformamide (DEF), N,N-dimethylacetimide (DMAc), acetonitrile (ACN), toluene, dioxane, chlorobenzene, methylethylketone (MEK), pyridine, or a combination thereof.
5. The supramolecular metal-organic framework material of claim 1 , which is capable of undergoing sol-gel transitions upon subsequent alternate additions of the copper nitrate (Cu(NO 3 ) 2 ) and the benzene substituted with 3 carboxyl groups.
6. The supramolecular metal-organic framework material of claim 1 , which is capable of transforming into a sol state when being subjected to a mechanical force.
7. The supramolecular metal-organic framework material of claim 1 , wherein the supramolecular metal-organic framework material in a sol state transforms into a gel state again by any of a heat-treatment, an ultrasonification, and an allowance to stand.
8. The supramolecular metal-organic framework material of claim 1 , which is capable of transforming into nanoparticles by drying or immersing in a polar organic solvent.
9. The supramolecular metal-organic framework material of claim 1 , wherein the supramolecular metal-organic framework material has a lamella structure.
10. A method of preparing the supramolecular metal-organic framework material, of claim 2 the method comprising:
reacting copper nitrate (Cu(NO 3 ) 2 ), triethylamine (NEt 3 ), and 1,3,5-benzenetricarboxylic acid (BTC) in a non-aqueous solvent that is an organic solvent and does not include water,
wherein the non-aqueous solvent includes one of a C 1 -C 10 alkanol, dimethyl sulfoxide (DMSO), N,N-dimethyl formamide (DMF), N,N-diethyl formamide (DEF), N,N-dimethylacetimide (DMAc), acetonitrile (ACN), toluene, dioxane, chlorobenzene, methylethylketone (MEK), pyridine, and a combination thereof, and
wherein a molar concentration of the NEt 3 in the non-aqueous solvent is greater than a molar concentration of the copper nitrate solution in the non-aqueous solvent when forming the reaction product, and the molar concentration of the copper nitrate solution in the non-aqueous solvent is greater than a molar concentration of the BTC in the non-aqueous solvent when forming the reaction product.
11. The method of claim 10 , wherein:
the reacting reacts a solution including the copper nitrate (Cu(NO 3 ) 2 ) with a solution including the triethylamine (NEt 3 ) and 1,3,5-benzenetricarboxylic acid (BTC).
12. The method of claim 10 , further comprising:
subsequently alternately adding the copper nitrate (Cu(NO 3 ) 2 ) and the BTC to cause sol-gel transitions of the supramolecular metal-organic framework material.
13. The method of claim 10 , further comprising:
applying mechanical force to the supramolecular metal-organic framework material to cause a transition into a sol state.
14. The method of claim 13 , further comprising:
one of heat-treating, ultrasonificating, and standing the supramolecular metal-organic framework material in a sol state to transform it into a gel state again.
15. A molded article comprising the supramolecular metal-organic framework material of claim 2 .
16. The molded article of claim 15 , wherein the molded article is a film.
17. An electronic device comprising the molded article of claim 15 .
18. A supramolecular metal-organic framework material in a fiber phase comprising:
the supramolecular metal-organic framework material of claim 2 , wherein
the reaction product is formed in the non-aqueous solvent without adding water to the non-aqueous solvent during a reaction to form the reaction product, and
the non-aqueous solvent includes one of dimethyl sulfoxide (DMSO), N,N-dimethyl formamide (DMF), acetonitrile (ACN), methanol, or ethanol.
19. The supramolecular metal-organic framework material of claim 1 , wherein the supramolecular metal-organic framework material consists of the reaction product of the copper nitrate (Cu(NO 3 ) 2 ), the trialkylamine represented by Chemical Formula 1, and the benzene substituted with 3 carboxyl groups in the non-aqueous solvent that is an organic solvent and does not include water.
20. The supramolecular metal-organic framework material of claim 2 , wherein the supramolecular metal-organic framework material consists of the reaction product of the copper nitrate (Cu(NO 3 ) 2 ), the triethylamine (NEt 3 ), and the 1,3,5-benzenetricarboxylic acid (BTC) in the non-aqueous solvent that is an organic solvent and does not include water.