Molecularly tunable heterogeneous catalysts by edge functionalization of graphitic carbons

Patent metadata

Field	Value
Publication number	US-11005108-B2
Application number	US-201615236963-A
Country	US
Kind code	B2
Filing date	Aug 15, 2016
Priority date	Aug 14, 2015
Publication date	May 11, 2021
Grant date	May 11, 2021

Abstract

Disclosed are surface immobilized (electro)catalysts that may be prepared by a condensation reaction that generates an aromatic unit that is robust to acid and base and elevated temperatures. Among their many desirable characteristics, the catalysts are far less prone to the bimolecular deactivation pathways commonly observed for homogeneous catalysts, and may be used in solvents with a range of polarities and dielectric strengths. The catalysts are suitable for a wide array of thermal catalytic reactions (polymerization, oxidation, hydrogenation, cross-coupling etc.) and as anodes and/or cathodes in fuel cells, electrolyzers, and in batteries and supercapacitors.

First claim

We claim:

1. A composition, comprising graphene, and one or more substituents represented by a Formula selected from the group consisting of

wherein, independently for each occurrence:
a and b represent covalent bonds to the graphene;
M is a metal atom or metal ion;
R 1 , independently at each occurrence, is selected from the group consisting of halo, alkyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, hydroxy, sulfhydryl, aminosulfonyl, sulfinic acid, aminosulfinyl, formyl, carboxyl, amino, amido, aminosulfonyl, aminosulfinyl, cyano, nitro, azido, phosphinyl, phosphoryl, silyl, and silyloxy; and
optionally the metal atom or the metal ion is associated with additional ligands.

2. The composition of claim 1 , wherein the graphene is present in a form selected from the group consisting of reduced graphene oxide, graphene nanoribbon, graphene quantum dots, glassy carbon, pyrolytic graphite, graphite powder, Vulcan carbon, monarch carbon, ketjen black, single-walled carbon nanotubes, and multi-walled carbon nanotubes.

3. The composition of claim 2 , wherein the metal atom or the metal ion is independently selected from the group consisting of iridium, palladium, platinum, rhenium, rhodium, and ruthenium.

4. The composition of claim 1 , wherein the metal atom or the metal ion is associated with additional ligands.

5. The composition of claim 4 , wherein the additional ligands are selected from the group consisting of halo, 2,2′-bipyridine, carbon monoxide (CO), 1,5-cyclooctadiene, cyclopentadienyl (Cp), dibenzothiophene, 2,5-dimethylthiophene, pentamethylcyclopentadiene (Cp*), thiophene, and 2,2′,2″-tripyridine.

6. The composition of claim 1 , wherein the metal atom or the metal ion is independently selected from the group consisting of iridium, palladium, platinum, rhenium, rhodium, and ruthenium.

7. The composition of claim 1 , wherein the one or more substituents are represented by the following Formula:

8. The composition of claim 7 , wherein the metal atom or the metal ion is independently selected from the group consisting of iridium, palladium, platinum, rhenium, rhodium, and ruthenium.

9. The composition of claim 8 , wherein the graphene is present in a form selected from the group consisting of reduced graphene oxide, graphene nanoribbon, graphene quantum dots, glassy carbon, pyrolytic graphite, graphite powder, Vulcan carbon, monarch carbon, ketjen black, single-walled carbon nanotubes, and multi-walled carbon nanotubes.

10. The composition of claim 7 , wherein the graphene is present in a form selected from the group consisting of reduced graphene oxide, graphene nanoribbon, graphene quantum dots, glassy carbon, pyrolytic graphite, graphite powder, Vulcan carbon, monarch carbon, ketjen black, single-walled carbon nanotubes, and multi-walled carbon nanotubes.

11. The composition of claim 1 , wherein the one or more substituents are represented by the following Formula:

12. The composition of claim 11 , wherein the metal atom or the metal ion is independently selected from the group consisting of iridium, palladium, platinum, rhenium, rhodium, and ruthenium.

13. The composition of claim 12 , wherein the graphene is present in a form selected from the group consisting of reduced graphene oxide, graphene nanoribbon, graphene quantum dots, glassy carbon, pyrolytic graphite, graphite powder, Vulcan carbon, monarch carbon, ketjen black, single-walled carbon nanotubes, and multi-walled carbon nanotubes.

14. The composition of claim 11 , wherein the graphene is present in a form selected from the group consisting of reduced graphene oxide, graphene nanoribbon, graphene quantum dots, glassy carbon, pyrolytic graphite, graphite powder, Vulcan carbon, monarch carbon, ketjen black, single-walled carbon nanotubes, and multi-walled carbon nanotubes.

Assignees

• Massachusetts Inst Technology

Inventors

• Surendranath Yogesh
• Fukushima Tomohiro
• O'Reilly Matthew E
• Oh Seokjoon
• Murray Alexander T
• Kaminsky Corey Jarin
• Chu Sterling Ben
• Jackson Megan N

Classifications

• C07F15/0053

  without a metal-carbon linkage · CPC title

• C07F15/0033

  Iridium compounds · CPC title

• H01M8/083

  Alkaline fuel cells · CPC title

• H01M4/9008 Primary

  Organic or organo-metallic compounds · CPC title

• C07F15/0046

  Ruthenium compounds · CPC title