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Reductive-defect-suppressed titanium oxynitrides via Ca3N2-assisted topochemical nitridation
Yuki Sasahara1, Kento Yoshii1, Daichi Kato1
1Department of Energy and Hydrocarbon Chemistry, Graduate School of Engineering, Kyoto University Kyoto 615-8510 Japan kage@scl.kyoto-u.ac.jp.
None:
Transition-metal oxynitrides are promising for photocatalysis and dielectric applications owing to their visible-light absorption and tunable band structures. Conventional ammonolysis, however, proceeds under reducing conditions that cause electron doping and limited compositional control. Here, we present a one-step, ammonia-free topochemical nitridation using Ca3N2 as a solid nitrogen source. BaTiO3 reacts with Ca3N2 at 550 °C via a stoichiometric 3O2-/2N3- anion-exchange process to yield orange BaTiO3-3x/2N x with Ti3+-related reductive defects suppressed below detectable levels. The resultant oxynitrides exhibit tunable bandgaps, high crystallinity, and visible-light photoactivity, while the CaO byproduct can be readily removed by washing. This method establishes Ca3N2 as a safe and effective reagent for controlled, ammonia-free oxynitride synthesis.
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