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Title: Combining theory and experiment for multitechnique characterization of activated CO2 on transition metal carbide (001) surfaces
Author: Kunkel, Christian
Viñes Solana, Francesc
Ramírez, Pedro J.
Rodríguez, José A.
Illas i Riera, Francesc
Keywords: Teoria del funcional de densitat
Dissociació (Química)
Density functionals
Issue Date: 15-Jan-2018
Publisher: American Chemical Society
Abstract: Early transition metal carbides (TMC; TM = Ti, Zr, Hf, V, Nb, Ta, Mo) with face-centered cubic crystallographic structure have emerged as promising materials for CO2 capture and activation. Density functional theory (DFT) calculations using the Perdew-Burke-Ernzerhof exchange-correlation functional evidence charge transfer from the TMC surface to CO2 on the two possible adsorption sites, namely, MMC and TopC, and the electronic structure and binding strength differences are discussed. Further, the suitability of multiple experimental techniques with respect to (1) adsorbed CO2 recognition and (2) MMC/TopC adsorption distinction is assessed from extensive DFT simulations. Results show that ultraviolet photoemission spectroscopies (UPS), work function changes, core level X-ray photoemission spectroscopy (XPS), and changes in linear optical properties could well allow for adsorbed CO2 detection. Only infrared (IR) spectra and scanning tunnelling microscopy (STM) seem to additionally allow for MMC/TopC adsorption site distinction. These findings are confirmed with experimental XPS measurements, demonstrating CO2 binding on single crystal (001) surfaces of TiC, ZrC, and VC. The experiments also help resolving ambiguities for VC, where CO2 activation was unexpected due to low adsorption energy, but could be related to kinetic trapping involving a desorption barrier. With a wealth of data reported and direct experimental evidence provided, this study aims to motivate further basic surface science experiments on an interesting case of CO2 activating materials, allowing also for a benchmark of employed theoretical models.
Note: Versió postprint del document publicat a:
It is part of: Journal of Physical Chemistry C, 2018, vol. 123, num. 13, p. 7567-7576
Related resource:
ISSN: 1932-7447
Appears in Collections:Articles publicats en revistes (Ciència dels Materials i Química Física)

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