Decoupling Redox Hopping and Catalysis in Metal-Organic Frameworks -based Electrocatalytic CO2 Reduction |
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Authors: | Xinlin Li Sreehari Surendran Rajasree Dr Venkatesh Gude Karan Maindan Prof?Dr Pravas Deria |
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Institution: | School of Chemical and Biomolecular Sciences, Southern Illinois University Carbondale, 1245 Lincoln Dr., 62901 Carbondale, IL, USA |
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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 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. |
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Keywords: | CO2 Reduction Electrocatalysis Electron Transport Metal-Organic Frameworks Molecular Catalysts |
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