Low-nuclearity CuZn ensembles on ZnZrOx catalyze methanol synthesis from CO2.

Metal promotion could unlock high performance in zinc-zirconium catalysts, ZnZrOx, for CO2 hydrogenation to methanol. Still, with most efforts devoted to costly palladium, the optimal metal choice and necessary atomic-level architecture remain unclear. Herein, we investigate the promotion of ZnZrOx catalysts with small amounts (0.5 mol%) of diverse hydrogenation metals (Re, Co, Au, Ni, Rh, Ag, Ir, Ru, Pt, Pd, and Cu) prepared via a standardized flame spray pyrolysis approach. Cu emerges as the most effective promoter, doubling methanol productivity. Operando X-ray absorption, infrared, and electron paramagnetic resonance spectroscopic analyses and density functional theory simulations reveal that Cu0 species form Zn-rich low-nuclearity CuZn clusters on the ZrO2 surface during reaction, which correlates with the generation of oxygen vacancies in their vicinity. Mechanistic studies demonstrate that this catalytic ensemble promotes the rapid hydrogenation of intermediate formate into methanol while effectively suppressing CO production, showcasing the potential of low-nuclearity metal ensembles in CO2-based methanol synthesis.

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.