Molecular Engineering of Metal Complexes for Electrocatalytic Carbon Dioxide Reduction: From Adjustment of Intrinsic Activity to Molecular Immobilization

Abstract

The electrocatalytic CO 2 reduction reaction (ECO 2 RR) is one promising method for storing intermittent clean energy in chemical bonds and producing fuels. Among various kinds of catalysts for ECO 2 RR, molecular metal complexes with well-defined structures are convenient for studies of their rational design, structure-reactivity relationships, and mechanisms. In this Review, we summarize the molecular engineering of several N-based metal complexes including Re/Mn bipyridine compounds and metal macrocycles, concluding with general modification strategies to devise novel molecular catalysts with high intrinsic activity. Through physical adsorption, covalent linking, and formation of a periodic backbone, these active molecules can be heterogenized into immobilized catalysts with more practical prospects. Finally, significant challenges and opportunities based on molecular catalysts are discussed.

Charged Microdroplets as Microelectrochemical Cells for CO2 Reduction and C–C Coupling

“…21 Such behavior facilitates the homogeneous molecular catalysts to effectively cover the gas−liquid interface, aiding in the efficient storage and transfer of electrons for electrochemical reactions. 36 The structure and derivatives of this molecular catalyst have been extensively studied, 37−40 enabling us to trace and identify its evolution in microdroplets. Gas mass flow controllers are employed to accurately control the gas flow rate.…”

“…Previous studies have indicated that in the presence of an electric field, polar solute molecules tend to occupy the entire surface of microdroplets . Such behavior facilitates the homogeneous molecular catalysts to effectively cover the gas–liquid interface, aiding in the efficient storage and transfer of electrons for electrochemical reactions . The structure and derivatives of this molecular catalyst have been extensively studied, − enabling us to trace and identify its evolution in microdroplets.…”