Red Light-Active Porphyrin-based Zr-MOF Nanorods Enable Highly Selective Aerobic Oxidation of Sulfides and Amines

Abstract

The strategic utilization of red-light-responsive photocatalysts presents a unique opportunity to perform organic reactions under mild conditions, thereby minimizing side reactions and broadening the scope of viable substrates. Herein, red light active porphyrin-based Zr-MOFs nanorods (NU-902-NR) were synthesized by a microwave method. The as-prepared NU-902-NR exhibits high surface areas, hybrid micro/mesopore structure, excellent stability and dispersity in water, and a wide adsorption band in the visible light region, especially in red light range, making them excellent candidates for photocatalysis.NU-902-NR demonstrates excellent catalytic activities toward the selective aerobic oxidation of sulfides and amines under red light irradiation at room temperature. Detailed mechanism studies revealed that the NU-902-NR is capable of activating O 2 to generate 1 O 2 and O 2 •-under red light irradiation, thus oxidizing sulfides and benzylamines to sulfoxides and imines, respectively. Importantly, a higher selectivity of imine product was achieved when the reaction was performed under red light irradiation rather than under blue light irradiation, indicating the advantages of low-energy red light in minimizing side reactions. The simplicity and rapid synthetic approach together with the versatile photochromic moieties hold great promise for synthesizing water-stable and red-light responsive porphyrinic Zr-MOF nanomaterials. This work also offers new potentials for the selective aerobic photooxidation of sulfides and amines under green and mild way.