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Iron (II) phthalocyanine (FePc) is loaded on the surface of the tourmaline (TM) by the reflow method to obtain FePc/TM. This research effectively prevents the π-π stacking of FePc, increased the effective utilization rate of PMS activation under solar light, and further improved the catalytic performance of the catalytic system. The catalytic oxidation efficiency of FePc/TM on carbamazepine (CBZ) and sulfadiazine (SD) can reach 99% under solar light for 15 and 5 min, the total organic carbon (TOC) removal rate can reach 58% and 69% under solar light for 120 min. After 6 cycles, the CBZ removal rate remained above 95%. In addition, the FePc/TM catalytic system has an excellent removal rate for other pharmaceuticals. The results of spin-trapped electron paramagnetic resonance and classical quenching experiments show that FePc/TM can effectively activate PMS to generate active species under solar light, including superoxide radical (•O2−), singlet oxygen (1O2), hydroxyl radicals(•OH), and sulphate radicals (SO4•−). The intermediates of CBZ were identified by Ultra-high performance liquid chromatography and high resolution mass spectrometry, and the degradation pathway was proposed. As the reaction progresses, all CBZ and intermediates are reduced and converted into small acids, or mineralized to H2O, CO2. This work provides an alternative method for the design of efficient activation of PMS activation catalysts under solar light to eliminate residual pharmaceuticals in actual water bodies.

Carboxylic acid-functionalized CNF was used to attach cobalt tetraaminophthalocyanine (CoTAPc) by amide bonds for obtaining carbon nanofiber-supported cobalt phthalocyanine (CoTAPc-CNF). This catalyst was characterized by atomic absorption spectrometry, UV-vis spectroscopy, ATR-FTIR spectroscopy. The catalytic performance of CoTAPc-CNF was investigated by the oxidative degradation of Rhodamine 6G (Rh6G) with xanthine structure, and the effects of various conditions including temperature, pH, the addition of NaCl and isopropanol were discussed. The results indicated that CoTAPc-CNF has a higher catalytic activity for the oxidation of dye at room temperature in neutral aqueous solution. The catalytic activity was raised with the increasing of temperature and pH. Moreover, the efficiency of Rh6G oxidation was improved while NaCl or isopropanol was presented in this reaction system. This phenomenon was different from some common AOPs, in which chloride ion and isopropanol might serve as scavenger for hydroxyl radicals to inhibit the oxidation of dyes. EPR spin trapping technique indeed showed that the hydroxyl radical is not the major intermediate in the presence of CoTAPc-CNF. In addition, two different types of dyes including azo Acid Orange 7 (AO7) and triphenylmethane Basic Green 1 (BG1) could be also effectively degraded. This study provides a new idea for exploring the catalytic system with non-hydroxyl radical mechanism for the treatment of real wastewaters.

A zinc tetraaminophthalocyanine derivative, zinc tetra(methacryloyl moiety)aminophthalocyanine (MeZnAPc) (with a double bond) was synthesized by the reaction between zinc tetraaminophthalocyanine (ZnTAPc) and methacryloyl chloride. Atom transfer radical polymerization (ATRP) was employed as the polymerization technique to obtain a novel pH-responsive polymeric photosensitizer (PEG110-b-P(DPA n -co-MeZnAPc m )) by copolymerizing of methoxypolyethylene glycols (MPEG) (as reducing agent), 2-(isopropylamino)ethyl methacrylate (DPA) and MeZnAPc. This photosensitizer was characterized by UV-vis spectroscopy, FTIR, 1H NMR, etc. The results indicated that the photosensitizer presented the well pH-responsive behavior around the pH range 6.0–6.5 and the high photoactivity to 1,3-diphenylisobenzofuran (DPBF). The result of photocatalysis oxidation of l-tryptophan (l-Try) suggested that zinc phthalocyanine could present high photoactivity due to its dispersivity at pH 5.5 without formation of micelles, and its photoactivity decreased dramatically at pH 7.4 due to wrapping ZnTAPc into the micelles. Therefore, the novel pH-responsive polymeric photosensitizer has better application prospects in the field of photodynamic therapy.