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Computational investigation on the catalytic activity of Rh6 and Rh4Ru2 clusters towards methanol activation

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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 Rh6 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 Rh6 cluster and is smaller than the values reported for a number of other small metallic clusters.

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Acknowledgments

The authors acknowledge the Centre of excellence in Computational Chemistry at CSIR–NCL, Pune, for the calculations presented and the CSIR XII 5-year plan for a Multiscale Simulation of Materials (MSM) project grant. Sourav Pal acknowledges grant from SSB project of CSIR and the J. C. Bose Fellowship grant of DST towards partial fulfilment of this work. Kamalika Ghatak acknowledges Susanta Das and Dar Manzoor of CSIR-NCL for insightful discussions.

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Authors and Affiliations

  1. Physical Chemistry Division, CSIR-National Chemical Laboratory, Pune, 411008, India

    Kamalika Ghatak, Turbasu Sengupta & Sourav Pal

  2. Functional Materials Division, CSIR-Central Electrochemical Research Institute, Karaikudi, 630006, India

    Sailaja Krishnamurty

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  1. Kamalika Ghatak
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  2. Turbasu Sengupta
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  3. Sailaja Krishnamurty
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  4. Sourav Pal
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Correspondence to Sourav Pal.

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Ghatak, K., Sengupta, T., Krishnamurty, S. et al. Computational investigation on the catalytic activity of Rh6 and Rh4Ru2 clusters towards methanol activation. Theor Chem Acc 134, 1597 (2015). https://doi.org/10.1007/s00214-014-1597-z

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