Flame-made ternary Pd-In2O3-ZrO2 catalyst with enhanced oxygen vacancy generation for CO2 hydrogenation to methanol

Palladium promotion and deposition on monoclinic zirconia are effective strategies to boost the performance of bulk In2O3 in CO2-to-methanol and could unlock superior reactivity if well integrated into a single catalytic system. However, harnessing synergic effects of the individual components is crucial and very challenging as it requires precise control over their assembly. Herein, we present ternary Pd-In2O3-ZrO2 catalysts prepared by flame spray pyrolysis (FSP) with remarkable methanol productivity and improved metal utilization, surpassing their binary counterparts. Unlike established impregnation and co-precipitation methods, FSP produces materials combining low-nuclearity palladium species associated with In2O3 monolayers highly dispersed on the ZrO2 carrier, whose surface partially transforms from a tetragonal into a monoclinic-like structure upon reaction. A pioneering protocol developed to quantify oxygen vacancies using in situ electron paramagnetic resonance spectroscopy reveals their enhanced generation because of this unique catalyst architecture, thereby rationalizing its high and sustained methanol productivity. Assembling multicomponent catalysts to harness synergic effects is challenging. Now, flame spray pyrolysis permits the synthesis of ternary Pd-In2O3-ZrO2 catalysts with an optimal architecture and an enriched density of oxygen vacancies for maximal performance in CO2-based methanol synthesis.

Automated summary

This study presents the synthesis of ternary Pd-In2O3-ZrO2 catalysts with remarkable methanol productivity and improved metal utilization using flame spray pyrolysis (FSP). Unlike traditional methods, the materials prepared by FSP combine low-nuclearity palladium species with highly dispersed In2O3 monolayers on the ZrO2 carrier. A pioneering protocol using in situ electron paramagnetic resonance spectroscopy reveals enhanced generation of oxygen vacancies in this unique catalyst architecture, explaining its high and sustained methanol productivity.