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

Research output: Contribution to journal › Article › peer-review

71 Scopus citations

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.

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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@article{05b8a8ecbaba4da4b4f2f00a044feb30,

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.\}",

note = "Publisher Copyright: {\textcopyright} 2018 American Chemical Society.",

year = "2018",

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doi = "10.1021/acscatal.8b00141",

language = "English",

volume = "8",

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journal = "ACS Catalysis",

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publisher = "American Chemical Society",

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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

UR - https://www.scopus.com/pages/publications/85046621331

U2 - 10.1021/acscatal.8b00141

DO - 10.1021/acscatal.8b00141

M3 - Article

AN - SCOPUS:85046621331

SN - 2155-5435

VL - 8

SP - 3875

EP - 3884

JO - ACS Catalysis

JF - ACS Catalysis

IS - 5

ER -

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

Abstract

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Keywords

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