Experiment–Theory Synergy: Connecting the Kinetics of the Molecular Catalysis of Electrochemical Reactions with Calculated Energy Landscapes

ACS Catalysis, Год журнала: 2025, Номер unknown, С. 2504 - 2514

Опубликована: Янв. 27, 2025

While energy profiles from quantum mechanical calculations suggest mechanisms for molecular catalysis of electrochemical reactions, they frequently lack experimental kinetic validation due to limited data or ambiguities linking calculated and observables. Herein, we expand the "energetic span model", traditionally applied in homogeneous systems, molecularly catalyzed reactions focusing on EC1..CnE′-type mechanisms. We thus establish a framework aligning theoretical turnover frequency estimates with practical cyclic voltammetry measurements i.e., extracted rate constants accounting diffusion–reaction layer complexities. The analysis also identifies specific zones, defining conditions under which different catalyst intermediates dominate layer. This approach helps refine energetic model may improve alignment calculation. It is experimentally well-studied reduction CO2 CO using an iron tetraphenylporphyrin phenol as proton donor. Previously explored pathways align partly data, but important discrepancies exist, especially regarding reaction's dependence binding donor concentration. findings highlight challenges predicting behavior underscore significance intermediate energetics reaction modeling. Nonetheless, cross-talk between solid studies should be reasonable path toward reaching mechanistic consensus.

Язык: Английский

Beyond scaling relations in electrocatalysis: unifying concepts from molecular systems and metallic surfaces

Chemical Science, Год журнала: 2025, Номер unknown

Опубликована: Янв. 1, 2025

Developing and benchmarking new, efficient catalysts for the electrochemical CO 2 reduction reaction is paramount its application in global transition toward non-fossil carbon feedstocks energy sources.

Язык: Английский