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Title: Room Temperature Methane Capture and Activation by Ni Clusters Supported on TiC(001): Effects of Metal–Carbide Interactions on the Cleavage of the C–H Bond

Abstract

Methane is an extremely stable molecule, a major component of natural gas, and also one of the most potent greenhouse gases contributing to global warming. Consequently, the capture and activation of methane is a challenging and intensively studied topic. A major research goal is to find systems that can activate methane, even at low temperatures. In this work, combining ultrahigh vacuum catalytic experiments, X-ray photoemission spectra, and accurate density functional theory (DFT) based calculations, we show that small Ni clusters dispersed on the (001) surface of TiC are able to capture and dissociate methane at room temperature. Our DFT calculations reveal that two-dimensional Ni clusters are responsible for this chemical transformation, confirming that the lability of the supported clusters appears to be a critical aspect in the strong adsorption of methane. A small energy barrier of 0.18 eV is predicted for CH 4 dissociation into adsorbed methyl and atomic hydrogen species. In addition, the calculated reaction free energy profile at 300 K and 1 atm of CH 4 shows no effective energy barriers in the system. Comparison with other reported systems which activate methane at room temperature, including oxide and zeolite-based materials, indicates that a different chemistry takes place onmore » our metal/carbide system. Lastly, the discovery of a carbide-based surface able to activate methane at low temperatures paves the road for the design of new types of catalysts which can efficiently convert this hydrocarbon into other added-value chemicals, with implications in climate change mitigation.« less

Authors:
 [1];  [2];  [1]; ORCiD logo [1]; ORCiD logo [3];  [4]; ORCiD logo [5]; ORCiD logo [1]
  1. Universitat de Barcelona (Spain)
  2. Brookhaven National Lab. (BNL), Upton, NY (United States); Universidad Central de Venezuela, Caracas (Venezuela)
  3. Universitat de Barcelona (Spain); Institució Catalana de Recerca i Estudis Avançats (ICREA), Barcelona (Spain)
  4. Universidad Central de Venezuela, Caracas (Venezuela)
  5. Brookhaven National Lab. (BNL), Upton, NY (United States)
Publication Date:
Research Org.:
Brookhaven National Lab. (BNL), Upton, NY (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1501595
Report Number(s):
BNL-211389-2019-JAAM
Journal ID: ISSN 0002-7863
Grant/Contract Number:  
SC0012704
Resource Type:
Accepted Manuscript
Journal Name:
Journal of the American Chemical Society
Additional Journal Information:
Journal Name: Journal of the American Chemical Society; Journal ID: ISSN 0002-7863
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; 54 ENVIRONMENTAL SCIENCES

Citation Formats

Prats, Hèctor, Gutiérrez, Ramón A., Piñero, Juan José, Viñes, Francesc, Bromley, Stefan T., Ramírez, Pedro J., Rodriguez, José A., and Illas, Francesc. Room Temperature Methane Capture and Activation by Ni Clusters Supported on TiC(001): Effects of Metal–Carbide Interactions on the Cleavage of the C–H Bond. United States: N. p., 2019. Web. doi:10.1021/jacs.8b13552.
Prats, Hèctor, Gutiérrez, Ramón A., Piñero, Juan José, Viñes, Francesc, Bromley, Stefan T., Ramírez, Pedro J., Rodriguez, José A., & Illas, Francesc. Room Temperature Methane Capture and Activation by Ni Clusters Supported on TiC(001): Effects of Metal–Carbide Interactions on the Cleavage of the C–H Bond. United States. doi:10.1021/jacs.8b13552.
Prats, Hèctor, Gutiérrez, Ramón A., Piñero, Juan José, Viñes, Francesc, Bromley, Stefan T., Ramírez, Pedro J., Rodriguez, José A., and Illas, Francesc. Fri . "Room Temperature Methane Capture and Activation by Ni Clusters Supported on TiC(001): Effects of Metal–Carbide Interactions on the Cleavage of the C–H Bond". United States. doi:10.1021/jacs.8b13552.
@article{osti_1501595,
title = {Room Temperature Methane Capture and Activation by Ni Clusters Supported on TiC(001): Effects of Metal–Carbide Interactions on the Cleavage of the C–H Bond},
author = {Prats, Hèctor and Gutiérrez, Ramón A. and Piñero, Juan José and Viñes, Francesc and Bromley, Stefan T. and Ramírez, Pedro J. and Rodriguez, José A. and Illas, Francesc},
abstractNote = {Methane is an extremely stable molecule, a major component of natural gas, and also one of the most potent greenhouse gases contributing to global warming. Consequently, the capture and activation of methane is a challenging and intensively studied topic. A major research goal is to find systems that can activate methane, even at low temperatures. In this work, combining ultrahigh vacuum catalytic experiments, X-ray photoemission spectra, and accurate density functional theory (DFT) based calculations, we show that small Ni clusters dispersed on the (001) surface of TiC are able to capture and dissociate methane at room temperature. Our DFT calculations reveal that two-dimensional Ni clusters are responsible for this chemical transformation, confirming that the lability of the supported clusters appears to be a critical aspect in the strong adsorption of methane. A small energy barrier of 0.18 eV is predicted for CH4 dissociation into adsorbed methyl and atomic hydrogen species. In addition, the calculated reaction free energy profile at 300 K and 1 atm of CH4 shows no effective energy barriers in the system. Comparison with other reported systems which activate methane at room temperature, including oxide and zeolite-based materials, indicates that a different chemistry takes place on our metal/carbide system. Lastly, the discovery of a carbide-based surface able to activate methane at low temperatures paves the road for the design of new types of catalysts which can efficiently convert this hydrocarbon into other added-value chemicals, with implications in climate change mitigation.},
doi = {10.1021/jacs.8b13552},
journal = {Journal of the American Chemical Society},
number = ,
volume = ,
place = {United States},
year = {2019},
month = {3}
}

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This content will become publicly available on March 8, 2020
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