Facile and Fast Microwave-Assisted Synthesis of Metalated PCN-222 for Light-Driven Hydrogen Evolution Reaction.

Porphyrinic metal-organic frameworks (PMOFs) have the capacity to incorporate metalloporphyrins (MPs) into their structure. While this ability opens the door to many potential applications, the synthesis of metal-incorporated PMOFs typically involves multistep protocols, which have so far limited their exploration and scope. Providing a swift and universal synthesis route is an essential part of developing these porous materials for catalytic applications. Herein, Zr-PCN-222 and a broad series of its metalated derivatives (Pd, Zn, Ni, Cu, and Pb) were prepared by adopting a facile and rapid method based on a three-step microwave-assisted procedure. A variety of diffraction and spectroscopic techniques were used to characterize the PMOF compounds and confirm the incorporation of MP moieties into the frameworks, while their photocatalytic performance was systematically assessed in light-driven hydrogen evolution reaction (HER) experiments. We demonstrate that the highest performing Zr-PCN-222-(Pd) analogue exhibits HER activity under both UV- and visible-light illumination with activity levels comparable to those of previously reported benchmarks prepared using more tedious preparation protocols. Our results pave the way toward the exploration of a range of metal-incorporated PMOFs in applications where efficient charge separation and distinct optoelectronic properties are advantageous.