Catalytic activation of peroxymonosulfate (PMS) to generate radicals has received considerable and increasing attention in environmental catalysis field. The development of highly efficient and environmentally friendly oxidation processes has been one of the most important and greatly challenging goals in PMS activation field. Herein, an effective and stable catalyst (ACFs-CoPc) was proposed for PMS activation by supporting cobalt phthalocyanine (CoPc) onto activated carbon fibers (ACFs) covalently. With the dye of Acid Red 1 (AR1) as probe compound, ACFs-CoPc could effectively activate PMS to eliminate AR1, and the catalytic activity of ACFs-CoPc was almost not impaired during ten successive runs without detectable cobalt leaching, indicating that ACFs-CoPc/PMS system was a pro-environmental and efficient oxidation system. A hybrid method that combines electron paramagnetic resonance (EPR) technology with different radical scavengers effect on PMS activation was employed for the investigation of active species during the catalytic reaction. It was found that both hydroxyl and sulfate radical (OH, SO4−) were generated; importantly, SO4− was speculated to serve as the dominant active species in the catalytic oxidation of AR1. Based on these results, a possible mechanism was proposed.

Novel green activation processes and mechanism of peroxymonosulfate based on supported cobalt phthalocyanine catalyst

The preparation and optical properties of peripherally substituted phthalocyanines and their analogs (i.e. naphthalocyanines, anthracyanines, aza-analogs of phthalocyanines, and tetraazaporphyrins) have been widely discussed. This review highlights methodologies that have been published in poorly known and mostly unavailable Russian journals.

The key role of peripheral substituents in the chemistry of phthalocyanines and their analogs

A set of substituted (sulfonate, amino) nickel porphyrin derivatives such as phthalocyanine and phenylporphyrin was studied by spectroscopic (UV-vis, FTIR, XPS) and quantum-chemical methods. The Q and Soret bands were identified in the UV-vis spectra of aquo solutions of the tetrasulfo-substituted complexes and in DMF and ACN solutions of the amino-substituted phenylporphyrin and phthalocyanine Ni(II) complexes, respectively. In all the complexes the frontier molecular orbitals predict that the oxidation and reduction sites are localized on the ligand rather than in the metal atom. A natural bonding orbital (NBO) analysis of all the complexes showed that a two-center bond NBO between the pyrrolic nitrogens (Npyrr) and the nickel atom does not exist, the Npyrr...Ni interaction occurring instead by a delocalization from one lone pair of each Npyrr toward one lone pair of the nickel atom, as estimated by second-order perturbation theory. The calculated values of electronic transitions between the frontier molecular orbitals are in good agreeement with the UV-vis data. At the theoretical level, we found that while the ligand effect is more important in the Q-band (approximately 16 kcal/mol), the substituent effect is more significant in the Soret band (approximately 9 kcal/mol). A good agreement was also found between the experimental and calculated infrared spectra, which allowed the assignment of many experimental bands. The XPS results indicate that the Ni(II) present in the phenylporphyrin structure is not affected by a change of the substituent (sulfonate or amino).

Theoretical and spectroscopic study of nickel(II) porphyrin derivatives.

The selective elimination of recalcitrant organic pollutants in high backgrounds of complex constituents has proven a significant challenge. Inspired by the naturally occurring oxidation reactions catalyzed by metalloporphyrin-based enzymes, where the target substrates can be oxidized selectively due to the specific enzyme environment and the axial fifth ligands of metalloporphyrins, we developed a bioinspired catalytic system based on cellulosic fiber-boned cobalt phthalocyanine for capturing and oxidizing dyes by H2O2 activation in the presence of high additive concentrations. In this system, the cellulosic fibers provided the amorphous regions, functioning as cavities in the same manner as the protein backbones of enzymes for the selective accessibility of dyes; cobalt phthalocyanine was introduced as the catalytic entity; and linear alkylbenzene sulfonate (one of the most widespread surfactants in industrial and domestic wastewater) was employed as the fifth ligand to help generate high-valent cobalt-oxo intermediates by the heterolytic cleavage of the peroxide O O bond. According to detailed density functional theory calculations, the spin populations are predominantly located around the cobalt-oxo center, achieving an electrophilic attack on the electron-rich azo bond and the aromatic ring of the target model dyes.

Formation of high-valent cobalt-oxo phthalocyanine species in a cellulose matrix for eliminating organic pollutants

Radionuclide with Cerenkov radiation (CR) can serve as an internal excitation source to activate photosensitizers for photodynamic therapy (PDT) in deep tumor. However, the low efficiency of CR limits its therapeutic efficacy. A 131 I labeled zinc tetra(4-carboxyphenoxy) phthalocyaninate (ZnPcC4) conjugated Cr3+ -doped zinc gallate (ZnGa2 O4 :Cr3+ , ZGCs) nanoplatform (131 I-ZGCs-ZnPcC4) is developed for radiotherapy (RT) and radiation-induced PDT. 131 I can not only activate ZGCs for long-lasting luminescence via both Cerenkov luminescence (CL) and ionizing radiation, which further continuously activate photosensitizer ZnPcC4 for PDT, but also can directly kill cancerous cells. This 131 I-ZGCs-ZnPcC4 exhibits excellent tumor inhibition both in vitro and in vivo. Combining self-activated PDT and RT, it is believed that the 131 I-ZGCs-ZnPcC4 can greatly benefit the deep tumor therapy.

Radioiodinated Persistent Luminescence Nanoplatform for Radiation-Induced Photodynamic Therapy and Radiotherapy

Novel aqueous soluble cobalt phthalocyanine: synthesis and catalytic activity on oxidation of 2-mercaptoethanol

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Novel aqueous soluble cobalt phthalocyanine: synthesis and catalytic activity on oxidation of 2-mercaptoethanol