Identification of active Zr–WOx clusters on a ZrO2 support for solid acid catalysts

Tungstated zirconia is a robust solid acid catalyst for light alkane (C4–C8) isomerization. Several structural models for catalytically active sites have been proposed, but the topic remains controversial, partly because of the absence of direct structural imaging information on the various supported WOx species. High-angle annular dark-field imaging of WO3/ZrO2 catalysts in an aberration-corrected analytical electron microscope allows, for the first time, direct imaging of the various species present. Comparison of the relative distribution of these WOx species in materials showing low and high catalytic activities has allowed the deduction of the likely identity of the catalytic active site—namely, subnanometre Zr–WOx clusters. This information has subsequently been used in the design of new catalysts, in which the activity of a poor catalyst has been increased by two orders of magnitude using a synthesis procedure that deliberately increases the number density of catalytically relevant active species. Small alkanes are typically isomerized on tungstated-alumina solid-acid catalysts, but the origin of the activity has been unclear. Now, high-resolution imaging has revealed subnanometre Zr-WOx clusters to be the active sites.