Heterogeneous metal-free catalyst

Patent metadata

Field	Value
Publication number	US-10329234-B2
Application number	US-201715670732-A
Country	US
Kind code	B2
Filing date	Aug 7, 2017
Priority date	Dec 7, 2012
Publication date	Jun 25, 2019
Grant date	Jun 25, 2019

Abstract

The inventive concepts disclosed and/or claimed herein relate generally to catalysts and, more particularly, but not by way of limitation, to a heterogeneous, metal-free hydrogenation catalyst containing frustrated Lewis pairs. In one non-limiting embodiment, the heterogeneous, metal-free catalyst comprises hexagonal boron nitride (h-BN) having frustrated Lewis pairs therein.

First claim

What is claimed is:

1. A heterogeneous hydrogenation catalyst, comprising:
a solid surface substantially free of metals, the solid surface having at least one Lewis acid site and at least one Lewis base site; and
at least one defect frustrating at least one pair of Lewis acid and Lewis base sites, wherein the at least one frustrated pair of Lewis acid and Lewis base sites is catalytically active;

wherein the Lewis acids are selected from the group consisting of Group 13 elements in a trigonal planar configuration, halides of Group 15 elements, electron poor π-systems, and combinations thereof, and wherein the Lewis bases are selected from the group consisting of simple anions, lone-pair containing species, complex anions, electron rich π-systems, and combinations thereof.

2. A heterogeneous hydrogenation catalyst, comprising:
a solid surface having non-metallic Lewis acid moieties and non-metallic Lewis base moieties spaced a distance apart from one another such that (a) catalytic activity is present therebetween and (b) the formation of an acid-base adduct is prevented;

wherein the Lewis acid moieties are selected from the group consisting of Group 13 elements in a trigonal planar configuration, halides of Group 15 elements, electron poor π-systems, and combinations thereof, and wherein the Lewis base moieties are selected from the group consisting of simple anions, lone-pair-containing species, complex anions, electron rich π-systems, and combinations thereof.

3. The heterogeneous hydrogenation catalyst of claim 2 , wherein the Lewis acid moiety is a Group 13 element in a trigonal planar configuration and the Lewis base moiety is a lone-pair containing species.

4. The heterogeneous hydrogenation catalyst of claim 2 , wherein the hydrogenation catalyst at least partially comprises hexagonal boron nitride.

5. A heterogeneous hydrogenation catalyst, comprising:
a sheet of catalytically active material substantially free of metals having unsatisfied Lewis acid-base pairs along a surface of the sheet;

wherein the Lewis acids are selected from the group consisting of Group 13 elements in a trigonal planar configuration, halides of Group 15 elements, electron poor π-systems, and combinations thereof, and wherein the Lewis bases are selected from the group consisting of simple anions, lone-pair containing species, complex anions, electron rich π-systems, and combinations thereof.

6. The heterogeneous hydrogenation catalyst of claim 5 , wherein the heterogeneous hydrogenation catalyst comprises hexagonal boron nitride having at least one catalytically active defect on a surface thereof, wherein the hexagonal boron nitride is substantially free of metals.

7. The heterogeneous hydrogenation catalyst of claim 6 , wherein the catalytically active defect Is selected from the group consisting of Stone-Wales defects, B/N defects, boron substituted nitrogen, nitrogen substituted for boron, carbon substituted for nitrogen, carbon substituted for boron, boron vacancy, nitrogen vacancy, and combinations thereof.

8. The heterogeneous hydrogenation catalyst of claim 5 , wherein the catalyst is capable of catalytically hydrogenating an alkene.

9. A hydrogenation process comprising:
contacting a hydrogenatable compound with hydrogen gas and a catalyst in a reactor, wherein the catalyst comprises a solid material having at least one frustrated Lewis acid-base pair; and
catalytically hydrogenating the hydrogenatable compound;

wherein the Lewis acids are selected from the group consisting of Group 13 elements in a trigonal planar configuration, halides of Group 15 elements, electron poor π-systems, and combinations thereof, and wherein the Lewis bases are selected from the group consisting of simple anions, lone-pair containing species, complex anions, electron rich π-systems, and combinations thereof.

10. The process of claim 9 , wherein the hydrogenatable compound is a compound having functional groups selected from the group consisting of alkene, alkyne, aldehyde, ketone, ester, imine, amide, nitrile, nitro, and combinations thereof.

11. The process of claim 9 , further wherein the solid material having at least one frustrated Lewis pair comprises a solid surface substantially free of metals, the solid surface having at least one Lewis acid site and at least one Lewis base site, and at least one defect frustrating at least one pair of Lewis acid and Lewis base sites, wherein the at least one frustrated pair of Lewis acid and Lewis base sites is catalytically active.

12. The process of claim 9 , further wherein the solid material having at least one frustrated Lewis pair comprises a solid surface having non-metallic Lewis acid moieties and non-metallic Lewis base moieties spaced a distance apart from one another such that (a) catalytic activity is present therebetween and (b) the formation of an acid-base adduct therefrom is prevented.

13. The process of claim 12 , wherein the Lewis acid moiety is a Group 13 element in a trigonal planar configuration and the Lewis base moiety is a lone-pair containing species.

14. The process of claim 12 , wherein the hydrogenation catalyst at least partially comprises hexagonal boron nitride.

15. The process of claim 9 , further wherein the catalyst comprises a sheet of catalytically active material substantially free of metals having unsatisfied Lewis acid-base pairs along a surface of the sheet.

16. The process of claim 9 , wherein the catalyst comprises hexagonal boron nitride having a catalytically active defect on a surface thereof, wherein the hexagonal boron nitride is substantially free of metals.

17. The process of claim 16 , wherein the catalytically active defect is selected from the group consisting of Stone-Wales defects, B/N defects, boron substituted for nitrogen, nitrogen substituted for boron, carbon substituted for nitrogen, carbon substituted for boron, boron vacancy, nitrogen vacancy, and combinations thereof.

18. The process of claim 9 , wherein the catalyst is capable of catalytically hydrogenating an alkene.

19. The heterogeneous hydrogenation catalyst of claim 1 , wherein the heterogeneous hydrogenation catalyst comprises hexagonal boron nitride having at least one catalytically active defect on a surface thereof, wherein the hexagonal boron nitride is substantially free of metals.

20. The heterogeneous hydrogenation catalyst of claim 19 , wherein the catalytically active defect is selected from the group consisting of Stone-Wales defects, B/N defects, boron substituted nitrogen, nitrogen substituted for boron, carbon substituted for nitrogen, carbon substituted for boron, boron vacancy, nitrogen vacancy, and combinations thereof.

21. The heterogeneous hydrogenation catalyst of claim 1 , wherein the catalyst is capable of catalytically hydrogenating an alkene.

22. The heterogeneous hydrogenation catalyst of claim 2 , wherein the heterogeneous hydrogenation catalyst comprises hexagonal boron nitride having at least one catalytically active defect on a surface thereof, wherein the hexagonal boron nitride is substantially free of metals.

23. The heterogeneous hydrogenation catalyst of claim 22 , wherein the catalytically active defect is selected from the group consisting of Stone-Wales defects, B/N defects, boron substituted nitrogen, nitrogen substituted for boron, carbon substituted for nitrogen, carbon substituted for boron, boron vacancy, nitrogen vacancy, and combinations thereof.

Assignees

• Univ Central Florida Res Found Inc

Inventors

• Blair Richard G

Classifications

• C07C45/62

  by hydrogenation of carbon-to-carbon double or triple bonds · CPC title

• C01B21/0648

  After-treatment, e.g. grinding, purification (transformation of hexagonal into cubic or wurtzitic boron nitride C04B35/5831) · CPC title

• C07C255/07

  Mononitriles · CPC title

• C07C255/03

  Mononitriles · CPC title

• B01J37/0036

  Grinding · CPC title