Optimizing Catalysis by Combining Molecular Scaling Relationships: Iron Porphyrin-Catalyzed Electrochemical Oxygen Reduction as a Case Study

Groff, Benjamin D.; Mayer, James M.

doi:10.1021/acscatal.2c04190

Title: Optimizing Catalysis by Combining Molecular Scaling Relationships: Iron Porphyrin-Catalyzed Electrochemical Oxygen Reduction as a Case Study

Journal Article · 11 September 2022 · ACS Catalysis

DOI: https://doi.org/10.1021/acscatal.2c04190 · OSTI ID:2460521

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Yale Univ., New Haven, CT (United States)

Here, the present work demonstrates the generality of molecular scaling relationships toward achieving faster catalysis at lower overpotentials. In iron porphyrin-catalyzed oxygen reduction, independent tuning of the catalyst E_1/2 and buffer pK_a resulted in improvement of both the maximum turnover frequency (TOF_max) and the effective overpotential (η_eff). Interestingly, the most optimal system is achieved with the most reducing catalyst and a weak buffered acid—a perhaps counterintuitive conclusion. More generally, this study illustrates a path to optimization of catalytic systems through their differing responses to changes in the intrinsic features of the system.

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Research Organization:: Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC05-76RL01830

OSTI ID:: 2460521

Report Number(s):: PNNL-SA--174749

Journal Information:: ACS Catalysis, Journal Name: ACS Catalysis Journal Issue: 19 Vol. 12; ISSN 2155-5435

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
electrocatalysis
oxygen reduction reaction
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Title: Optimizing Catalysis by Combining Molecular Scaling Relationships: Iron Porphyrin-Catalyzed Electrochemical Oxygen Reduction as a Case Study

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