Modulator engineering of bifunctional metal-organic framework for synergistic catalysis

Abstract

Pursuing both structural uniformity/crystallinity and functional complexity is a long-term goal in functional materials engineering. Often, efforts to enhance one attribute may compromise the other. Herein, we report an elaborate strategy of integrating a catalytic center into a modulator, which enables the one-pot synthesis of a bifunctional metal-organic framework (MOF), Zr-TBAPy-TSA (TBAPy = 1,3,6,8-tetrakis(p-benzoic acid)pyrene; TSA = o-thiosalicylic acid). TSA serves as both a modulator for metal-organic framework (MOF) preparation and a catalytic center. Zr-TBAPy-TSA is distinguished by its highly uniform and crystalline structure, as evidenced by detailed characterizations including single-crystal X-ray diffraction. Additionally, Zr-TBAPy-TSA incorporating both photosensitizer and thiol active centers showcases superior catalytic performance in the activation of element–H bonds (elements include C, B, Si, and P). Due to its less defective structure, extra high turnover numbers of up to 14,200 and good catalyst recyclability are obtained.