Thermal decomposition and spectral characterization of di[carbonatotetraamminecobalt(III)] sulfate trihydrate and the nature of its thermal decomposition products.

Detailed vibrational (IR, Raman, far-IR) and thermal (TGA, TG–MS, DSC) analysis has been performed on di[κ¹O,κ²O-carbonatotetraamminecobalt(III)] sulfate trihydrate, ([Co(NH₃)₄CO₃]₂SO₄·3H₂O (1). Its isothermic heating at 100 °C leads to formation of [Co(NH₃)₄CO₃]₂SO₄ (compound 2). UV and IR studies showed that the distorted octahedral arrangement around cis-O₂CoN₄ core in compound 1 does not change during dehydration, which explains the reversible water loss and ability of compound 2 to rehydrate into compound 1. Compound 2 decomposes at ~ 240 °C in inert atmosphere giving final decomposition products, which are two modifications of nanosized metallic cobalt (hcp-15 nm, fcc-250 nm) and CoO (55 nm). The redox reaction results in N₂ as an ammonia oxidation product. The decomposition intermediate is a cobalt(II) compound, Co₂O_1,14+δ(SO₄)_0.86 (δ = the oxygen surplus due to the presence of 2.8% of Co(III) ion). The same reaction in air atmosphere resulted in Co₂O_1.25+δ(SO₄)_0.75 (δ = the oxygen surplus due to the presence of 5.3% of Co(III) ion (compound 3a). Compound 3a is oxidized in air at 793 °C into Co₃O₄. The compound 3a exhibits catalytic activity in photodegradation in Congo red. The photodegradation process follows pseudo-first-order kinetic (k_app = 1.0 and 7.0. at pH = 3.4 and 5.25, respectively). [ABSTRACT FROM AUTHOR]