The Influence of a Changing Local Environment during Photoinduced CO2 Dissociation

• Published in: Angewandte Chemie International Edition 2021-08, Vol.60 (33), p.18217-18222
• Main Authors: Vyshnepolsky, Michael, Ding, Zhao‐Bin, Srivastava, Prashant, Tesarik, Patrik, Mazhar, Hussain, Maestri, Matteo, Morgenstern, Karina
• Format: Article
• Language: English
• Subjects: Carbon dioxide; Catalysts; Changing environments; Copper; density functional theory; Photochemical reactions; Photochemicals; poisoning; scanning tunneling microscopy; Silver; single-molecule studies; Volcanoes
• ISSN: 1433-7851; 1521-3773
• DOI: 10.1002/anie.202105468

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. Following individual molecules and their changing environment during photoinduced dissociation reveals the importance of local changes during a reaction on its efficiency. Two counteracting processes lead to a volcano‐shaped reactivity.