Photoreactions with CO/CO2 Promoted By Hot Electrons in Plasmonic Metastructures

Abstract

Nanostructures and metastructures can be used for generation of energetic (hot) electrons which is a promising mechanism for solar photo-catalysis and photo-detectors. By building metal clusters into metamaterials and using large absorption cross sections of the plasmonic components, one can created hybrid systems where energetic (hot) electrons should make metal clusters more active in catalytic reactions, for example, in the CO2 reduction reaction. However, the central questions in the problem include two parts: how many hot electrons generated in such metamaterials; the other one is how the hot electrons catalyze the chemical reactions. In particular, we show that generation of hot electrons in metamaterials[1-4] leads to various chemical reaction mechanism and reaction pathways, which could be the guideline for producing direct CH4 and other multi-carbon alcohols (C2H3O, C2H4O, C2H5O etc.). Hot-electron generation[2, 4] together with the catalytic reaction mechanism represent efficient methods to transfer and localize optical and photo-chemical energies. Govorov, A.O., H. Zhang, H.V. Demir, and Y.K. Gun’ko, Nano Today, 2014. 9(1): p. 85-101. Hartland, G.V., L.V. Besteiro, P. Johns, and A.O. Govorov, ACS Energy Lett., 2017. 2(7): p. 1641-1653. Sykes, M.E., J.W. Stewart, G.M. Akselrod, X.-T. Kong, Z. Wang, D.J. Gosztola, A.B.F. Martinson, D. Rosenmann, M.H. Mikkelsen, A.O. Govorov, and G.P. Wiederrecht, Nature Commun., 2017. 8(1): p. 986. Sousa-Castillo, A., M. Comesaña-Hermo, B. Rodríguez-González, M. Pérez-Lorenzo, Z. Wang, X.-T. Kong, A.O. Govorov, and M.A. Correa-Duarte, J. Phys. Chem. C, 2016. 120(21): p. 11690-11699.