Please use this identifier to cite or link to this item: http://hdl.handle.net/2445/165741
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 Garcia, Hèctor
Gutierrez, Ramon A.
Piñero, Juan José
Viñes Solana, Francesc
Bromley, Stefan Thomas
Ramirez, Pedro J.
Rodríguez, José A.
Illas i Riera, Francesc
Keywords: Carburs
Titani
Teoria del funcional de densitat
Hidrocarburs
Carbides
Titanium
Density functionals
Hydrocarbons
Issue Date: 3-Apr-2019
Publisher: American Chemical Society
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 temperature. Here, combining ultrahigh vacuum catalytic experiments followed by 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 of this chemical transformation, evidencing 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 hydrogen atom 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. Comparing 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. 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 towards an efficient conversion of this hydrocarbon into other added-value chemicals, with implications in climate change mitigation.
Note: Versió postprint del document publicat a: https://doi.org/10.1021/jacs.8b13552
It is part of: Journal of the American Chemical Society, 2019, vol. 141, num. 13, p. 5303-5313
URI: http://hdl.handle.net/2445/165741
Related resource: https://doi.org/10.1021/jacs.8b13552
ISSN: 0002-7863
Appears in Collections:Articles publicats en revistes (Ciència dels Materials i Química Física)

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