Mechanistically Guided Materials Chemistry: Synthesis of Ternary Nitrides, CaZrN2 and CaHfN2

• Published in: Journal of the American Chemical Society Vol. 146; no. 6; pp. 4001 - 4012
• Main Authors: Rom, Christopher L., Novick, Andrew, McDermott, Matthew J., Yakovenko, Andrey A., Gallawa, Jessica R., Tran, Gia Thinh, Asebiah, Dominic C., Storck, Emily N., McBride, Brennan C., Miller, Rebecca C., Prieto, Amy L., Persson, Kristin A., Toberer, Eric, Stevanović, Vladan, Zakutayev, Andriy, Neilson, James R.
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 14.02.2024; American Chemical Society (ACS)
• Subjects: inorganic; INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; MATERIALS SCIENCE; nitride; semiconductor; solid; synthesis
• ISSN: 0002-7863; 1520-5126
• DOI: 10.1021/jacs.3c12114

Recent computational studies have predicted many new ternary nitrides, revealing synthetic opportunities in this underexplored phase space. However, synthesizing new ternary nitrides is difficult, in part because intermediate and product phases often have high cohesive energies that inhibit diffusion. Here, we report the synthesis of two new phases, calcium zirconium nitride (CaZrN2) and calcium hafnium nitride (CaHfN2), by solid state metathesis reactions between Ca3N2 and MCl4 (M = Zr, Hf). Although the reaction nominally proceeds to the target phases in a 1:1 ratio of the precursors via Ca3N2 + MCl4 → CaMN2 + 2 CaCl2, reactions prepared this way result in Ca-poor materials (Ca x M 2–x N2, x < 1). A small excess of Ca3N2 (ca. 20 mol %) is needed to yield stoichiometric CaMN2, as confirmed by high-resolution synchrotron powder X-ray diffraction. In situ synchrotron X-ray diffraction studies reveal that nominally stoichiometric reactions produce Zr3+ intermediates early in the reaction pathway, and the excess Ca3N2 is needed to reoxidize Zr3+ intermediates back to the Zr4+ oxidation state of CaZrN2. Analysis of computationally derived chemical potential diagrams rationalizes this synthetic approach and its contrast from the synthesis of MgZrN2. These findings additionally highlight the utility of in situ diffraction studies and computational thermochemistry to provide mechanistic guidance for synthesis.