Catalytic behavior of metal-organic frameworks and zeolites: Rationalization and comparative analysis

• The catalytic performance of MOFs and zeolites was compared in a set of reactions.
• Factors determining activity of selected catalysts have been discussed.
• Specific interactions of reactants with MOF active sites are decisive for activity.

The catalytic performance of selected MOFs (Cu3(BTC)2 and MIL-100(Fe)) and zeolites (BEA and USY) have been investigated in a set of acid-catalyzed reactions (Pechmann and Knoevenagel condensations, Friedel–Crafts acylation, Beckmann rearrangement, and Prins and annulation reactions). Characteristics determining the activity and selectivity of the catalysts (particularly their relation to the type and concentration of acid sites, the size of the channels, and structure of the active centers) were discussed in detail. The regular arrangement of active sites in MOFs was shown to provide their superior behavior in Pechmann and Knoevenagel condensation reaction, while higher porosity and concentration of mild Lewis acid centers allows the conversion of bulky substrates to desired products over MOFs in Beckmann rearrangement, Friedel–Crafts acylation, and annulation reactions. Advantages and drawbacks of MOFs as catalysts were fairly compared with zeolites based on results obtained under the same reaction conditions for all investigated materials.

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