Drastic Events and Gradual Change Define the Structure of an Active Copper-Zinc-Alumina Catalyst for Methanol Synthesis

The copper-zinc-alumina (CZA) catalyst is one of the most important catalysts. Nevertheless, understanding of the complex CZA structure is still limited and hampers further optimization. Critical to the production of a highly active and stable catalyst are optimal start-up procedures in hydrogen. Here, by employing operando X-ray absorption spectroscopy and X-ray diffraction, we follow how the industrial CZA precursor evolves into the working catalyst. Two major events in the activation drastically alter the copper- and zinc-containing components in the CZA catalyst and define the final working catalyst structure: the reduction of the starting copper(II) oxide, and the ripening and re-oxidation of zinc oxide upon the switch to catalytic conditions. These drastic events are also accompanied by other gradual, structural changes. Understanding what happens during these events is key to develop tailored start-up protocols that are aimed at maximal longevity and activity of the catalysts.