Control of the Photocatalytic Activity of Metastable Layered Oxynitride K₂LaTa₂O₆N through Topochemical Transformation of Tuned Oxide Precursors

In the development of oxynitride photocatalysts, thermal ammonolysis of a metal oxide precursor has often been conducted by varying the reaction conditions (e.g., temperatures, reaction times, and ammonia gas flow rates) to obtain high-quality oxynitride particles that efficiently function as photocatalysts. However, this approach may suffer from undesirable changes in the physicochemical properties of the resulting oxynitride, leading to the lowering of the photocatalytic activity. Here, we show that it is possible to control the photocatalytic activity of Ruddlesden-Popper metastable layered oxynitride K2LaTa2O6N, obtained from the Dion-Jacobson phase KLaTa2O7 through a topochemical ammonolysis reaction, by controlling the quality of the KLaTa2O7 template. During the ammonolysis of KLaTa2O7, in the presence of K2CO3, to K2LaTa2O6N, the structural properties (e.g., degree of crystallinity and particle size) of the oxide precursor were replicated in the resulting oxynitride. Namely, the use of KLaTa2O7, possessing a higher degree of crystallinity, led to larger K2LaTa2O6N particles being formed. By increasing the crystallinity of KLaTa2O7, the photocatalytic activity of the resulting K2LaTa2O6N for H2 evolution was improved for reaction in aqueous NaI solution under visible light irradiation. This improvement in performance was due to the longer lifetime of the photogenerated mobile electrons in high-crystallinity K2LaTa2O6N compared with that in the low-crystallinity analogue, as confirmed by femtosecond transient absorption spectroscopy. However, the photocatalytic activity of K2LaTa2O6N derived from well-grown larger KLaTa2O7 particles was an order of magnitude lower than that of the best-performing material. Physicochemical measurements revealed that the large K2LaTa2O6N particles contained a relatively high density of anionic defects on the surface, which shortened the lifetime of the photogenerated charge carriers, leading to lower photocatalytic activity.