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The influence of the crystallographic phase of ZrO2 on its catalytic performance in the MPV reduction of cyclohexanone with propan-2-ol has been systematically investigated by combining accurate synthesis procedures, XRD and HRTEM characterization, kinetic measurements and DFT calculations, and compared to that of Zr-beta zeolite. The higher intrinsic activity of monoclinic zirconia as compared to other ZrO2 phases is not due to a lower activation energy for the rate-determining step, but to an adequate distribution of reactant fragments on the catalyst surface, indicating a structure–activity relationship for this reaction when catalyzed by ZrO2 and also by Zr-beta zeolite. Inexpensive and stable ZrO2 catalysts for the MPV reaction have been obtained by controlling the crystallographic phase of the synthesized material.

Structure–reactivity relationship in isolated Zr sites present in Zr-zeolite and ZrO2 for the Meerwein–Ponndorf–Verley reaction

Structure–reactivity relationship in isolated Zr sites present in Zr-zeolite and ZrO₂ for the Meerwein–Ponndorf–Verley reaction