Термическое разложение двойных комплексных соединений 3d-металлов.

Abstract

The paper is devoted to the study of thermolysis of double complex compounds (DCС) of metalsin the I transition series. 30 DCСwith various combinations of metal-central atoms (Co-Fe, Cu-Fe, Ni-Fe Cr-Fe, Cr-Co,) and ligands (ammonia, urea (ur), ethylenediamine (en), 1,3-diaminopropane (tn), cyanide, oxalate and nitrite anions) were synthesized and characterized. A complete study of the thermal proper-ties of these DCCs in three atmospheres was carried out: oxidizing (air), inert (Ar, N2, partly He) and re-ducing (H2), in the temperature range of 20–1000°Cand at constant heating rate of 10°C/min. The solid and gaseous thermolysis products were studied. In the air solid thermolysis products are represented by mixtures of central ions oxides or mixed oxides of the MIMII2O4type. The main gaseous products of thermolysis underthe temperature below 300°Cinclude NH3, HNCO (for urea DCС) and HCN (for cya-nocomplexes), and above 300°C —СО2. In addition, undecomposed ligands, CO, nitrogen oxides and probably nitrogen are presented in the gas phase. Thermolysis of the studied DCCgoesin the most com-plex way in inert atmospheres. Solid thermolysis products are heterogeneous mixtures of metals (Cu, Fe), solid solutions of CoxFe1-x, Ni3Fe intermetallic compounds, oxides, carbides and nitrides of central ions and amorphous carbon; the content of the latter reaches 58% of the initial content in the complex. The gaseous products of thermolysis include the same compounds, except for CO2, as in the atmosphere of air, but also in different ratios. In an H2atmosphere, all studied DCCs, except Cr-containing ones, are re-duced to the sum of central ions —Cu + Fe or solid solutions Co-Fe and Ni-Fe, practically free of carbon. Gaseous products are the same as in an inert atmosphere, butan increased yield of NH3and a reduced yield of CO2and/or HCN speak in favor of partial hydrogenation of the ligands to hydrocarbons. A review of the catalytic properties of solid products of DCC thermolysis (~170 samples) showed that about 1/3 of themare active in model reactions (catalytic decomposition of hydrogen peroxide, thermal decomposi-tion of ammonium perchlorate).