Journal
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
Volume 16, Issue 28, Pages 14912-14921Publisher
ROYAL SOC CHEMISTRY
DOI: 10.1039/c4cp01943a
Keywords
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Funding
- Spanish MINECO [CTQ2012-30751]
- Generalitat de Catalunya [2014SGR97, XRQTC]
- U. S. Department of Energy, Chemical Sciences Division [DE-AC02-98CH10886]
- Spanish MEC predoctoral grant [CTQ2012-30751]
- MINECO [JCI-2010-06372]
- ICREA Academia award for excellence in research
- INTEVEP
- IDB
- Red Espanola de Supercomputacion
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The adsorption and activation of a CO2 molecule on cubic delta-MoC(001) and orthorhombic beta-Mo2C(001) surfaces have been investigated by means of periodic density functional theory based calculations using the Perdew-Burke-Ernzerhof exchange-correlation functional and explicitly accounting for (or neglecting) the dispersive force term description as proposed by Grimme. The DFT results indicate that an orthorhombic beta-Mo2C(001) Mo-terminated polar surface provokes the spontaneous cleavage of a C-O bond in CO2 and carbon monoxide formation, whereas on a beta-Mo2C(001) C-terminated polar surface or on a delta-MoC(001) nonpolar surface the CO2 molecule is activated yet the C-O bond prevails. Experimental tests showed that Mo-terminated beta-Mo2C(001) easily adsorbs and decomposes the CO2 molecule. This surface is an active catalyst for the hydrogenation of CO2 to methanol and methane. Although MoC does not dissociate C-O bonds on its own, it binds CO2 better than transition metal surfaces and is an active and selective catalyst for the CO2 + 3H(2) -> CH3OH + H2O reaction. Our theoretical and experimental results illustrate the tremendous impact that the carbon/metal ratio has on the chemical and catalytic properties of molybdenum carbides. This ratio must be taken into consideration when designing catalysts for the activation and conversion of CO2.
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