TY - JOUR
T1 - Oxophilicity as a Descriptor for NO Cleavage Efficiency over Group IX Metal Clusters
AU - Yamaguchi, Masato
AU - Zhang, Yufei
AU - Kudoh, Satoshi
AU - Koyama, Kohei
AU - Lushchikova, Olga V.
AU - Bakker, Joost M.
AU - Mafuné, Fumitaka
AU - Mafuné, Fumitaka
N1 - Funding Information:
We gratefully acknowledge the Nederlandse Organisatie voor Wetenschappelijk Onderzoek (NWO) for the support of the FELIX Laboratory and thank the FELIX staff, particularly Dr. Britta Redlich for her skillful assistance. This work was supported in part by JSPS KAKENHI, Grant-in-Aid for JSPS Fellows (no. JP18J21934). We used supercomputers at the Research Center for Computational Science, Okazaki Research Facilities, National Institutes of Natural Sciences.
Publisher Copyright:
Copyright © 2020 American Chemical Society.
PY - 2020/6/4
Y1 - 2020/6/4
N2 - Iridium and rhodium are group IX elements that can both catalytically reduce NO. To understand the difference in their reactivity toward NO, the adsorption forms of NO onto clusters of Ir and Rh are compared using vibrational spectra, recorded via infrared multiple-photon dissociation spectroscopy. The spectra give evidence for the existence of at least two specific adsorption forms. The main Ir6+NO isomer is one in which NO is dissociated, whereas one other is a local minimum structure in the reaction pathway leading to dissociative adsorption. In contrast to adsorption onto Rh6+, where less than 10% of the isomeric population was found in the global minimum associated with dissociative adsorption, a substantial fraction (about 50%) of NO dissociates on Ir6+. This higher efficiency is attributed to a considerably reduced activation barrier for dissociation on Ir6+. The key chemical property identified for dissociation efficiency is the cluster's affinity to atomic oxygen.
AB - Iridium and rhodium are group IX elements that can both catalytically reduce NO. To understand the difference in their reactivity toward NO, the adsorption forms of NO onto clusters of Ir and Rh are compared using vibrational spectra, recorded via infrared multiple-photon dissociation spectroscopy. The spectra give evidence for the existence of at least two specific adsorption forms. The main Ir6+NO isomer is one in which NO is dissociated, whereas one other is a local minimum structure in the reaction pathway leading to dissociative adsorption. In contrast to adsorption onto Rh6+, where less than 10% of the isomeric population was found in the global minimum associated with dissociative adsorption, a substantial fraction (about 50%) of NO dissociates on Ir6+. This higher efficiency is attributed to a considerably reduced activation barrier for dissociation on Ir6+. The key chemical property identified for dissociation efficiency is the cluster's affinity to atomic oxygen.
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U2 - 10.1021/acs.jpclett.0c01133
DO - 10.1021/acs.jpclett.0c01133
M3 - Article
C2 - 32396005
AN - SCOPUS:85085962465
SN - 1948-7185
VL - 11
SP - 4408
EP - 4412
JO - Journal of Physical Chemistry Letters
JF - Journal of Physical Chemistry Letters
IS - 11
ER -