Zn Redistribution and Volatility in ZnZrO x Catalysts for CO 2 Hydrogenation.

ZnO-ZrO ₂ mixed oxide (ZnZrO _x ) catalysts are widely studied as selective catalysts for CO ₂ hydrogenation into methanol at high-temperature conditions (300-350 °C) that are preferred for the subsequent in situ zeolite-catalyzed conversion of methanol into hydrocarbons in a tandem process. Zn, a key ingredient of these mixed oxide catalysts, is known to volatilize from ZnO under high-temperature conditions, but little is known about Zn mobility and volatility in mixed oxides. Here, an array of ex situ and in situ characterization techniques (scanning electron microscopy/energy dispersive X-ray spectroscopy (SEM/EDX), transmission electron microscopy (TEM), powder X-ray diffraction (PXRD), X-ray absorption spectroscopy (XAS), X-ray photoelectron spectroscopy (XPS), Infrared (IR)) was used to reveal that Zn ²⁺ species are mobile between the solid solution phase with ZrO ₂ and segregated and/or embedded ZnO clusters. Upon reductive heat treatments, partially reversible ZnO cluster growth was observed above 250 °C and eventual Zn evaporation above 550 °C. Extensive Zn evaporation leads to catalyst deactivation and methanol selectivity decline in CO ₂ hydrogenation. These findings extend the fundamental knowledge of Zn-containing mixed oxide catalysts and are highly relevant for the CO ₂ -to-hydrocarbon process optimization.
Competing Interests: The authors declare no competing financial interest.
(© 2023 The Authors. Published by American Chemical Society.)