Outer-coordination sphere in multi-H(+)/multi-e(–)molecular electrocatalysis

Electrocatalysis is an indispensable technique for small-molecule transformations, which are essential for the sustainability of society. Electrocatalysis utilizes electricity as an energy source for chemical reactions. Hydrogen is considered the “fuel for the future,” and designing electrocatalysts for hydrogen production has thus become critical. Furthermore, fuel cells are promising energy solutions that require robust electrocatalysts for key fuel cell reactions such as the interconversion of oxygen to water. Concerns regarding the rising concentration of atmospheric carbon dioxide have prompted the search for CO(2) conversion methods. One promising approach is the electrochemical conversion of CO(2) into commodity chemicals and/or liquid fuels, but such chemistry is highly energy demanding because of the thermodynamic stability of CO(2). All of the above-mentioned electrocatalytic processes rely on the selective input of multiple protons (H(+)) and electrons (e(–)) to yield the desired products. Biological enzymes evolved in nature to perform such redox catalysis and have inspired the design of catalysts at the molecular and atomic levels. While it is synthetically challenging to mimic the exact biological environment, incorporating functional outer coordination spheres into molecular catalysts has shown promise for advancing multi-H(+) and multi-e(–) electrocatalysis. From this Perspective, herein, catalysts with outer coordination sphere(s) are selected as the inspiration for developing new catalysts, particularly for the reductive conversion of H(+), O(2), and CO(2), which are highly relevant to sustainability. The recent progress in electrocatalysis and opportunities to explore beyond the second coordination sphere are also emphasized.