It has been demonstrated recently that optically excited plasmonic metal nanoparticles can induce chemical transformations. It has been proposed that these chemical transformations take place through a transfer of charge from the plasmonic catalyst to the adsorbate, leading to the charge-driven chemical transformations. While the general features of the process are reasonably well understood, there are certain aspects of the mechanism that are less clear. Among others, the nature of the interaction between the localized surface plasmon states (LSPR) and electronic adsorbate states is still under debate. In these studies, probe molecules were used along with silver nanoparticle catalysts in a number of Raman spectroscopy experiments to provide further insights into the mechanism of photo-chemical reaction on the surface of plasmonic metal nanoparticles. We will shed light on the nature of the interaction between localized surface plasmon states and the excited electronic adsorbate states and demonstrate how these interactions can lead to chemical transformations. We will discuss the implications of our studies on the chemical activity and selectivity of plasmon-mediated photo-chemical transformation on metal nanoparticles. 1. S. Linic, P. Christopher, M. Andiappan, H. Xin, Accounts of Chemical Research, 46, 1890, 2013. 2. M. Andiappan, J. Zhang, S. Linic, Tuning selectivity in propylene epoxidation by plasmon mediated photo-switching of Cu oxidization state Science, 339, 1590, 2013. 3. P. Christopher, H. Xin, M. Andiappan, S. Linic, Singular Characteristics and Unique Chemical Bond Activation Mechanisms of Photocatalytic Reactions on Plasmonic Nanostructures, Nature Materials, 11, 1044, 2012.

Probing the mechanistic of charge transfer from optically excited plasmonic metal nanoparticles to adsorbates leading to chemical transformations

249th National Meeting (2015)

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