Selective C−H Bond Cleavage in Methane by Small Gold Clusters

Lang, Sandra M.; Bernhardt, Thorsten M.; Chernyy, Valeriy; Bakker, Joost M.; Barnett, Robert N.; Landman, Uzi

doi:10.1002/ange.201706009

Title: Selective C−H Bond Cleavage in Methane by Small Gold Clusters

Abstract

Abstract Methane represents the major constituent of natural gas. It is primarily used only as a source of energy by means of combustion, but could also serve as an abundant hydrocarbon feedstock for high quality chemicals. One of the major challenges in catalysis research nowadays is therefore the development of materials that selectively cleave one of the four C−H bonds of methane and thus make it amenable for further chemical conversion into valuable compounds. By employing infrared spectroscopy and first‐principles calculations it is uncovered herein that the interaction of methane with small gold cluster cations leads to selective C−H bond dissociation and the formation of hydrido methyl complexes, H‐Au _x ⁺ ‐CH ₃ . The distinctive selectivity offered by these gold clusters originates from a fine interplay between the closed‐shell nature of the d states and relativistic effects in gold. Such fine balance in fundamental interactions could prove to be a tunable feature in the rational design of a catalyst.

Authors:

^[1]; Bernhardt, Thorsten M. ^[1]; Chernyy, Valeriy ^[2];

^[2]; Barnett, Robert N. ^[3];

^[3]

Institute of Surface Chemistry and Catalysis University of Ulm Albert-Einstein-Allee 47 89069 Ulm Germany
Institute for Molecules and Materials FELIX Laboratory Radboud University 6525 ED Nijmegen The Netherlands
School of Physics Georgia Institute of Technology Atlanta GA 30332-0430 USA

Publication Date:: Fri Sep 22 00:00:00 EDT 2017

Sponsoring Org.:: USDOE

OSTI Identifier:: 1394003

Grant/Contract Number:: FG05-86ER45234

Resource Type:: Publisher's Accepted Manuscript

Journal Name:: Angewandte Chemie

Additional Journal Information:: Journal Name: Angewandte Chemie Journal Volume: 129 Journal Issue: 43; Journal ID: ISSN 0044-8249

Publisher:: Wiley Blackwell (John Wiley & Sons)

Country of Publication:: Germany

Language:: English

Citation Formats


                    Lang, Sandra M., Bernhardt, Thorsten M., Chernyy, Valeriy, Bakker, Joost M., Barnett, Robert N., and Landman, Uzi. Selective C−H Bond Cleavage in Methane by Small Gold Clusters.  Germany: N. p., 2017. 
Web.  doi:10.1002/ange.201706009.

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                    Lang, Sandra M., Bernhardt, Thorsten M., Chernyy, Valeriy, Bakker, Joost M., Barnett, Robert N., & Landman, Uzi. Selective C−H Bond Cleavage in Methane by Small Gold Clusters.  Germany.  https://doi.org/10.1002/ange.201706009

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                    Lang, Sandra M., Bernhardt, Thorsten M., Chernyy, Valeriy, Bakker, Joost M., Barnett, Robert N., and Landman, Uzi. Fri .  
"Selective C−H Bond Cleavage in Methane by Small Gold Clusters".  Germany.  https://doi.org/10.1002/ange.201706009.

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@article{osti_1394003,

  title        = {Selective C−H Bond Cleavage in Methane by Small Gold Clusters},

  author       = {Lang, Sandra M. and Bernhardt, Thorsten M. and Chernyy, Valeriy and Bakker, Joost M. and Barnett, Robert N. and Landman, Uzi},

  abstractNote = {Abstract Methane represents the major constituent of natural gas. It is primarily used only as a source of energy by means of combustion, but could also serve as an abundant hydrocarbon feedstock for high quality chemicals. One of the major challenges in catalysis research nowadays is therefore the development of materials that selectively cleave one of the four C−H bonds of methane and thus make it amenable for further chemical conversion into valuable compounds. By employing infrared spectroscopy and first‐principles calculations it is uncovered herein that the interaction of methane with small gold cluster cations leads to selective C−H bond dissociation and the formation of hydrido methyl complexes, H‐Au x + ‐CH 3 . The distinctive selectivity offered by these gold clusters originates from a fine interplay between the closed‐shell nature of the d states and relativistic effects in gold. Such fine balance in fundamental interactions could prove to be a tunable feature in the rational design of a catalyst.},

  doi          = {10.1002/ange.201706009},

  journal      = {Angewandte Chemie},

  number       = 43,

  volume       = 129,

  place        = {Germany},

  year         = {Fri Sep 22 00:00:00 EDT 2017},

  month        = {Fri Sep 22 00:00:00 EDT 2017}

}

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Title: Selective C−H Bond Cleavage in Methane by Small Gold Clusters

Abstract

Citation Formats

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Dehydrogenation of Simple Hydrocarbons on Platinum Cluster Ions journal, November 2002

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Bond Dissociation Energies of Organic Molecules journal, April 2003

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Temperature-Tunable Selective Methane Catalysis on Au 2 + : From Cryogenic Partial Oxidation Yielding Formaldehyde to Cold Ethylene Production journal, March 2011

Reactions of Atomic Cations with Methane: Gas Phase Room-Temperature Kinetics and Periodicities in Reactivity journal, May 2009

CH- and NH-activation by gaseous Rh2+ and PtRh+ cluster ions journal, September 2004

Methanaktivierung und katalytische Ethylenbildung an freiem Au 2 + journal, January 2010

Gas-Phase Catalysis by Atomic and Cluster Metal Ions: The Ultimate Single-Site Catalysts journal, March 2005

Methane activation by rhodium cluster argon complexes journal, April 1997

Chemistry with Methane: Concepts Rather than Recipes journal, June 2011

Activation of methane and methane-d4 by ionic platinum clusters journal, August 2006

Gas phase metal cluster model systems for heterogeneous catalysis journal, January 2012

Methane activation by platinum cluster ions in the gas phase: effects of cluster charge on the Pt4 tetramer journal, March 2000

Methane oligomerization in the gas phase by third-row transition-metal ions journal, March 1991

Efficient pseudopotentials for plane-wave calculations journal, January 1991

Pt+-mediated activation of methane: theory and experiment journal, June 1995

Generalized Gradient Approximation Made Simple
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How and Why Do Cluster Size, Charge State, and Ligands Affect the Course of Metal-Mediated Gas-Phase Activation of Methane?
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Methane activation on unsupported platinum clusters
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Methane Activation and Catalytic Ethylene Formation on Free Au2+
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Additivity Effects in the Reactivities of Bimetallic Cluster Ions PtmAun+
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Organometallic alkane CH activation
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Structures of the Dehydrogenation Products of Methane Activation by 5d Transition Metal Cations
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Unexpected Mechanistic Variants in the Thermal Gas-Phase Activation of Methane
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Born-Oppenheimer molecular-dynamics simulations of finite systems: Structure and dynamics of ( $H_{2}$ O $)_{2}$
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Dehydrogenation of Simple Hydrocarbons on Platinum Cluster Ions
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Complementary Active Sites Cause Size-Selective Reactivity of Aluminum Cluster Anions with Water
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Bond Dissociation Energies of Organic Molecules
journal, April 2003

The Platinum Hydrido-Methyl Complex: A Frozen Reaction Intermediate?
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Temperature-Tunable Selective Methane Catalysis on Au ₂ ⁺ : From Cryogenic Partial Oxidation Yielding Formaldehyde to Cold Ethylene Production
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Reactions of Atomic Cations with Methane: Gas Phase Room-Temperature Kinetics and Periodicities in Reactivity
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Gas-Phase Catalysis by Atomic and Cluster Metal Ions: The Ultimate Single-Site Catalysts
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Methane activation by rhodium cluster argon complexes
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Activation of methane and methane-d4 by ionic platinum clusters
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Gas phase metal cluster model systems for heterogeneous catalysis
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Methane activation by platinum cluster ions in the gas phase: effects of cluster charge on the Pt4 tetramer
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Methane oligomerization in the gas phase by third-row transition-metal ions
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Efficient pseudopotentials for plane-wave calculations
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Pt+-mediated activation of methane: theory and experiment
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