Potential Utilization of Metal-Organic Frameworks in Heterogeneous Catalysis: A Case Study of Hydrogen-Bond Donating and Single-Site Catalysis.

Crystalline solid materials are platforms for the development of effective catalysts and have shown vast benefits at the frontiers between homogeneous and heterogeneous catalysts. Typically, these crystalline solid catalysts outperformed their homogeneous analogs due to their high stability, selectivity, better catalytic activity, reusability and recyclability in catalysis applications. This point of view, comprising significant features of a new class of porous crystalline materials termed as metal-organic frameworks (MOFs) engendered the attractive pathway to synthesize functionalized heterogeneous MOF catalysts. The present review includes the recent research progress in developing both hydrogen-bond donating (HBD) MOF catalysts and MOF-supported single-site catalysts (MSSCs). The first part deals with the novel designs of urea-, thiourea- and squaramide-containing MOF catalysts and study of their crucial role in HBD catalysis. In the second part, we discuss the important classification of MSSCs with existing examples and their use in desired catalytic reactions. In addition, we describe the relative catalytic efficiency of these MSSCs with their homogeneous and similarly reported analogs. The precise knowledge of discussed heterogeneous MOF catalysts in this review may open the door for new research advances in the field of MOF catalysis.