Zeinalipour-Yazdi, Constantinos D. ORCID: https://orcid.org/0000-0002-8388-1549 and van Santen, Rutger A. (2012) Coverage-dependent adsorption energy of carbon monoxide on a rhodium nanocluster. The Journal of Physical Chemistry C, 116 (15). pp. 8721-8730. ISSN 1932-7447 (Print), 1932-7455 (Online) (doi:10.1021/jp2090044)

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Abstract

Metal–adsorbate nanoclusters serve as useful models to study elementary catalytic and gas-sensor processes. However, little is known about their structural, energetic, and spectroscopic properties as a function of adsorbate surface coverage and structure. Here, we perform a systematic study of the adsorption of carbon monoxide (CO) on a tetra-atomic rhodium cluster to understand the coverage- and structure-dependent adsorption energy of CO as a function of CO coverage and to provide deeper insight into the metacarbonyl bond on metal nanoclusters. The coverage-dependent adsorption energy trends are rationalized with a use of a theoretical model, molecular orbital energy diagrams, electron density difference plots, molecular electrostatic potential plots, and simulated infrared spectra. Our model demonstrates that a critical parameter that determines the coverage-dependent energetics of the adsorption of CO at low coverages is the polarization of metal–metal π-bonds during the effective charge transfer, occurring from the metal cluster to the 2π*2py and 2π*2px states of CO, which enhances the adsorption of CO vertical to the metal–metal bond. This configuration specific effect explains the negative coverage-dependent adsorption energy trend observed at low coverages on metal nanoclusters.

Item Type:	Article
Uncontrolled Keywords:	CO adsorption, DFT, rhodium nanocluster, coverage-dependent
Subjects:	Q Science > QD Chemistry
Faculty / School / Research Centre / Research Group:	Faculty of Engineering & Science Faculty of Engineering & Science > School of Science (SCI)
Last Modified:	06 Oct 2018 21:09
URI:	http://gala.gre.ac.uk/id/eprint/21467

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