Synthesis of zincphthalocyanine-based conjugated microporous polymers with rigid-linker as novel and green heterogeneous photocatalysts

Abstract

The novel zincphthalocyanine-based conjugated microporous polymers with rigid-linker (α-ZnPc-CMP and β-ZnPc-CMP) were synthesized by copolymerization of zinc phthalocyanine (ZnPc) and 4, 6-diaminoresorcinol dihydrochloride (DADHC). The α-ZnPc-CMP and β-ZnPc-CMP were utilized as heterogeneous photocatalysts to degrade Rhodamine B (RhB) in aqueous solution. It is the first time for MPc-based CMPs used as heterogeneous photocatalysts for photodegradation of RhB to date. The highly ordered skeletal alignment and two-dimensional open-channel structure of α-ZnPc-CMP and β-ZnPc-CMP not only solve the aggregation of ZnPc and enhance its photocatalytic activity, but also facilitate the recycling and avoid the secondary pollution. The chemical structures and morphologies of α-ZnPc-CMP and β-ZnPc-CMP were well characterized by Fourier transform infrared spectra (FT-IR), solid-state ¹³C nuclear magnetic resonance (¹³C NMR), scanning electron microscopy (SEM), N₂-sorption/ desorption and X-ray diffraction (XRD). The solubility experiments and thermogravimetric analysis (TGA) showed they have good chemical stability and recyclability. Furthermore, the photocatalytic tests indicated α-ZnPc-CMP and β-ZnPc-CMP have excellent photocatalytic performances for degradation of RhB (3 h, degraded 98 and 97.47%) in the presence of H₂O₂ under visible-light irradiation. All results reveal that α-ZnPc-CMP and β-ZnPc-CMP have great potential as photocatalysts on the degradation of organic dye contaminants. Moreover, the possible reaction mechanism of α-ZnPc-CMP and β-ZnPc-CMP as photocatalysts for the degradation of RhB is proposed.

Keywords: Conjugated microporous polymers; Heterogeneous photocatalysts; Metallophthalocyanine; Rhodamine B.