The Influence of a Changing Local Environment during Photoinduced CO2 Dissociation

Vyshnepolsky, M. and Ding, Z.-B. and Srivastava, P. and Tesarik, P. and Mazhar, H. and Maestri, M. and Morgenstern, K.

Volume: Pages:
DOI: 10.1002/anie.202105468
Published: 2021

Though largely influencing the efficiency of a reaction, the molecular-scale details of the local environment of the reactants are experimentally inaccessible hindering an in-depth understanding of a catalyst's reactivity, a prerequisite to maximizing its efficiency. We introduce a method to follow individual molecules and their largely changing environment during a photochemical reaction. The method is illustrated for a rate-limiting step in a photolytic reaction, the dissociation of CO2 on two catalytically relevant surfaces, Ag(100) and Cu(111). We reveal with a single-molecule resolution how the reactant's surroundings evolve with progressing laser illumination and with it their propensity for dissociation. Counteracting processes lead to a volcano-like reactivity. Our unprecedented local view during a photoinduced reaction opens the avenue for understanding the influence of the products on reaction yields on the nanoscale. © 2021 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH

« back