Publication Date

8-14-2020

Department

Ames Laboratory; Chemistry

Campus Units

Ames Laboratory, Chemistry

OSTI ID+

1647483

Report Number

IS-J 10275

DOI

10.1038/s41467-020-17909-8

Journal Title

Nature Communications

Volume Number

11

First Page

4091

Abstract

Catalytic cleavage of strong bonds including hydrogen-hydrogen, carbon-oxygen, and carbon-hydrogen bonds is a highly desired yet challenging fundamental transformation for the production of chemicals and fuels. Transition metal-containing catalysts are employed, although accompanied with poor selectivity in hydrotreatment. Here we report metal-free nitrogen-assembly carbons (NACs) with closely-placed graphitic nitrogen as active sites, achieving dihydrogen dissociation and subsequent transformation of oxygenates. NACs exhibit high selectivity towards alkylarenes for hydrogenolysis of aryl ethers as model bio-oxygenates without over-hydrogeneration of arenes. Activities originate from cooperating graphitic nitrogen dopants induced by the diamine precursors, as demonstrated in mechanistic and computational studies. We further show that the NAC catalyst is versatile for dehydrogenation of ethylbenzene and tetrahydroquinoline as well as for hydrogenation of common unsaturated functionalities, including ketone, alkene, alkyne, and nitro groups. The discovery of nitrogen assembly as active sites can open up broad opportunities for rational design of new metal-free catalysts for challenging chemical reactions.

DOE Contract Number(s)

AC02‐07CH11358; SC0020300

Language

en

Department of Energy Subject Categories

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Publisher

Iowa State University Digital Repository, Ames IA (United States)

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