Affiliation:
1. School of Chemical and Biomolecular Sciences Southern Illinois University Carbondale 1245 Lincoln Dr. 62901 Carbondale IL USA
Abstract
AbstractTraditional MOF e‐CRR, constructed from catalytic linkers, manifest a kinetic bottleneck during their multi‐electron activation. Decoupling catalysis and charge transport can address such issues. Here, we build two MOF/e‐CRR systems, CoPc@NU‐1000 and TPP(Co)@NU‐1000, by installing cobalt metalated phthalocyanine and tetraphenylporphyrin electrocatalysts within the redox active NU‐1000 MOF. For CoPc@NU‐1000, the e‐CRR responsive CoI/0 potential is close to that of NU‐1000 reduction compared to the TPP(Co)@NU‐1000. Efficient charge delivery, defined by a higher diffusion (Dhop=4.1×10−12 cm2 s−1) and low charge‐transport resistance (
=59.5 Ω) in CoPC@NU‐1000 led FECO=80 %. In contrast, TPP(Co)@NU‐1000 fared a poor FECO=24 % (Dhop=1.4×10−12 cm2 s−1 and
=91.4 Ω). For such a decoupling strategy, careful choice of the host framework is critical in pairing up with the underlying electrochemical properties of the catalysts to facilitate the charge delivery for its activation.