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Circumventing Scaling Relations in Oxygen Electrochemistry using Metal-Organic Frameworks

preprint
submitted on 24.09.2020 and posted on 25.09.2020 by Tyler Sours, Anjli Patel, Jens Kehlet Nørskov, Samira Siahrostami, Ambarish Kulkarni
It has been well-established that unfavorable scaling relationships between *OOH, *OH, and *O are responsible for the high overpotentials associated with oxygen electrochemistry. A number of strategies have been proposed for breaking these linear constraints for traditional electrocatalysts (e.g. metals, alloys, metal-doped carbons); such approaches have not yet been validated experimentally for heterogenous catalysts. Development of a new class of catalysts capable of circumventing such scaling relations remains an ongoing challenge in the field. In this work, we use density functional theory (DFT) calculations to demonstrate that bimetallic porphyrin-based MOFs (PMOFs) are an ideal materials platform for rationally-designing the 3D active site environments for oxygen reduction reaction (ORR). Specifically, we show that the *OOH binding energy and the theoretical limiting potential can be optimized by appropriately tuning the transition metal active site, the oxophilic spectator, and the MOF topology. Our calculations predict theoretical limiting potentials as high as 1.07 V for Fe/Cr-PMOF-Al, which exceeds the Pt/C benchmark for 4e ORR. More broadly, by highlighting their unique characteristics, this works aims to establish bimetallic porphyrin-based MOFs as a viable materials platform for future experimental and theoretical ORR studies.

History

Email Address of Submitting Author

arkulkarni@ucdavis.edu

Institution

University of California, Davis

Country

USA

ORCID For Submitting Author

0000-0001-9834-8264

Declaration of Conflict of Interest

None

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