Decoupling Redox Hopping and Catalysis in Metal‐Organic Frameworks ‐based Electrocatalytic CO <sub>2</sub> Reduction
Xinlin Li, Sreehari Surendran Rajasree, Venkatesh Gude, Karan Maindan, Pravas Deria
Abstract
Abstract Traditional 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 Co I/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 ( D hop =4.1×10 −12 cm 2 s −1 ) and low charge‐transport resistance ( =59.5 Ω) in CoPC@NU‐1000 led FE CO =80 %. In contrast, TPP(Co)@NU‐1000 fared a poor FE CO =24 % ( D hop =1.4×10 −12 cm 2 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.