Low-nuclearity CuZn ensembles on ZnZrOx catalyze methanol synthesis from CO2
Creators
- 1. ETH Zurich
- 2. ICIQ
- 3. IUMA
Description
Metal promotion could unlock high performance in zinc-zirconium catalysts, ZnZrOx, for CO2 hydrogenation to methanol. Still, the optimal choice of metal and the atomic-level architecture required to enhance the performance remain poorly understood. Herein, we investigate the promotion of ZnZrOx catalysts by a myriad of hydrogenation metals (Re, Co, Au, Ni, Rh, Ag, Ir, Ru, Pt, Pd, and Cu) via a standardized flame spray pyrolysis synthesis approach. Cu is unveiled as the most promising promoter, leading to ca. 2-fold improved methanol productivity. Operando characterization and theoretical simulations reveal that Cu0 species form Zn-rich low-nuclearity clusters (CuZnx) on the ZrO2 surface upon reaction, which is key to improving performance. Operando electron paramagnetic resonance spectroscopy results indicate that the formation of CuZnx species is associated with the generation of oxygen vacancies in their vicinity. The resulting catalytic ensemble promotes the rapid hydrogenation of the formate intermediate into methanol while effectively suppressing CO production, as confirmed by operando infrared spectroscopy. The findings highlight the potential of in situ formed low-nuclearity metal ensembles in unlocking unique reactivity in CO2-based methanol synthesis.
Files
Files
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