Synergistic catalysis of Pd nanoparticles with both Lewis and Bronsted acid sites encapsulated within a sulfonated metal-organic frameworks toward one-pot tandem reactions.

ABSTRACT

The development of a suitable catalytic system in the single catalyst has always been the pursuit for synthetic chemists in order to perform the traditional stepwise reactions in one-pot mode. In this work, an ultra-stable bifunctional catalyst of Pd@MIL-101-SO3H was successfully constructed and applied in the one-pot oxidation-acetalization reaction whose products have been widely utilized as fuel additives, perfumes, pharmaceuticals and polymer chemistry. The excellent catalytic performance (>99% yields), on the one hand, can be ascribed to the synergistic effects of Pd NPs with both Lewis and Bronsted acid encapsulated within a sulfonated MIL-101(Cr). On the other hand, the exceptionally high capacity of water adsorption in MIL-101(Cr) could promote the equilibrium movement via interrupting the reversible process. More importantly, Pd@MIL-101-SO3H is recyclable and can be reused for at least 8 times without sacrificing its catalytic activities. As far as we know, this is the first time that a water adsorption enhanced equilibrium movement of reversible reaction by porous catalyst to achieve high yields has been realized in Pd@MIL-101-SO3H, which may provide an absolutely new and efficient strategy especially for designing reaction-oriented catalysts.