Electronic-reconstruction-enhanced hydrogen evolution catalysis in oxide polymorphs.

Li, Yangyang; Yu, Zhi Gen; Wang, Ling; Weng, Yakui; Tang, Chi Sin; Yin, Xinmao; Han, Kun; Wu, Haijun et al. · Nat Commun · 2019

basic_science · Level V

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Abstract

Transition metal oxides exhibit strong structure-property correlations, which has been extensively investigated and utilized for achieving efficient oxygen electrocatalysts. However, high-performance oxide-based electrocatalysts for hydrogen evolution are quite limited, and the mechanism still remains elusive. Here we demonstrate the strong correlations between the electronic structure and hydrogen electrocatalytic activity within a single oxide system Ti<sub>2</sub>O<sub>3</sub>. Taking advantage of the epitaxial stabilization, the polymorphism of Ti<sub>2</sub>O<sub>3</sub> is extended by stabilizing bulk-absent polymorphs in the film-form. Electronic reconstructions are realized in the bulk-absent Ti<sub>2</sub>O<sub>3</sub> polymorphs, which are further correlated to their electrocatalytic activity. We identify that smaller charge-transfer energy leads to a substantial enhancement in the electrocatalytic efficiency with stronger hybridization of Ti 3d and O 2p orbitals. Our study highlights the importance of the electronic structures on the hydrogen evolution activity of oxide electrocatalysts, and also provides a strategy to achieve efficient oxide-based hydrogen electrocatalysts by epitaxial stabilization of bulk-absent polymorphs.