In situ self-cleaning removal of emerging organic contaminants with covalent organic framework armed with arylbiguanide

Abstract

An in situ self-cleaning covalent organic framework featuring arylbiguanide arms (Aryl-BIG-COF) was first developed to remove emerging organic pollutants such as propranolol (PRO) from water. The main breakthroughs addressed the scarcity of functional active sites, the impracticality of ex situ regeneration, and the rapid recombination of electronhole pairs in the application of COFs. Owing to the directional capture ability and electronic structure regulation of the arylbiguanide arms, the adsorption capacity and photocatalytic degradation rate of the newly synthesized COF increased by nearly four and seven times, respectively. Its self-cleaning ability, driven by the photocatalytic regeneration of active sites, enabled in situ removal of PRO and sustained over 90% removal efficiency after six cycles. Moreover, it demonstrated broad applicability for removing PRO and other emerging pollutants, such as bisphenol A (BPA), tetracycline (TC), and norfloxacin (NOR), across various water matrices with less residual toxicity. The coexisting organic matter and ions in natural water promoted the removal of PRO. The enhancement mechanism involved arylbiguanide arms narrowing the band gap and inducing local charge polarization, thereby increasing the separation efficiency of electronhole pairs. This work provides significant insights into the structural design and practical applications of COFs for purifying water.