Enhancing CO2 Conversion to CO over Plasma-Deposited Composites Based on Mixed Co and Fe Oxides

Abstract

The hydrogenation of CO2 to produce CO and H2O, known as reverse-water-gas shift reaction (RWGS) is considered to be an important CO2 valorization pathway. This work is aimed at proposing the thin-film catalysts based on iron and cobalt oxides for this purpose. A series of Fe–Co nanocomposites were prepared by the plasma-enhanced chemical vapor deposition (PECVD) from organic cobalt and iron precursors on a wire-mesh support. The catalysts were characterized by SEM/EDX, XPS, XRD, and Raman spectroscopy and studied for hydrogenation of CO2 in a tubular reactor operating in the temperature range of 250–400 °C and atmospheric pressure. The Co-based catalyst, containing crystalline CoO phase, exhibited high activity toward CH4, while the Fe-based catalyst, containing crystalline Fe2O3/Fe3O4 phases, was less active and converted CO2 mainly into CO. Regarding the Fe–Co nanocomposites (incl. Fe2O3/Fe3O4 and CoO), even a small fraction of iron dramatically inhibited the production of methane. With increasing the atomic fraction of iron in the Fe–Co systems, the efficiency of the RWGS reaction at 400 °C increased up to 95% selectivity to CO and 30% conversion of CO2, which significantly exceeded the conversion for pure iron–based films (approx. 9%). The superior performance of the Fe–Co nanocomposites compared to “pure” Co and Fe–based films was proposed to be explained by assuming changes in the electronic structure of the catalyst resulting from the formation of p–n junctions between nanoparticles of cobalt and iron oxides.