Synthesis of anti-perovskite-type carbides and nitrides from metal oxides and melamine

Abstract

Four anti-perovskite-type compounds, ZnNNi3, ZnCNi3, SnNCo3, and SnCCo3, are synthesised through reactions between ingredient metal oxides and organic compound melamine (C3H6N6). ZnNNi3 and ZnCNi3 are selectively synthesised by choosing different reaction temperatures and nominal oxide-to-melamine ratios. SnNCo3 is synthesised for the first time by this melamine method. Resistivity, magnetisation, and heat capacity measurements reveal that SnNCo3 is a correlated metal with a high density of states at the Fermi level. Our results demonstrate that this feasible synthetic route using melamine is useful in the search for complex metal carbides and nitrides toward novel functional materials.

Interfacial Electron Delocalization in Engineering Nanosized Anti-Perovskite Nitride for Efficient CO2 Electroreduction

“…With a well-defined crystal structure and highly flexible composition, theoretically, such anti-perovskite materials are suitable for investigation of structure–activity relationship in chemistry; nevertheless, the synthesis of nanosized anti-perovskites or their application in chemistry has been much less reported. Among various anti-perovskites, transition metal nitrides have been explored in solid-state chemistry. ,, For instance, Cu 3 NPd nanocrystals were explored as electrocatalysts for oxygen reduction reaction; CuNCo 3– x V x and the Cu 1– x NNi 3– y /FeNiCu composites demonstrated excellent performance for oxygen evolution reaction. , Methods such as chemical vapor deposition, chemical solution deposition, spark-plasma sintering, and so forth − were developed to prepare these transition metal nitrides using N 2 or NH 3 as the most common nitrogen source. Nevertheless, synthesis of such transition metal nitrides usually requires high temperature; as a result, most of the existing anti-perovskite nitrides occur in the micrometer regime, which limits their application in heterogeneous catalysis.…”

Metal‐Rich Ternary Perovskite Nitrides

“…[131,158a] Recently, cubic Co 3 SnN was synthesized after prediction of its stability via a high-throughput screening by DFT methods. [161,162] Cubic Co 3 InN and Co 3 GeN show spinglass behavior, probably as a result of minor disorder or -more likely -main-group metal vacancies. [153,160,163] For Co-rich perovskite nitrides with iron see the comments in paragraph 4.2.1.…”

“…[90,97,99,101,105,112] Recently, Ni 3 ZnN, Co 3 SnN and their analogous carbides were synthesized from reactions of their corresponding oxide mixtures with gaseous decomposition products of melamine. [161] The nitrides within this technique form at lower temperatures than the carbides. However, no clear evidence for formation of pure nitrides or carbides was presented.…”

“…Apparently, compounds with Zn and Mg form in addition to the cubic ferromagnet Co 3 CdN and its solid solution with Ni 3 CdN ,. [158a] Recently, cubic Co 3 SnN was synthesized after prediction of its stability via a high‐throughput screening by DFT methods , . Cubic Co 3 InN and Co 3 GeN show spin‐glass behavior, probably as a result of minor disorder or – more likely – main‐group metal vacancies , , .…”

“…Alternatives employ mixtures of oxides and metals, mixed‐transition metal oxalates or even sol‐gel‐techniques, for example via the citrate route, for atomic‐level intermixture of metallic components prior to ammonolysis , , , , , . Recently, Ni 3 ZnN, Co 3 SnN and their analogous carbides were synthesized from reactions of their corresponding oxide mixtures with gaseous decomposition products of melamine . The nitrides within this technique form at lower temperatures than the carbides.…”