Monolayer porphyrin assembled SPSf/PES membrane reactor for degradation of dyes under visible light irradiation coupling with continuous filtration✰

Abstract Porphyrin-based catalytic oxidation of hydrocarbon bonds is considered to be the most representative biomimetic catalysis. To mimic the biomimetic catalytic oxidation of nature under illumination of visible light, a monolayer of meso-tetrakis (1-methylpyridinium-4-yl) porphyrin immobilized sulfonated polysulfone/ polyethersulfone blend membrane (TMPyP@SPSf/PES) was prepared via a facile electrostatic assembly method. The visible light response region of TMPyP was expanded after it was immobilized on the SPSf/PES membrane surface, which resulted in the increase of the photocatalytic performance, and the Rhodamine B (RhB) degradation was increased from 30.0% to 93.4%. A photocatalytic membrane reactor (PMR) equipped with TMPyP@SPSf/PES membrane was employed for RhB treatment under continuous flow filtration coupling with photocatalysis, and the optimized degradation was up to 98.3%. Moreover, the TMPyP@SPSf/PES membrane can be reused for photocatalytic degradation of RhB after regeneration in TMPyP solution. More importantly, the TMPyP@SPSf/PES membrane can also efficiently degrade other cationic and anionic dyes (such as degradation of methylene blue 99.1%, acid fuchsin 96.8%). Finally, the oxidation mechanism and degradation pathway of RhB were further investigated by electron spin resonance (ESR), ultra-performance liquid chromatography and high-definition mass spectrometry (UPLC HDMS) and gas chromatography-Mass spectrometry (GC–MS). It was revealed that the photogenerated hole (h+), superoxide radical (·O2−), and singlet oxygen (1O2) controlled the oxidation process. The degradation of RhB includes N-de-ethylate, wrecked of chromophore structures and opening-ring of benzene.