# US 2018/0022679 A1 · Heterogeneous metal-free catalyst

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- Number: US 2018/0022679 A1
- Document ID: US20180022679A1
- Status: Published application
- Kind: A1
- Application number: 15/670,732
- Filed: 2017-08-07
- Published: 2018-01-25
- Earliest claimed: 2012-12-07
- Assignees: University of Central Florida Research Foundation, Inc.
- Applicants: University of Central Florida Research Foundation, Inc.
- Inventors: Richard G. Blair
- Web page: https://patentgrep.com/patent/US20180022679A1

## CPC

- C07C 51/36: by hydrogenation of carbon-to-carbon unsaturated bonds
- B01J 27/24: Nitrogen compounds
- B01J 37/00: Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J 37/0036: {Grinding}
- B01J 37/343: {of ultrasonic wave energy}
- C01B 21/0648: {After-treatment, e.g. grinding, purification (transformation of hexagonal into cubic or wurtzitic boron nitride C04B35/5831)}
- C07C 5/03: of non-aromatic carbon-to-carbon double bonds
- C07C 45/62: by hydrogenation of carbon-to-carbon double or triple bonds
- C07C 231/00: Preparation of carboxylic acid amides
- C07C 253/00: Preparation of carboxylic acid nitriles (of cyanogen or compounds thereof C01C3/00)
- B01J 2231/643: of R2C=O or R2C=NR (R= C, H)
- B01J 2231/645: of C=C or C-C triple bonds
- B01J 2235/00: Indexing scheme associated with group B01J35/00, related to the analysis techniques used to determine the catalysts form or properties
- B01J 2235/30: Scanning electron microscopy; Transmission electron microscopy
- C01P 2002/85: by XPS, EDX or EDAX data
- C01P 2004/03: obtained by SEM
- C07C 2527/24: Nitrogen compounds
- C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS
- B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- C01B: NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; {METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C}
- C01P: INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS

## 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.

## Claims

### Claim 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 site sites, wherein the at least one frustrated pair of Lewis acid and Lewis base sites is catalytically active.

### Claim 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.

### Claim 3 (depends on 2)

The heterogeneous hydrogenation catalyst of claim 2, 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.

### Claim 4 (depends on 2)

The heterogeneous hydrogenation catalyst of claim 2, 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.

### Claim 5 (depends on 2)

The heterogeneous hydrogenation catalyst of claim 2, 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 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.

### Claim 6 (depends on 2)

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.

### Claim 7 (depends on 2)

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

### Claim 8

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.

### Claim 9 (depends on 8)

The heterogeneous hydrogenation catalyst of claim 8, 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.

### Claim 10 (depends on 9)

The heterogeneous hydrogenation catalyst of claim 9, 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.

### Claim 11

(canceled)

### Claim 12

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

### Claim 13

A method of making a hydrogenation catalyst, comprising:
mechanically processing hexagonal boron nitride in the presence of an alkali metal element or hydrogen to produce a catalytically active defect on a surface of the hexagonal boron nitride.

### Claim 14 (depends on 13)

The method of claim 13, wherein the alkali metal element is lithium.

### Claim 15

(canceled)

### Claim 16 (depends on 13)

The method of claim 13, wherein the mechanical process is selected from the group consisting of grinding, sonochemical processing, and combinations thereof.

### Claim 17

(canceled)

### Claim 18

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 frustrated Lewis pairs; and
catalytically hydrogenating the hydrogenatable compound.

### Claim 19 (depends on 18)

The process of claim 18, 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.

### Claim 20

(canceled)

### Claim 21 (depends on 18)

The process of claim 18, further wherein the solid material having frustrated Lewis pairs 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.

### Claim 22 (depends on 18)

The process of claim 18, further wherein the solid material having frustrated Lewis pairs 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.

### Claim 23 (depends on 22)

The process of claim 22, 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.

### Claim 24 (depends on 22)

The process of claim 22, wherein the Lewis base moieties are selected from the group consisting of simple anions, lone-pair-containing species, complex anions, electron rich -systems, and combinations thereof.

### Claim 25 (depends on 22)

The process of claim 22, 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 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.

### Claim 26 (depends on 22)

The process of claim 22, 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.

### Claim 27 (depends on 22)

The process of claim 22, wherein the hydrogenation catalyst at least partially comprises hexagonal boron nitride.

### Claim 28 (depends on 18)

The process of claim 18, 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.

### Claim 29 (depends on 18)

The process of claim 18, 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.

### Claim 30 (depends on 29)

The process of claim 29, 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.

### Claim 31

(canceled)

### Claim 32 (depends on 18)

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

### Claim 33 (depends on 1)

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.

### Claim 34 (depends on 33)

The heterogeneous hydrogenation catalyst of claim 33, 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.

### Claim 35 (depends on 1)

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

### Claim 36 (depends on 2)

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.

### Claim 37 (depends on 36)

The heterogeneous hydrogenation catalyst of claim 36, 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.

### Claim 38 (depends on 2)

The heterogeneous hydrogenation catalyst of claim 2, wherein the catalyst is capable of catalytically hydrogenating an alkene.