Direct sulfation of a Zr-based metal-organic framework to attain strong acid catalysts

[EN] The application of Metal-Organic Frameworks (MOFs) in gas phase heterogeneous catalysis is still not widely spread because of their limited stability under reaction conditions. Obtaining stable acidic MOFs to be used in reactions that demand strong acid sites remains a challenge up to the present time. In this work, it is shown that nanocrystals of Zirconium MOF UiO-66 can be conveniently and easily functionalized through a simple one-pot synthetic approach, i.e. the direct treatment of UiO-66 with ammonium sulfate followed by an adequate thermal treatment, giving rise to a highly acidic and thermally stable material (named as S-UiO-66). This material can act as catalyst in the gas phase isobutene dimerization demonstrating high catalytic activity at moderate temperatures while maintaining the structural integrity of the MOF after several catalytic evaluations and/or after reuse cycles. The S-UiO-66 material represents a novel alternative in the search of robust MOF-based catalysts to be applied in gas phase heterogeneous catalytic reactions that demand strong acid sites.We acknowledge the financial support from the Spanish Government (projects CTQ2017-89443-C3-1-R and CTQ2017-89443-C3-3-R). Juan M. Zamaro thanks CONICET of Argentina for the support given to carry out a research stay at ICP-CSIC, Spain