Site Engineering of Covalent Organic Frameworks for Regulating Peroxymonosulfate Activation to Generate Singlet Oxygen with 100 % Selectivity

Abstract Singlet oxygen ( 1 O 2 ) is an excellent reactive oxygen species (ROSs) for the selective conversion of organic matter, especially in advanced oxidation processes (AOPs). However, due to the huge dilemma in synthesizing single‐site type catalysts, the control and regulation of 1 O 2 generation in AOPs is still challenging and the underlying mechanism remains largely obscure. Here, taking advantage of the well‐defined and flexibly tunable sites of covalent organic frameworks (COFs), we report the first achievement in precisely regulating ROSs generation in peroxymonosulfate (PMS)‐based AOPs by site engineering of COFs. Remarkably, COFs with bipyridine units (BPY‐COFs) facilitate PMS activation via a nonradical pathway with 100 % 1 O 2 , whereas biphenyl‐based COFs (BPD‐COFs) with almost identical structures activate PMS to produce radicals (⋅OH and SO 4 .− ). The BPY‐COFs/PMS system delivers boosted performance for selective degradation of target pollutants from water, which is ca. 9.4 times that of its BPD‐COFs counterpart, surpassing most reported PMS‐based AOPs systems. Mechanism analysis indicated that highly electronegative pyridine‐N atoms on BPY‐COFs provide extra sites to adsorb the terminal H atoms of PMS, resulting in simultaneous adsorption of O and H atoms of PMS on one pyridine ring, which facilitates the cleavage of its S−O bond to generate 1 O 2 .