A green route to prepare metal-free phthalocyanine crystals with controllable structures by a simple solvothermal method.

Exploring the environmentally friendly and low-cost synthesis strategies of phthalocyanine (Pc) crystals in just one step is an absolute challenge. The solvothermal synthesis of phthalocyanine crystals shows the advantages of high-quality crystalline products, facile reaction and purification, and low cost. Nevertheless, only a few metal phthalocyanine crystals have been successfully synthesized via solvothermal reactions. In this study, we found that the crystalline ß metal-free phthalocyanine needles could be directly prepared via the tetrapolymerization of phthalodinitrile catalyzed by DBU in solvothermal reactions. Similar to the preparation of ß-phthalocyanine crystals, the α metal-free phthalocyanine crystals with the specific multiply-laminated structures can be obtained through solvothermal reactions assisted by DBN. SEM characterization showed that the individual ß metal-free phthalocyanine has a well-defined quadrangular shape with smooth faces. However, the α metal-free phthalocyanine exhibits a distinctive undulating surface morphology. Both phthalocyanines showed satisfactory thermal stability (from room temperature to about 300 °C), excellent resistance to acid/alkali solution, and fast photoelectric response properties (order of magnitude of response time, 10-6 s) as tested by TG-DSC and TPV, respectively. It is noted that ethanol was used as the reaction medium and the resulting phthalocyanine crystals can be facilely purified using hot ethanol to dissolve the impurities adsorbed on the surfaces of phthalocyanine crystals. Compared to the traditional methods, no re-crystallization operation was carried out for our method. To the best of our knowledge, this is the first report on the solvothermal synthesis of metal-free phthalocyanine crystals with controllable crystal form adjusted by DBU/DBN in one step.

A simple and facile bioinspired catalytic strategy to decolorize dye wastewater by using metal octacarboxyphthalocyanine particles.

To explore the simple, facile, environmental friendly and low cost catalytic technique to decolorize harmful dye contaminants in solution and understand the mechanism is an interesting and practical research. In this paper, we provide a highly efficient and convenient method for fast decolorization of dyes (methylene blue and rhodamine B) in aqueous solution catalyzed by iron octacarboxyphthalocyanine (FeOCPc) or cobalt octacarboxyphthalocyanine (CoOCPc). Compared to the traditional methods, our method is very simple. The 30 mg/L methylene blue could be decolorized almost absolutely less than 30 min just by dispersing FeOCPc powders into the dye solution. The decolorization of rhodamine B at high concentration (30 mg/L) could be achieved to 100% decolorization degree less than 20 min in the presence of FeOCPc and tert-butyl hydroperoxide (BuOOH). Moreover, the ESR and HPLC-MS measurement were performed to determine the active radicals and various intermediates in decolorization processes and the possible catalytic mechanism was proposed. It is noted that both FeOCPc and CoOCPc catalysts show the different catalytic oxidation behaviors depending on the oxidant (O2 or BuOOH). Our investigation provides a novel, low cost and convenient strategy to purify the environmental pollutions.