The Bending Machine: CO2 Activation and Hydrogenation on d-MoC(001) and b-Mo2C(001) Surfaces.

The adsorption and activation of a CO2 molecule on cubic d-MoC(001) and orthorhombic b-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 neglec...

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Bibliographic Details
Authors: Posada Pérez, Sergio, Viñes Solana, Francesc, Ramírez, Pedro J., Vidal, Alba B., Rodríguez, José A., Illas i Riera, Francesc
Format: article
Status:Versión aceptada para publicación
Publication Date:2014
Country:España
Institution:Universidad de Barcelona
Repository:Dipòsit Digital de la UB
OAI Identifier:oai:diposit.ub.edu:2445/118384
Online Access:https://hdl.handle.net/2445/118384
Access Level:Open access
Keyword:Teoria del funcional de densitat
Diòxid de carboni
Hidrogenació
Molibdè
Carburs
Density functionals
Carbon dioxide
Hydrogenation
Molybdenum
Carbides
Description
Summary:The adsorption and activation of a CO2 molecule on cubic d-MoC(001) and orthorhombic b-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 b-Mo2C(001) Mo-terminated polar surface provokes the spontaneous cleavage of a C-O bond in CO2 and carbon monoxide formation, whereas on a b-Mo2C(001) C-terminated polar surface or on a d-MoC(001) nonpolar surface the CO2 molecule is activated yet the C-O bond prevails. Experimental tests showed that Mo-terminated b-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+3H2-> 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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