A novel and efficient visible-light-induced Ti-doped BiOBr photocatalyst was successfully obtained by double self-assemble method. The resultant samples were characterized by XRD, FE-SEM, HR-TEM, EDS, and UV–vis adsorption spectra. The possible formation process of the as-prepared samples and titanium doping in the lattice of BiOBr were investigated in this paper. The Ti-doped BiOBr microspheres exhibited higher visible-light-induced photocatalytic activity for the degradation of rhodamine B (RhB) than BiOBr due to the synergetic effect of the unique structure and the titanium doping as well as larger specific surface area, which effectively improved photogenerated electrons and holes transferring.The novel and efficient visible-light-induced Ti-doped BiOBr microspheres were successfully obtained by double self-assemble method. And the Ti0.22BiO1.48Br photocatalyst exhibited higher visible-light-induced photocatalytic activity for the degradation of rhodamine B (RhB) than BiOBr due to the synergetic effect of the unique structure and the titanium doping as well as larger specific surface area.Highlights► A novel Ti-doped BiOBr photocatalyst was obtained by double self-assemble method. ► The possible formation process of the Ti0.22BiO1.48Br samples was investigated. ► The Ti0.22BiO1.48Br samples exhibited higher photocatalytic activity than BiOBr.

A one-step solvothermal method was used to prepare TiO2/halloysite composites. TiO2 nanoparticles were deposited on the platform of the halloysite nanotubes (HNTs). XRD, FT-IR, FE-SEM, and TEM were applied to investigate the structures and morphologies of the resultant samples. The as-prepared TiO2/HNTs photocatalyst exhibits pH sensibility on the degradation of methanol and a higher photocatalytic activity on the degradation of acetic acid. The combination of the photocatalytic property of TiO2 and the unique structure of halloysite endowed this material with a bright perspective in degradation of organic pollutant.Keywords: halloysite nanotubes; photocatalyst; solvothermal method; TiO2;

A nanomaterial-based metallophthalocyanine catalyst (CoTAPc-MWCNTs) was prepared by covalently immobilizing cobalt tetraaminophthalocyanine (CoTAPc) on multiwalled carbon nanotubes (MWCNTs). The decomposition reaction of H2O2 was chosen to investigate the coupled catalytic performance. The results of electron paramagnetic resonance and online electrochemical experiments indicated that the catalytic mechanism of CoTAPc-MWCNTs is different from that of cobalt phthalocyanine molecular catalysts. The catalytic pathway of CoTAPc-MWCNTs involves the following steps: first, electron transfer from CoTAPc to H2O2 occurs through the coordination between the central cobalt ion and H2O2, reducing H2O2 to H2O; second, electrons are transferred from MWCNTs to the oxidized CoTAPc, forming hole-doped MWCNTs; finally, hole-doped MWCNTs accept electrons from H2O2, oxidizing H2O2 to O2. When using N,N-diethyl-1,4-phenylenediamine as a chromogenic substance, one obtained a quantitative estimate of holes injected in MWCNTs, corresponding to 1 hole for about 55 carbon atoms. Furthermore, CoTAPc-MWCNTs exhibit very unusual characteristics of controlled catalysis due to the special hydrophobic surface of the MWCNTs, and can be used as an interfacial catalyst for the determination of H2O2 concentration.

Multiwalled carbon nanotubes (MWCNTs) used to support a metallophthalocyanine catalyst (CoTAPc–MWCNTs) were prepared using covalent immobilization of cobalt tetraaminophthalocyanine (CoTAPc) on them, and characterized by X-ray photoelectron spectroscopy, attenuated total reflection Fourier transform infrared spectra and thermogravimetric analysis. The oxidative decoloration of rhodamine 6G (Rh6G) in the presence of CoTAPc–MWCNTs and H2O2 was investigated by examination of UV–Vis absorption spectra. The results showed that Rh6G was oxidized efficiently in the CoTAPc–MWCNTs/H2O2 system. The introduction of MWCNTs resulted in a marked enhanced catalytic activity that CoTAPc does not have. Electron paramagnetic resonance spin-trap experiments indicated that CoTAPc–MWCNTs have a novel non-radical pathway, which is different from common CoTAPc catalytic systems. Furthermore, the result of online electrochemical measurement in the CoTAPc–MWCNTs/H2O2 system suggested that MWCNTs might participate directly in the electron transfer process in the catalytic oxidation of this conjugated dye. In this catalytic system, MWCNTs provide strong adsorption to conjugated Rh6G due to their special sp2-hybridized surface, and are able to rapidly oxidize the conjugated dye by a special electron transfer pathway.

A novel water-soluble and polymerizable photosensitizer, zinc tetra(N-carbonylacrylic)aminophthalocyanine (Zn-MPc), was synthesized by the ornament of zinc tetraaminophthalocyanine (Zn-APc) with maleic anhydride and characterized by 1H NMR, FT-IR, and MALDI-TOF mass spectra. The photoactivity of Zn-MPc was determined by tracking the degradation of 1,3-diphenylisobenzofuran (DPBF). The results indicated that Zn-MPc is an efficient photosensitizer and has a high photostability. The apparent rate constant, ka, of DPBF photodegradation increased with the increase of the Zn-MPc concentration or light intensity, but declined with the increase of the initial concentration of DPBF. Furthermore, the kinetics equation was deduced as Rd = 1.12 × 10−5[DPBF]0.51[Zn-MPc]0.54E1.35. The results in this work provide a basis for the further development of more desirable phtotosensitizers and their applications in photodynamic therapy (PDT) of cancer.Modification of zinc tetraaminophthalocyanine with maleic anhydride afforded a water-soluble, polymerizable zinc tetra(N-carbonylacrylic)aminophthalocyanine. It is an efficient photosensitizer in terms of the rate of DPBF degradation and the photostability. The kinetics equation of the initial degradation rate of DPBF is Rd = 1.12 × 10−5[DPBF]0.51[Zn-MPc]0.54E1.35, which can provide a novel thought for the application of photosensitizers in PDT and the design of other efficient photosensitizers.

A novel reactive metallophthalocyanine derivative, zinc tetra(2,4-dichloro-1,3,5-triazine)aminophthalocyanine (Zn-TDTAPc), was prepared and immobilized on poly(N-isopropylacrylamide) (PNIPAAm) by covalent bonding to obtain a thermosensitive polymer (Zn-TDTAPc-g-PNIPAAm). Compared with zinc tetraaminophthalocyanine (Zn-TAPc), Zn-TDTAPc-g-PNIPAAm exhibits excellent solubility in water and in most organic solvents. Furthermore, it has a special thermosensitive property in water and the lower critical solution temperature (LCST) is 34.1°C. It was found that both dissolved and precipitated Zn-TDTAPc-g-PNIPAAm present high photoactivity evidenced by the experiment of photocatalytic degradation of 1, 3-diphenylisobenzofuran (DPBF) in the presence of Zn-TDTAPc-g-PNIPAAm. These properties suggest that it can be used potentially in photodynamic therapy (PDT).

Two kinds of water-soluble metallophthalocyanines, binuclear phthalocyaninecobalt(II) (Co2Pc2) and binuclear phthalocyanineiron(III) (Fe2Pc2), have been investigated as catalysts for the oxidation of 2-mercaptoethanol (MEA). In aqueous solution, Co2Pc2 exhibited higher catalytic activity than Fe2Pc2 at pH 11 and 25 °C. Furthermore, synergistic effect had been found when two catalysts were mixed at molar ratio of 1:1, which was deeply discussed. To make best use of such perfect catalytic oxidation performance, a new supporting method was introduced to prepare the novel air-purifying material, binuclear metallophthalocyanine fibres (Mt2Pc2F). Mt2Pc2F could be used to eliminate efficiently the malodors of methanthiol and hydrogen sulfide by catalytic oxidation reaction.

In this paper, zinc tetraaminophthalocyanine (Zn-APc) was immobilized on cellulosic fiber by covalent bond to obtain a novel cellulosic fiber supported metallophthalocyanine, named Zn-TDTAPc-F. At pH 11, upon visible light irradiation for 6 h in the presence of O2, Zn-TDTAPc-F was found to be highly effective for the degradation of phenol in aqueous solution, and the degradation rate of phenol was more than 95%. HPLC was used to confirm formic acid, fumaric acid and maleic acid as its main degradation products.