Mechanistic Insight on the Formation of GaN:ZnO Solid Solution from Zn-Ga Layered Double Hydroxide Using Urea as the...

A solid solution of GaN and ZnO (GaN:ZnO) is promising as a photocatalyst for visible-light-driven overall water splitting to produce H₂. However, several obstacles still exist in the conventional preparation procedure of GaN:ZnO. For example, the atomic distributions of Zn and Ga are nonuniform in GaN:ZnO when a mixture of the metal oxides, i.e. Ga₂O₃ and ZnO, is used as a precursor. In addition, GaN:ZnO is generally prepared under a harmful NH₃ flow for long durations at high temperatures. Here, a facile synthesis of GaN:ZnO with homogeneous atomic composition via a simple and safe procedure is reported. A layered double hydroxide (LDH) containing Zn²⁺ and Ga³⁺ was used to increase the uniformity of the atomic distributions of Zn and Ga in GaN:ZnO. We employed urea as a nitriding agent instead of gaseous NH₃ to increase the safety of the reaction. Through the optimization of reaction conditions such as heat treatment temperature and content of urea, single-phase GaN:ZnO was successfully obtained. In addition, the nitridation mechanism using urea was investigated in detail. NH₃ released from the thermal decomposition of urea did not directly nitride the LDH precursor. X-ray absorption and infrared  spectroscopies revealed that Zn(CN₂)-like intermediate species were generated at the middle temperature range and Ga-N bonds formed at high temperature along with dissociation of CO and CO₂.