Atomically Dispersed Co and Cu on N-Doped Carbon for Reactions Involving C-H Activation

Jiahan Xie; James D. Kammert; Nicholas Kaylor; Jonathan W. Zheng; Eunjin Choi; Hien N. Pham; Xiahan Sang; Eli Stavitski; Klaus Attenkofer; Raymond R. Unocic; Abhaya K. Datye; Robert J. Davis

doi:10.1021/acscatal.8b00141

Atomically Dispersed Co and Cu on N-Doped Carbon for Reactions Involving C-H Activation

Jiahan Xie, James D. Kammert, Nicholas Kaylor, Jonathan W. Zheng, Eunjin Choi, Hien N. Pham, Xiahan Sang, Eli Stavitski, Klaus Attenkofer, Raymond R. Unocic, Abhaya K. Datye, Robert J. Davis

Materials MicroAnalysis

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Abstract

Atomically dispersed Co(II) cations coordinated to nitrogen in a carbon matrix (Co-N-C) catalyze oxidative dehydrogenation of benzyl alcohol in water with a specific activity approaching that of supported Pt nanoparticles. Whereas Cu(II) cations in N-doped carbon also catalyze the reaction, they are about an order of magnitude less active compared with Co(II) cations. Results from X-ray absorption spectroscopy suggest that oxygen is also bound to N-coordinated Co(II) sites but that it can be partially removed by H₂ treatments at 523-750 K. The N-coordinated Co(II) sites remained cationic in H₂ up to 750 K, and these stable sites were demonstrated to be active for propane dehydrogenation. In situ characterization of Cu(II) in N-doped carbon revealed that reduction of the metal in H₂ started at about 473 K, indicating a much lower thermal stability of Cu(II) in H₂ relative to Co(II). The demonstrated high catalytic activity and thermal stability of Co-N-C in reducing environments suggests that this material may have broad utility in a variety of catalytic transformations.

Original language	English
Pages (from-to)	3875-3884
Number of pages	10
Journal	ACS Catalysis
Volume	8
Issue number	5
DOIs	https://doi.org/10.1021/acscatal.8b00141
State	Published - May 4 2018

Funding

This work was supported by the U.S. NSF under Grants EEC-0813570 (Center for Biorenewable Chemicals, CBiRC) and CBET-1157829. A portion of the microscopy research was conducted at the Center for Nanophase Materials Sciences at Oak Ridge National Laboratory, which is a DOE Office of Science User Facility. This research used beamline 8-ID (ISS) of the National Synchrotron Light Source II, a U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Brookhaven National Laboratory under Contract DE-SC0012704. Helpful discussions with Zhongwen Luo, Prof. T. Brent Gunnoe, and Prof. Matthew Neurock are acknowledged. This work was supported by the U.S. NSF under Grants EEC-0813570 (Center for Biorenewable Chemicals, CBiRC) and CBET-1157829. A portion of the microscopy research was conducted at the Center for Nanophase Materials Sciences at Oak Ridge National Laboratory, which is a DOE Office of Science User Facility. This research used beamline 8-ID (ISS) of the National Synchrotron Light Source II, a U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Brookhaven National Laboratory under Contract DE-SC0012704.

Funders	Funder number
CBiRC	CBET-1157829
DOE Office of Science
National Science Foundation	EEC-0813570
U.S. Department of Energy
Office of Science
Oak Ridge National Laboratory
Brookhaven National Laboratory	DE-SC0012704
Norsk Sykepleierforbund

Keywords

C-H activation
N-doped carbon
alcohol oxidation
coordination environment
heterogeneous catalyst
in situ XAS
nonprecious metal
propane dehydrogenation

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10.1021/acscatal.8b00141

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title = "Atomically Dispersed Co and Cu on N-Doped Carbon for Reactions Involving C-H Activation",

abstract = "Atomically dispersed Co(II) cations coordinated to nitrogen in a carbon matrix (Co-N-C) catalyze oxidative dehydrogenation of benzyl alcohol in water with a specific activity approaching that of supported Pt nanoparticles. Whereas Cu(II) cations in N-doped carbon also catalyze the reaction, they are about an order of magnitude less active compared with Co(II) cations. Results from X-ray absorption spectroscopy suggest that oxygen is also bound to N-coordinated Co(II) sites but that it can be partially removed by H2 treatments at 523-750 K. The N-coordinated Co(II) sites remained cationic in H2 up to 750 K, and these stable sites were demonstrated to be active for propane dehydrogenation. In situ characterization of Cu(II) in N-doped carbon revealed that reduction of the metal in H2 started at about 473 K, indicating a much lower thermal stability of Cu(II) in H2 relative to Co(II). The demonstrated high catalytic activity and thermal stability of Co-N-C in reducing environments suggests that this material may have broad utility in a variety of catalytic transformations.",

keywords = "C-H activation, N-doped carbon, alcohol oxidation, coordination environment, heterogeneous catalyst, in situ XAS, nonprecious metal, propane dehydrogenation",

author = "Jiahan Xie and Kammert, {James D.} and Nicholas Kaylor and Zheng, {Jonathan W.} and Eunjin Choi and Pham, {Hien N.} and Xiahan Sang and Eli Stavitski and Klaus Attenkofer and Unocic, {Raymond R.} and Datye, {Abhaya K.} and Davis, {Robert J.}",

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doi = "10.1021/acscatal.8b00141",

language = "English",

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T1 - Atomically Dispersed Co and Cu on N-Doped Carbon for Reactions Involving C-H Activation

AU - Xie, Jiahan

AU - Kammert, James D.

AU - Kaylor, Nicholas

AU - Zheng, Jonathan W.

AU - Choi, Eunjin

AU - Pham, Hien N.

AU - Sang, Xiahan

AU - Stavitski, Eli

AU - Attenkofer, Klaus

AU - Unocic, Raymond R.

AU - Datye, Abhaya K.

AU - Davis, Robert J.

PY - 2018/5/4

Y1 - 2018/5/4

N2 - Atomically dispersed Co(II) cations coordinated to nitrogen in a carbon matrix (Co-N-C) catalyze oxidative dehydrogenation of benzyl alcohol in water with a specific activity approaching that of supported Pt nanoparticles. Whereas Cu(II) cations in N-doped carbon also catalyze the reaction, they are about an order of magnitude less active compared with Co(II) cations. Results from X-ray absorption spectroscopy suggest that oxygen is also bound to N-coordinated Co(II) sites but that it can be partially removed by H2 treatments at 523-750 K. The N-coordinated Co(II) sites remained cationic in H2 up to 750 K, and these stable sites were demonstrated to be active for propane dehydrogenation. In situ characterization of Cu(II) in N-doped carbon revealed that reduction of the metal in H2 started at about 473 K, indicating a much lower thermal stability of Cu(II) in H2 relative to Co(II). The demonstrated high catalytic activity and thermal stability of Co-N-C in reducing environments suggests that this material may have broad utility in a variety of catalytic transformations.

AB - Atomically dispersed Co(II) cations coordinated to nitrogen in a carbon matrix (Co-N-C) catalyze oxidative dehydrogenation of benzyl alcohol in water with a specific activity approaching that of supported Pt nanoparticles. Whereas Cu(II) cations in N-doped carbon also catalyze the reaction, they are about an order of magnitude less active compared with Co(II) cations. Results from X-ray absorption spectroscopy suggest that oxygen is also bound to N-coordinated Co(II) sites but that it can be partially removed by H2 treatments at 523-750 K. The N-coordinated Co(II) sites remained cationic in H2 up to 750 K, and these stable sites were demonstrated to be active for propane dehydrogenation. In situ characterization of Cu(II) in N-doped carbon revealed that reduction of the metal in H2 started at about 473 K, indicating a much lower thermal stability of Cu(II) in H2 relative to Co(II). The demonstrated high catalytic activity and thermal stability of Co-N-C in reducing environments suggests that this material may have broad utility in a variety of catalytic transformations.

KW - C-H activation

KW - N-doped carbon

KW - alcohol oxidation

KW - coordination environment

KW - heterogeneous catalyst

KW - in situ XAS

KW - nonprecious metal

KW - propane dehydrogenation

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Atomically Dispersed Co and Cu on N-Doped Carbon for Reactions Involving C-H Activation

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