Effect of transition and alkali metals on Mo2C/Al2O3 catalysts for syngas to higher alcohols

Abstract

Direct production of higher alcohols remains a great challenge in syngas conversion process. Herein, MMo2C/Al2O3 and KMMo2C/Al2O3 catalysts promoted by different transition metals M (M=Co, Fe, Cu, Ni, Zn, Nb) and alkali metal (K) were prepared by impregnation method to investigate the effect on CO hydrogenation to higher alcohols under milder reaction conditions (300°C, 3.0 MPa). The catalysts were characterized with XRD, H2-TPR, and XPS. It was found that the addition of transition metals and K resulted in the decrease of low-valent Mo species on the catalyst surface, which facilitated the generation of Mo4+ during the reaction. Increase in Mo4+ content facilitates the conversion of CO to CO*, which provides more CO insertion sites for the generation of alcohols. Moreover, the introduction of K also enhances the interaction of transition metals with Mo, which accelerates the formation of alcohols in the reaction. Meanwhile, the transition metal and Mo2C work together to promote the dissociative adsorption of CO. The production of higher alcohols is facilitated by the synergistic effect of the two mentioned above. Overall, the KCoMo/Al2O3 and KFeMo/Al2O3 catalysts exhibited high selectivity for higher alcohols, reaching 73.9 % and 71.3 % for C2+OH in the alcohol products, respectively. CO conversion of KFeMo/Al2O3 catalyst can reach 84.9 % with excellent stability in the reaction. Moreover, the possible pathways of the reaction were obtained by in-situ DRIFT characterization.