Elucidation of Design Criteria for V‐based Redox Mediators: Structure‐Function Relationships that Dictate Rates of Heterogeneous Electron Transfer

Dagar, Mamta; Brennessel, William W.; Matson, Ellen M.

doi:10.1002/chem.202400764

Title: Elucidation of Design Criteria for V‐based Redox Mediators: Structure‐Function Relationships that Dictate Rates of Heterogeneous Electron Transfer

Journal Article · 03 May 2024 · Chemistry - A European Journal

DOI: https://doi.org/10.1002/chem.202400764 · OSTI ID:2345807

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University of Rochester Department of Chemistry Rochester NY 14627 USA

Abstract Redox mediators are attractive solutions for addressing the stringent kinetic stipulations required for efficient energy conversion processes. In this work, we compare the electrochemical properties of four vanadium complexes, namely [V(acac) ₃ ], [V ₆ O ₇ (OMe) ₁₂ ], [ ⁿ Bu ₄ N] ₃ [V ₆ O ₁₃ (TRIS ^NO2 ) ₂ ], and [ ⁿ Bu ₄ N] ₅ [V ₁₈ O ₄₆ (NO ₃ )] in non‐aqueous solutions on glassy carbon electrodes. The goal of this study is to investigate the electron transfer kinetics and diffusivity of these compounds under identical experimental conditions to develop an understanding of structure‐function relationships that dictate the physicochemical properties of vanadium oxide assemblies. Complex selection was dictated by two criteria – (1) nuclearity of the transition metal complexes (2) distribution of electron density in the native electronic configuration. Our analyses establish that electronic communication between metal centers significantly impacts charge transfer kinetics of these vanadium‐based compounds.

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Sponsoring Organization:: USDOE

Grant/Contract Number:: SC0002106

OSTI ID:: 2345807

Journal Information:: Chemistry - A European Journal, Journal Name: Chemistry - A European Journal Vol. 30 Journal Issue: 32; ISSN 0947-6539

Publisher:: Wiley Blackwell (John Wiley & Sons)Copyright Statement

Country of Publication:: Germany

Language:: English

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