<p> A wide
array of systems, ranging from enzymes to synthetic catalysts, exert adaptive
motifs to maximize their functionality. In a related manner, select
metal-organic frameworks (MOFs) and related systems exhibit structural
modulations under stimuli such as the infiltration of guest species. Probing
their responsive behavior <i>in-situ</i> is
a challenging but important step towards understanding their function and
subsequently building from there. In this report, we investigate the dynamic
behavior of an electrocatalytic Mn-porphyrin containing MOF system (Mn-MOF). We
discover, using a combination of electrochemistry and <i>in-situ</i> probes of UV-Vis absorption, resonance Raman and infrared
spectroscopy, a restructuration of this system via a reversible cleavage of the
porphyrin carboxylate ligands under an applied voltage. We further show, by
combining experimental data and DFT calculations, as a proof of concept, the
capacity to utilize the Mn-MOF for electrochemical CO<sub>2</sub> fixation and
to spectroscopically capture the reaction intermediates in its catalytic cycle.
The findings of this work and methodology developed opens opportunities in the
application of MOFs as dynamic, enzyme-inspired electrocatalytic systems.</p>
Electrochemically Triggered Dynamics Within a Hybrid Metal-Organic Electrocatalyst
