The Influence of a Changing Local Environment during Photoinduced CO₂ Dissociation

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.

Mechanistic and multiscale aspects of thermo-catalytic CO2conversion to C1products

“…An important concept to take into account when analyzing catalytic systems is that the reaction mechanism and the distribution of the active sites of a catalyst evolve under reaction conditions. 85,86 Indeed, the local reaction environment that forms during the reaction highly affects the reaction rates, 87 and catalyst materials can also undergo morphological transformation such as surface reconstruction, phase transition, and deactivation by sintering or coking. These are multiscale phenomena, which need a proper description based on the combination of experimental and theoretical analyses representing the different time and length scales ( i.e.…”

Perspectives on Advancing Sustainable CO2 Conversion Processes: Trinomial Technology, Environment, and Economy

“…270 Deactivation of the Catalysts/Carbon Formation. The local environment formed during the reaction affects the reaction rates, 274 and the catalyst can be morphologically transformed or deactivated by sintering or coking. 152 Such catalytic deactivation has motivated different studies for the development of a thermally stable material, whereas noble metals have been generally found to be highly active and, at the same time, more resistant to coke formation.…”