Authors
Mingyu Liu, Shaowei Mei, Muhammad Afsar Khan, Wei Pei, Fei Lu, Liangliang Min, Min Zhou
Published in
Small (Weinheim an der Bergstrasse, Germany). Pages e75711. Sep 09, 2026. Epub Sep 09, 2026.
Abstract
Electrochemical two-electron water oxidation (2e-WOR) offers a promising direct route to on-site hydrogen peroxide (H2O2) production, yet state-of-the-art catalysts still suffer from intrinsically low selectivity and large overpotentials, especially in near-neutral media. Equally unresolved is how the electrolyte composition steers the competition between 2e-WOR and the thermodynamically favored four-electron oxygen evolution reaction (OER). Here we employed a monolayer TiO2 nanosheet platform to anchor atomically dispersed 3d/4d transition-metal centers (Ru1, Cu1, Co1, and Fe1). Among them, Ru1-TiO2 delivers an optimal Faradaic efficiency (FE) of 60.8% at a low overpotential of 130 mV. Further analysis reveals that the oxygen-bridged Ru─Ti (Ru─O─Ti) asymmetric dimer establishes a gradient d-p-d orbital coupling. This electronic motif strengthens the adsorption of HCO3* while attenuating the over-binding of OH*, thereby switching the surface termination from OH* to HCO3*-rich. Consequently, a bicarbonate-mediated 2e-WOR pathway is selectively activated over the Ru─O─Ti sites, which is much more favorable than the conventional OH*-OH* coupling route. These findings underscore that gradient orbital coupling across asymmetric atomic pairs act as an electronic lever to redirect the catalytic trajectory, furnishing a general principle for pathway control in diverse electrosynthesis systems.
PMID:
42717502
Bibliographic data and abstract were imported from PubMed on 10 Sep 2026.
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