Highly selective CO formation via CO2 hydrogenation over novel ceria-based high-entropy oxides (HEOs)

• Ce 0.5 Ni 0.1 Co 0.1 Cu 0.1 Zn 0.1 Mg 0.1 O x prepared by a citrate-based sol–gel method. • Calcination and reduction temperatures remarkably affect activity and selectivity. • Treatments at or below 500 °C led to active but poorly selective catalysts. • Treatments at 750 °C lead to almost 100 % CO selectivity between 300 °C and 700 °C. • Entropy-stabilized (NiCoCuZnMg)O x species exsolve after high-temperature treatments. In the present study, new ceria-based high-entropy oxides (HEOs) were investigated as CO 2 hydrogenation catalysts. The nominal composition was (Ce 0.5 Ni 0.1 Co 0.1 Cu 0.1 Zn 0.1 Mg 0.1 )O x and the synthesis was accomplished through the citrate complexing sol–gel method. Characterization techniques utilized including ICP-AES, in situ XRD and in situ XPS, SEM-EDS, HR-TEM and HAADF-STEM, Raman spectroscopy, H 2 -TPR, CO 2 -TPD and N 2 physical adsorption. The physicochemical characterization and the catalytic results revealed that the conditions of the thermal treatments at which the oxides were subjected critically determined the catalytic performance, especially the CO 2 hydrogenation products selectivities. Calcination in air and/or reduction in hydrogen conducted at temperatures below 500 °C led to active but poorly selective catalysts that produced both methane and CO with significant yields. This was mainly attributed to the presence of metallic Cu, Ni and Co on the catalysts that appeared to be supported on ceria doped with the rest of the formulation elements. In contrast, thermal treatments at 750 °C favored the formation of a rocksalt entropy-stabilized (NiCoCuZnMg)O x HEO supported on ceria that has stood out for showing an excellent selectivity towards the reverse water–gas shift (RWGS) reaction. This catalyst led to CO selectivities of almost 100 % over a very wide range of reaction temperatures (300–700 °C). Long-term stability tests (100 h) showed only a slight decrease in CO 2 conversion, while CO selectivity remained stable at nearly 100 % at 400 °C. XRD characterization of the used catalysts evidenced that, whereas the basic catalyst structure remained, some metallic copper exsolved during reduction and reaction period. These results are relevant and very promising, opening a door to the development of new catalysts for the valorization of CO 2 through the RWGS reaction, thus expanding the low-temperature limit at which this process can be carried out selectively.