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Selective Aerobic Oxidation of Alcohols over Atomically‐Dispersed Non‐Precious Metal Catalysts
Author(s) -
Xie Jiahan,
Yin Kehua,
Serov Alexey,
Artyushkova Kateryna,
Pham Hien N.,
Sang Xiahan,
Unocic Raymond R.,
Atanassov Plamen,
Datye Abhaya K.,
Davis Robert J.
Publication year - 2017
Publication title -
chemsuschem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 2.412
H-Index - 157
eISSN - 1864-564X
pISSN - 1864-5631
DOI - 10.1002/cssc.201601364
Subject(s) - catalysis , alcohol oxidation , chemistry , benzyl alcohol , carbon fibers , alcohol , transition metal , metal , heterogeneous catalysis , inorganic chemistry , organic chemistry , materials science , composite number , composite material
Catalytic oxidation of alcohols often requires the presence of expensive transition metals. Herein, it is shown that earth‐abundant Fe atoms dispersed throughout a nitrogen‐containing carbon matrix catalyze the oxidation of benzyl alcohol and 5‐hydroxymethylfurfural by O 2 in the aqueous phase. The activity of the catalyst can be regenerated by a mild treatment in H 2 . An observed kinetic isotope effect indicates that β‐H elimination from the alcohol is the kinetically relevant step in the mechanism, which can be accelerated by substituting Fe with Cu. Dispersed Cr, Co, and Ni also convert alcohols, demonstrating the general utility of metal–nitrogen–carbon materials for alcohol oxidation catalysis. Oxidation of aliphatic alcohols is substantially slower than that of aromatic alcohols, but addition of 2,2,6,6‐tetramethyl‐1‐piperidinyloxy as a co‐catalyst with Fe can significantly improve the reaction rate.