Interweavable Metalloporphyrin‐Based Fibers for Indirect Electrocatalysis

Abstract The applications of indirect electrocatalysis toward potential industrial processes are drastically limited by the utilization or processing forms of electrocatalysts. The remaining challenges of electrocatalysts like the recycling in homogeneous systems or pulverization in heterogeneous systems call for advanced processing forms to meet the desired requirements. Here, we report a series of metalloporphyrin‐based polymer fibers (M−PF, M=Ni, Cu and Zn) through a rigid‐flexible polymerization strategy based on rigid metalloporphyrin and flexible thiourea units that can be applied as heterogeneous redox‐mediators in indirect electrocatalysis. These functional fibers with high strength and flexibility exhibit interweavable and designable functions that can be processed into different fiber‐forms like knotted, two‐spiral, three‐ply, five‐ply fibers or even interweaved networks. Interestingly, they can be readily applied in S−S bond cleaving/cyclization reaction or extended oxidative self‐coupling reaction of thiols with high efficiency. Remarkably, it enables the scale‐up production (1.25 g in a batch‐experiment) under laboratory conditions.