Synthesis of a Visible-Light-Responsive Perovskite SmTiO<sub>2</sub> N Bifunctional Photocatalyst via an Evaporation-Assisted Layered-Precursor Strategy.

Bao, Yunfeng; Du, Shiwen; Qi, Yu; Li, Gao; Zhang, Peng; Shao, Guosheng; Zhang, Fuxiang · Adv Mater · 2021

basic_science · Level V

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Abstract

Development of visible-light-responsive oxynitride photocatalysts has been highly inspired for promising solar-to-chemical conversion, but the number of Ti-based oxynitrides is scarce because of the relatively low thermal stability of Ti<sup>4+</sup> ions under ammonia flow. Here, the feasible synthesis of a novel perovskite SmTiO<sub>2</sub> N from the layered NaSmTiO<sub>4</sub> precursor is demonstrated to exhibit wide visible-light response with a bandgap of ≈2.1 eV and to show effective water reduction and oxidation functionalities under visible-light irradiation. The successful preparation mainly results from the synergistic effect of the layered structure of NaSmTiO<sub>4</sub> and the evaporation spillover of Na<sup>+</sup> ions, both of which are favorable for ammonia diffusion to accelerate the substitution of nitrogen to oxygen atoms and to shorten the nitridation time. The thermodynamic and kinetic feasibility of SmTiO<sub>2</sub> N for water splitting are investigated in detail, and its optimal apparent quantum efficiency (AQE) of water oxidation reaches 16.7% at 420 ± 10 nm, higher by far than that of most previous visible-light-responsive photocatalysts. Interestingly, a series of oxynitrides RTiO<sub>2</sub> N (R = La, Pr, Nd) are similarly synthesized by the alkali-metal evaporation-assisted layered-precursor strategy, demonstrating its generality to prepare visible-light-responsive (oxy)nitride photocatalysts containing reducible metals for solar energy conversion.