Nanotip-Engineered TiO<sub>2</sub> Photoanodes Enable Efficient Hydroxyl Radical Synthesis via Selective Water Oxidation.

Zhang, Jun; Yu, Ruiquan; Qu, Songying; Mao, Jie; Ling, Li · Nano Lett · 2025

basic_science · Level V

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Abstract

Hydroxyl radicals (·OH) are pivotal for green synthesis, anticancer therapy, and environmental remediation, yet controllable synthesis remains challenging. Photoelectrochemical single-electron water oxidation (1e<sup>-</sup> WOR) provides a sustainable route for on-demand ·OH generation but is hindered by competing 4e<sup>-</sup> oxidation pathways and sluggish interfacial mass transport. Here, we overcome these limitations through a nanotip engineering strategy that integrates synergistic microfield regulation and interface optimization. Using TiO<sub>2</sub> nanocones, we demonstrate nanotip-generated localized positive-charge-enhanced electric fields and reagent/temperature gradients. This configuration enhances OH<sup>-</sup> adsorption, elevates the *OH → *O energy barrier, and boosts mass transport, collectively promoting ·OH generation. Furthermore, inherent aerophobicity enables rapid O<sub>2</sub> bubble detachment, suppressing detrimental *OH-O<sub>2</sub> hydrogen bonding (thermodynamically favoring the 1e<sup>-</sup> pathway) while dynamically renewing active sites (kinetically reducing steric hindrance). These synergistic effects yield a record ·OH synthesis rate (∼92.2 μM/min) and near-complete pollutant degradation (>6.7-fold enhancement over previous reports). Our work establishes rational design principles for high-efficiency ·OH-driven photoelectrodes.