Tuning of Redox Conductivity and Electrocatalytic Activity in Metal-Organic Framework Films Via Control of Defect Site Density

Redox-active Metal-Organic Frameworks (MOFs) are considered as promising platforms for assembling high quantities of solution-accessible molecular catalysts on conductive surfaces, toward their utilization in electrochemical solar fuel related reactions. Nevertheless, slow redox hopping-based conductivity often constitutes a kinetic bottleneck hindering the overall electrocatalytic performance of these systems. In this work, we show that, by a systematic control of MOF defect site density, one can modulate the spatial distribution of post synthetically installed molecular catalyst and hence accelerate charge transport rates by an order of magnitude. Moreover, the improved MOF conductivity also yields an enhancement in its intrinsic electrocatalytic activity. Consequently, these results offer new possibilities for designing efficient MOF-based electrocatalytic systems.