Identification of active Zr-WO(x) clusters on a ZrO2 support for solid acid catalysts

Tungstated zirconia is a robust solid acid catalyst for light alkane (C(4)-C(8)) 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 WO(x) species. High-angle annular dark-field imaging of WO(3)/ZrO(2) 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 WO(x) 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-WO(x) 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.