Adsorption and dissociation of molecular hydrogen on orthorhombic β- Mo2C and cubic δ-MoC (001) surfaces

Molybdenum carbides are increasingly used in heterogeneously catalyzed hydrogenation reactions, which imply the adsorption and dissociation of molecular hydrogen. Here a systematic density functional theory based study, including or excluding dispersion terms, concerning the interaction and stabilit...

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Bibliographic Details
Authors: Posada Pérez, Sergio, Viñes Solana, Francesc, Valero Montero, Rosendo, Rodríguez, José A., Illas i Riera, Francesc
Format: article
Status:Versión aceptada para publicación
Publication Date:2016
Country:España
Institution:Universidad de Barcelona
Repository:Dipòsit Digital de la UB
OAI Identifier:oai:diposit.ub.edu:2445/112844
Online Access:https://hdl.handle.net/2445/112844
Access Level:Open access
Keyword:Espectroscòpia infraroja
Carburs
Dissociació (Química)
Hidrogenació
Termodinàmica
Física nuclear
Infrared spectroscopy
Carbides
Dissociation
Hydrogenation
Thermodynamics
Nuclear physics
Description
Summary:Molybdenum carbides are increasingly used in heterogeneously catalyzed hydrogenation reactions, which imply the adsorption and dissociation of molecular hydrogen. Here a systematic density functional theory based study, including or excluding dispersion terms, concerning the interaction and stability of H2 with cubic δ-MoC(001) and orthorhombic β-Mo2C(001) surfaces is presented. In the latter case the two possible C or Mo terminations are considered. In addition, different situations for the H covered surfaces are examined. Computational results including dispersive forces predict as essentially spontaneous dissociation of H2 on β-Mo2C(001) independently of the surface termination, whereas on δ-MoC(001) molecular hydrogen dissociation implies a small but noticeable energy barrier. Furthermore, the ab initio thermodynamics formalism has been used to compare the stability of different H coverages. Finally, core level binding energies and vibrational frequencies are presented with the aim to assist the interpretation of yet unavailable data from X-ray photoelectron and infrared spectroscopies.