Selective Aerobic Oxidation of Alcohols over Atomically-Dispersed Non-Precious Metal Catalysts

Jiahan Xie; Kehua Yin; Alexey Serov; Kateryna Artyushkova; Hien N. Pham; Xiahan Sang; Raymond R. Unocic; Plamen Atanassov; Abhaya K. Datye; Robert J. Davis

doi:10.1002/cssc.201601364

Selective Aerobic Oxidation of Alcohols over Atomically-Dispersed Non-Precious Metal Catalysts

Jiahan Xie, Kehua Yin, Alexey Serov, Kateryna Artyushkova, Hien N. Pham, Xiahan Sang, Raymond R. Unocic, Plamen Atanassov, Abhaya K. Datye, Robert J. Davis

Materials MicroAnalysis

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79 Scopus citations

Abstract

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 O₂ in the aqueous phase. The activity of the catalyst can be regenerated by a mild treatment in H₂. 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.

Original language	English
Pages (from-to)	359-362
Number of pages	4
Journal	ChemSusChem
Volume	10
Issue number	2
DOIs	https://doi.org/10.1002/cssc.201601364
State	Published - Jan 20 2017

Funding

This work is supported by the US NSF under grant numbers EEC-0813570 (Center for Biorenewable Chemicals, CBiRC) and CBET-1157829, and in part by the US DOE-EERE Fuel Cell Technology Program (subcontract to Northeastern University, with PI Sanjeev Mukerjee). A portion of the microscopy research was conducted at the Center for Nanophase Materials Sciences in Oak Ridge National Lab, which is a DOE Office of Science User Facility.

Keywords

N-doped carbon
heterogeneous catalyst
non-precious metal
oxidation
reaction mechanism

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10.1002/cssc.201601364

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title = "Selective Aerobic Oxidation of Alcohols over Atomically-Dispersed Non-Precious Metal Catalysts",

abstract = "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 O2 in the aqueous phase. The activity of the catalyst can be regenerated by a mild treatment in H2. 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.",

keywords = "N-doped carbon, heterogeneous catalyst, non-precious metal, oxidation, reaction mechanism",

author = "Jiahan Xie and Kehua Yin and Alexey Serov and Kateryna Artyushkova and Pham, \{Hien N.\} and Xiahan Sang and Unocic, \{Raymond R.\} and Plamen Atanassov and Datye, \{Abhaya K.\} and Davis, \{Robert J.\}",

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year = "2017",

month = jan,

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doi = "10.1002/cssc.201601364",

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T1 - Selective Aerobic Oxidation of Alcohols over Atomically-Dispersed Non-Precious Metal Catalysts

AU - Xie, Jiahan

AU - Yin, Kehua

AU - Serov, Alexey

AU - Artyushkova, Kateryna

AU - Pham, Hien N.

AU - Sang, Xiahan

AU - Unocic, Raymond R.

AU - Atanassov, Plamen

AU - Datye, Abhaya K.

AU - Davis, Robert J.

PY - 2017/1/20

Y1 - 2017/1/20

N2 - 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 O2 in the aqueous phase. The activity of the catalyst can be regenerated by a mild treatment in H2. 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.

AB - 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 O2 in the aqueous phase. The activity of the catalyst can be regenerated by a mild treatment in H2. 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.

KW - N-doped carbon

KW - heterogeneous catalyst

KW - non-precious metal

KW - oxidation

KW - reaction mechanism

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DO - 10.1002/cssc.201601364

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SN - 1864-5631

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JO - ChemSusChem

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ER -

Selective Aerobic Oxidation of Alcohols over Atomically-Dispersed Non-Precious Metal Catalysts

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Keywords

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