Computational investigation on the catalytic activity of Rh-6 and Rh4Ru2 clusters towards methanol activation

TitleComputational investigation on the catalytic activity of Rh-6 and Rh4Ru2 clusters towards methanol activation
Publication TypeJournal Article
Year of Publication2014
AuthorsGhatak, K, Sengupta, T, Krishnamurty, S, Pal, S
JournalTheoretical Chemistry Accounts
Volume134
Issue1
Pagination1597
Date PublishedDEC
Type of ArticleArticle
ISSN1432-881X
KeywordsBimetallic Clusters, Density Functional Theory (DFT), Doping, Methanol Activation, Rhodium Clusters
Abstract

Catalysis of molecular activation of small molecules through scission of strong chemical bonds is one of the major challenges faced by chemists. More specifically, activation of the strong C-H and O-H bonds of various alcohols, especially methanol, is one of the various important intermediate steps of key organic reactions. Our present work explores a suitable metal cluster catalyst towards methanol dissociation. In particular, we have examined the effect of ruthenium doping (Rh:Ru = 2:1) on the catalytic activity of Rh-6 cluster towards methanol dissociation. Density functional theory-based calculations illustrate two competitive pathways for methanol dissociation, which are via O-H and C-H bond breaking. Both the pathways are found to be energetically favourable in the presence of bimetallic and mono-metallic clusters. Importantly, energy barrier for O-H bond dissociation reduces considerably in doped cluster as compared to pure Rh-6 cluster and is smaller than the values reported for a number of other small metallic clusters.

DOI10.1007/s00214-014-1597-z
Type of Journal (Indian or Foreign)

Foreign

Impact Factor (IF)

1.806

Divison category: 
Physical and Materials Chemistry