Assembly of a Metal–Organic Framework (MOF) Membrane on a Solid Electrocatalyst: Introducing Molecular‐Level Control Over Heterogeneous CO2 Reduction

Abstract Electrochemically active Metal‐Organic Frameworks (MOFs) have been progressively recognized for their use in solar fuel production schemes. Typically, they are utilized as platforms for heterogeneous tethering of exceptionally large concentration of molecular electrocatalysts onto electrodes. Yet so far, the potential influence of their extraordinary chemical modularity on electrocatalysis has been overlooked. Herein, we demonstrate that, when assembled on a solid Ag CO 2 reduction electrocatalyst, a non‐catalytic UiO‐66 MOF acts as a porous membrane that systematically tunes the active site's immediate chemical environment, leading to a drastic enhancement of electrocatalytic activity and selectivity. Electrochemical analysis shows that the MOF membrane improves catalytic performance through physical and electrostatic regulation of reactants delivery towards the catalytic sites. The MOF also stabilizes catalytic intermediates via modulation of active site's secondary coordination sphere. This concept can be expanded to a wide range of proton‐coupled electrochemical reactions, providing new means for precise, molecular‐level manipulation of heterogeneous solar fuels systems.