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.

The Influence of a Changing Local Environment during Photoinduced CO2 Dissociation

Maestri M.;
2021

Abstract

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.
density functional theory
poisoning
scanning tunneling microscopy
single-molecule studies
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Utilizza questo identificativo per citare o creare un link a questo documento: http://hdl.handle.net/11311/1207000
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