Heterogenised Molecular Catalysts for Sustainable Electrochemical CO₂ Reduction

Abstract

There has been a rapid rise in interest regarding the advantages of support materials to protect and immobilise molecular catalysts for the carbon dioxide reduction reaction (CO2RR) in order to overcome the weaknesses of many well‐known catalysts in terms of their stability and selectivity. In this Review, the state of the art of different catalyst‐support systems for the CO2RR is discussed with the intention of leading towards standard benchmarking for comparison of such systems across the most relevant supports and immobilisation strategies, taking into account these multiple pertinent metrics, and also enabling clearer consideration of the necessary steps for further progress. The most promising support systems are described, along with a final note on the need for developing more advanced experimental and computational techniques to aid the rational design principles that are prerequisite to prospective industrial upscaling.

Electrocatalytic reduction of CO2 to CO by Fe(iii) carbazole–porphyrins in homogeneous molecular systems

“…9,10 On the other hand, homogeneous metal complexes are essential systems for studying CO 2 RR mechanisms at a molecular level, offering superior selectivity and exceptional activity. [11][12][13] Wang and co-workers found that homogeneous catalysts were actually dynamically adsorbed on the electrode surface in a homogeneous system. 14 These metal complexes allow for precise tailoring of well-defined active site structures.…”

Manipulating the Coordination Structure of Molecular Cobalt Sites in Periodic Mesoporous Organosilica for CO2 Photoreduction

“…However, these shortcomings can be mitigated via heterogenisation of the molecular complexes on solid supports, [12][13][14][15] which bridges between homogenous and heterogeneous systems and provides an opportunity to precisely regulate the structure of the active site on solid support at atomic levels. The primary coordination environment around the central metal active site plays a crucial role controlling the catalytic reaction.…”