Platinum organometallic complex functionalized amine-modified fibrous hierarchical zeolite and method of making the same
A functionalized fibrous hierarchical zeolite includes a framework comprising aluminum atoms, silicon atoms, and oxygen atoms, the framework further comprising a plurality of micropores and a plurality of mesopores. The functionalized fibrous hierarchical zeolite is functionalized with at least one terminal amine bonded to a silicon atom. Terminal organometallic functionalities are bonded to a nitrogen atom of the at least one terminal amine, the terminal organometallic functionalities comprising a platinum atom.
1. A functionalized fibrous hierarchical zeolite comprising
a framework comprising aluminum atoms, silicon atoms, and oxygen atoms, the framework further comprising a plurality of micropores and a plurality of mesopores, wherein:
the framework is functionalized with at least one terminal amine bonded to a silicon atom;
terminal organometallic functionalities are bonded to a nitrogen atom of the at least one terminal amine, the terminal organometallic functionalities comprising a platinum atom;
a mesopore structure of the functionalized fibrous hierarchical zeolite comprises interconnected intra-crystalline mesopores; and
the functionalized fibrous hierarchical zeolite is produced by forming a mixture comprising a cationic polymer, wherein the cationic polymer comprises a structure according to:
where:
n is the total number of repeating monomers in the polymer;
* denotes a point of attachment to a monomer in the polymer;
X and Y are anions independently selected from Cl − , Br − , F − , I − , − OH, ½SO 4 2− , ⅓PO 4 3− , ½S 2− , AlO 2 − , BF 4 − , SbF 6 − , and B [3,5-(CF 3 ) 2 C 6 H 3 ] 4 − ;
A and B are independently selected from nitrogen and phosphorous;
R 5 is a branched or unbranched hydrocarbon chain, optionally comprising one or more heteroatoms; and
R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , and R 13 are independently selected from a hydrogen atom or a hydrocarbon optionally.
2. The functionalized fibrous hierarchical zeolite of claim 1 , wherein the framework further comprises at least one terminal amine that forms a dative bond with one or more of the aluminum atoms of the framework.
3. The functionalized fibrous hierarchical zeolite of claim 1 , wherein the framework comprises a plurality of silylamine groups comprising at least one of the silicon atoms and a nitrogen atom of the least one terminal amine.
4. The functionalized fibrous hierarchical zeolite of claim 1 , wherein the framework is selected from the group consisting of an MFI, an FAU, a BEA, an MOR, and a combination of two or more thereof.
5. The functionalized fibrous hierarchical zeolite of claim 1 , wherein the framework is an MFI.
6. The functionalized fibrous hierarchical zeolite of claim 1 , wherein the terminal organometallic functionalities are selected from the group consisting of a complex of formula (1), a complex of formula (2), a complex of formula (3), a complex of formula (4), a complex of formula (5), a complex of formula (6), a complex of formula (7), a complex of formula (8), a complex of formula (9), and a combination of two or more thereof, where * denotes a point of attachment to the nitrogen atom of the at least one terminal amine
7. The functionalized fibrous hierarchical zeolite of claim 6 , wherein the terminal organometallic functionalities are a complex of formula (1).
8. The functionalized fibrous hierarchical zeolite of claim 1 , where:
n is an integer from 10 to 10,000;
A and B are nitrogen;
X and Y are Br;
R 5 is a hydrocarbon chain having 2 to 20 carbon atoms; and
R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , and R 13 are independently selected from a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, or a pentyl group.
9. The functionalized fibrous hierarchical zeolite of claim 1 , where the functionalized fibrous hierarchical zeolite comprises from 0.1 wt. % to 15 wt. % platinum.
10. A method for making the functionalized fibrous hierarchical zeolite of claim 1 comprising terminal organometallic functionalities comprising a platinum atom, the method comprising:
contacting a dehydroxylated fibrous hierarchical zeolite with an organometallic complex comprising a platinum atom, wherein the fibrous hierarchical zeolite comprises:
a framework comprising aluminum atoms, silicon atoms, and oxygen atoms, the framework further comprising a plurality of micropores and a plurality of mesopores, the framework being functionalized with at least one terminal amine bonded to a silicon atom;
wherein the terminal organometallic functionalities are bonded to a nitrogen atom of the at least one terminal amine, the terminal organometallic functionalities comprising the platinum atom, thereby producing a functionalized zeolite comprising terminal organometallic functionalities comprising a platinum atom.
11. The method of claim 10 , wherein the framework comprises a plurality of silylamine groups comprising at least one of the silicon atoms and a nitrogen atom of the least one terminal amine.
12. The method of claim 10 , wherein the framework is selected from the group consisting of an MFI, an FAU, a BEA, an MOR, and a combination of two or more thereof.
13. The method of claim 10 , wherein the framework is an MFI.
14. The method of claim 13 , wherein the platinum atom of the terminal organometallic functionalities is bound to a cyclooctene.
15. The method of claim 13 , wherein the contacting takes place at a temperature from 20° C. to 100° C.
16. The method of claim 10 , wherein the organometallic complex is selected from the group consisting of a complex of formula (1), a complex of formula (2), a complex of formula (3), a complex of formula (4), a complex of formula (5), a complex of formula (6), a complex of formula (7), a complex of formula (8), a complex of formula (9), and a combination of two or more thereof
17. The method of claim 16 , wherein the organometallic complex is a complex of formula (1).