Deciphering Local Structural Complexity in Zn/Ga-ZrO CO Hydrogenation Catalysts.

In the last few decades, massive effort has been expended in heterogeneous catalysis to develop new materials presenting high conversion, selectivity, and stability even under high-temperature and high-pressure conditions. In this context, CO hydrogenation is an interesting reaction where the catalyst local structure is strongly related to the development of an active and stable material under hydrothermal conditions at / > 300 °C/30 bar. In order to clarify the relationship between catalyst local ordering and its activity/stability, we herein report a combined laboratory and synchrotron investigation of aliovalent element (Ce/Zn/Ga)-containing ZrO matrixes. The results reveal the influence of similar average structures with different short-range orderings on the catalyst properties. Moreover, a further step toward the comprehension of the oxygen vacancy formation mechanism in Ce- and Ga-ZrO catalysts is reported. Finally, the reported results illustrate a robust method to guide local structure determination and ultimately help to avoid overuse of the "solid solution" definition.