Bidirectional electron donation in Cu<sub>1</sub>-Ti pairs on TiO<sub>x</sub> for efficient nitric oxide electroreduction.

Zhang, Yan; Yan, Ning; Zhou, Bing; Zhan, Guangming; Wang, Jiaxian; Zhao, Long; Hu, Lufa; Wang, Kaiyuan et al. · Nat Commun · 2026

basic_science · Level V

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Abstract

Electrocatalytic nitric oxide reduction (NORR) enables the efficient abatement of NO while simultaneously synthesizing valuable ammonia (NH<sub>3</sub>). However, the strong polarity of NO hinders its effective activation on conventional NORR catalysts because of their single-site interaction mode, wherein either the nitrogen (N) or oxygen (O) atom of NO binds to the catalyst through a unidirectional electron transfer. In this study, we construct dual-atom Cu<sub>1</sub>-Ti pairs on the titanium oxide (TiO<sub>x</sub>) substrate by using the complementary affinities of Ti for nitrogen and Cu for oxygen, which simultaneously activates both ends of the N=O bond. The designed Cu<sub>1</sub>-Ti pairs achieve competitive NORR performance with an NH<sub>3</sub> yield of 189.9 μmol h<sup>-1</sup> cm<sup>-2</sup> and a Faradaic efficiency of 93.7%. In situ techniques and theoretical calculations demonstrate that this dual-atom configuration shifts the mechanism from an end-on adsorption pathway observed on homonuclear pairs to a fully activating side-on mode. By highlighting the importance of adapted active site design in the electrocatalytic activation of polar molecules, this study facilitates the development of next-generation catalysts for complex transformations.