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Non-Covalent Assembly of Proton Donors and p-Benzoquinone Anions for Co-Electrocatalytic Reduction of Dioxygen

submitted on 03.03.2021, 20:14 and posted on 04.03.2021, 12:10 by Emma Cook, Shelby L. Hooe, Amelia Reid, Charles Machan

With weak acids (AH) at high concentrations, potential inversion can occur due to favorable hydrogen-bonding interactions with the intermediate monoanion [BQ(AH)m]•–. The solvation shell created by these interactions can mediate a proton-coupled electron transfer at more positive potentials, resulting in an overall two electron reduction ([BQ(AH)m]•– + nAH + e ⇌ [HBQ(AH)(m+n)-1(A)]2–). Here we show that the resultant hydrogen-bonded [HBQ] adduct mediates the transfer of electrons and the proton donor 2,2,2-trifluoroethanol (TFEOH) to a Mn-based complex during the electrocatalytic reduction of dioxygen (O2). The Mn electrocatalyst is selective for H2O2 with only TFEOH and O2 present, however, with BQ present under otherwise analogous conditions, an electrogenerated [HBQ(AH)4(A)]2– adduct (where AH = TFEOH) alters product selectivity to 96(±0.5)% H2O in a co-electrocatalytic fashion. These results suggest that hydrogen-bonded [HBQ] dianions can function in an analogous co-electrocatalytic manner to H2Q.


ACS PRF 61430-ND3


Email Address of Submitting Author


University of Virginia


United States

ORCID For Submitting Author


Declaration of Conflict of Interest

The authors declare no conflict of interest

Version Notes

version 01