Shaping the Electrocatalytic Performance of Metal Complexes for CO2 Reduction

• Published in: ChemElectroChem Vol. 8; no. 18; pp. 3472 - 3481
• Main Authors: Gotico, Philipp, Leibl, Winfried, Halime, Zakaria, Aukauloo, Ally
• Format: Journal Article
• Language: English
• Published: Weinheim John Wiley & Sons, Inc 13.09.2021; Weinheim : Wiley-VCH
• Subjects: Carbon dioxide; carbon dioxide reduction; Catalysis; Catalysts; Catalytic activity; Chemical Sciences; Chemists; Coordination chemistry; Coordination compounds; electrocatalysis; Hydrogen bonding; iron porphyrin; molecular catalyst; Porphyrins; Protons; Reduction (metal working); second coordination sphere
• ISSN: 2196-0216; 2196-0216
• DOI: 10.1002/celc.202100476

The mass scale catalytic transformation of carbon dioxide (CO2) into reduced forms of carbon is an imperative to address the ever‐increasing anthropogenic emission. Understanding the mechanistic routes leading to the multi‐electron‐proton conversion of CO2 provides handles for chemists to overcome the kinetically and thermodynamically hard challenges and further optimize these processes. Through extensive electrochemical investigations, Prof. J.‐M. Savéant and coworkers have made invaluable electro‐analytical tools accessible to chemists to address and position the electrocatalytic performance of molecular catalysts grounded on a theoretical basis. Furthermore, he has bequeathed lessons to future generations on ways to improve the catalytic activity and the electrocatalytic zone we must target. As a tribute to his accomplishments, we recall here a few aspects on the tuning of iron porphyrin catalysts by playing on electronic effects, proton delivery, hydrogen bonding and electrostatic interactions and its implications to other catalytic systems. Eyes on the Goal! Prof. J.‐M. Savéant has set a stage for performance benchmarking of molecular electrocatalysts for carbon dioxide reduction and importantly established catalyst design principles for catalysis improvement. This minireview highlights how his seminal works have inspired chemists to continually optimize iron porphyrins in terms of efficiency, robustness, and selectivity.