Xing Yuan

Fabrication of Z-scheme plasmonic photocatalyst Ag@AgBr/g-C3N4 with enhanced visible-light photocatalytic activity

A series of Ag@AgBr grafted graphitic carbon nitride (Ag@AgBr/g-C3N4) plasmonic photocatalysts are fabricated through photoreducing AgBr/g-C3N4 hybrids prepared by deposition-precipitation method. The phase and chemical structures, electronic and optical properties as well as morphologies of Ag@AgBr/g-C3N4 heterostructures are well-characterized. Subsequently, the photocatalytic activity of Ag@AgBr/g-C3N4 is evaluated by the degradation of methyl orange (MO) and rhodamin B (RB) under visible-light irradiation. The enhanced photocatalytic activity of Ag@AgBr/g-C3N4 compared with g-C3N4 and Ag@AgBr is obtained and explained in terms of the efficient visible-light utilization efficiency as well as the construction of Z-scheme, which keeps photogenerated electrons and holes with high reduction and oxidation capability, evidenced by photoelectrochemical tests and free radical and hole scavenging experiments. Based on the intermediates identified in the reaction system, the photocatalytic degradation pathway of MO is put forward.

H3PW12O40/TiO2 catalyst-induced photodegradation of bisphenol A (BPA): Kinetics, toxicity and degradation pathways

A series of experiments were conducted to investigate the kinetics of bisphenol A (2,2-bis(4-hydroxyphenyl)propane, BPA) degradation using H₃PW₁₂O₄₀/TiO₂ (PW₁₂/TiO₂) composite catalyst, toxicity of BPA intermediate products and degradation pathways. The results showed that the BPA photodegradation using PW₁₂/TiO₂ catalyst followed the first-order kinetics, and under the optimal experimental conditions at H₃PW₁₂O₄₀ loading amount of 6.3%, BPA initial concentration of 5 mg L(-1), and the solution pH of 8.2, the kinetic constant was 3.7-fold larger than that of pristine TiO₂. The hydroxyl radicals derived from the electroreduction of dissolved oxygen with electrons via chain reactions was the main reactive oxygen species. According to the identified intermediates, 4-isopropanolphenol, hydroquinone, 4-hydroxybenzoic acid, and phenol, the possible BPA photodegradation pathways were proposed. Upon 12h irradiation, 77% BPA (20 mg L(-1)) was mineralized and the toxicity to Daphnia magna (D. magna) was almost disappeared, implying the strong oxidation ability of PW₁₂/TiO₂ catalyst. The studies provide important information about the BPA degradation and promote the technical development for BPA removal.

QSAR study on the toxicity of substituted benzenes to the algae (Scenedesmus obliquus)

50% effective inhibition concentration 48h-EC50 of 40 substituted benzenes to the algae (Scenedesmus obliquus) was determined. The energy of the lowest unoccupied molecular orbital (E(LUMO)) was calculated by the quantum chemical method MOPAC6.0-AM1. By using E(LUMO) and the hydrophobicity parameter log K(OW) the quantitative structure-activity relationship model (QSAR) was developed: log1/EC50=0.272 logK(OW) - 0.659E(LUMO) + 2.54, R2 = 0.793, S.E. = 0.316, F = 71.07, n = 40. A series of equations were obtained about the measured EC50 values of different subclasses of compounds. For those compounds containing double -NO2, their toxicity may be related chiefly to the intracellular reduction of -NO2 obtaining electron, while for anilines and phenols, K(OW) contributes most to the QSAR and E(LUMO) very little.

Efficient degradation of tetrabromobisphenol A by heterostructured Ag/Bi5Nb3O15 material under the simulated sunlight irradiation.

Heterostructured metallic silver-layered bismuth niobate two-component system (Ag/Bi(5)Nb(3)O(15)) was developed for the first time by a mild hydrothermal method combined with photodeposition. The Ag/Bi(5)Nb(3)O(15) exhibited single-crystalline orthorhombic structure with small particle size (50-200 nm) and octahedral as well as sheet-like shape; additionally, it possessed photoresponse in both UV and visible region. As a novel alternative photocatalysts to TiO(2), the photocatalytic activity of the Ag/Bi(5)Nb(3)O(15) was evaluated by the degradation of tetrabromobisphenol A, a member from the family of the brominated flame retardant, under solar simulating Xe lamp irradiation, and enhanced photocatalytic activity in compared to Bi(5)Nb(3)O(15) itself and Degussa P25 was obtained.

Design of polyoxometallate–titania composite film (H3PW12O40/TiO2) for the degradation of an aqueous dye Rhodamine B under the simulated sunlight irradiation

A series of polyoxometallate/titania (H(3)PW(12)O(40)/TiO(2)) composite films with different H(3)PW(12)O(40) loadings (6.3%, 7.7%, 14.7% and 16.7%) were prepared by a modified sol-gel-hydrothermal route followed by a spin-coating method. The smooth films are constructed by the well-distributed H(3)PW(12)O(40)/TiO(2) sphere with particle size in the range from 80 to 100 nm, and the bandgap of the composite films is somewhat narrower compared with as-prepared pure TiO(2) film. As a novel photocatalytic material, the photocatalytic performances of the H(3)PW(12)O(40)/TiO(2) composite films were evaluated by the degradation and mineralization of an aqueous dye Rhodamine B (RB) under solar simulating Xe lamp irradiation (320 nm<λ<780 nm), and the enhanced photocatalytic activity in comparison to pure TiO(2) film as well as the H(3)PW(12)O(40)/TiO(2) and Degussa P25 TiO(2) powder was obtained. Additionally, the composite films can be reused at least for three times without losing their catalytic activity.

Simulated sunlight photodegradation of aqueous phthalate esters catalyzed by the polyoxotungstate/titania nanocomposite

A series of porous polyoxotungstate/titania nanocomposites (PW(12)/TiO(2)) with particle size lower than 10nm and BET surface area of ca. 200 m(2)g(-1) was prepared by sol-gel chemistry combined with solvothermal treatment. The composites were successfully applied to the degradation of aqueous phthalate esters (PAEs) including di-n-butyl phthalate (DBP), diethyl phthalate (DEP), and dimethyl phthalate (DMP) under the simulated sunlight irradiation (lambda=320-680 nm) for the first time, and the conversion of DBP, DEP, and DMP reached to 98%, 84%, and 80%, respectively, after the simulated sunlight irradiation the suspension including PAE (5 mg L(-1), 100 mL) and PW(12)/TiO(2)-19.8 (100 mg) for 90 min. In addition, nearly total mineralization of DBP and DEP was realized by further increasing light irradiation time to 12h. Based on the intermediates identified in the reaction system, the photocatalytic degradation pathway of PAEs was put forward.

Classification of toxicity of phenols to Tetrahymena pyriformis and subsequent derivation of QSARs from hydrophobic, ionization and electronic parameters.

Phenolic compounds were classified into different groups based on the structure and functional groups of the phenol. Quantitative structure-activity relationship (QSAR) analysis was performed between the toxicity and octanol/water partition coefficient (logP) for these groups. The results showed that the toxicity of non-ionisable phenols is dependent on their hydrophobicity. Poor relationships were found between the toxicity and logP for ionisable compounds, and the use of methods based on logP to predict the toxicity of ionisable compounds can result in considerable errors. Ionized and unionized forms have different contributions to toxicity; the unionized form plays a more important role than the ionized form because the toxicity of organic acids and phenols decreases as the pH increases. In order to investigate the effect of ionization, the fraction of ionized and unionized forms of phenols at different pH values were calculated from the pK(a) values, and a corrected distribution partition coefficient (D(T)) was derived from QSAR analysis for ionisable compounds. The prediction of toxicity of non-reactive ionisable compounds was improved remarkably by using the D(T) parameter. Ionization not only affects the bio-uptake of ionisable compounds, but interaction with the receptor micromolecule can also depend on the electronic situation, which is also related to the ionization. Stepwise regression showed that the reactivity of ionisable phenols was strongly correlated with the fraction of negatively charged form (F(-)). Interpretable QSAR equations with good statistical fits were developed from hydrophobic, ionization and electronic parameters for 207 phenols.

Quantitative structure-activity relationships of nitroaromatic compounds to four aquatic organisms☆

Abstract Quantitative structure-activity relationships of 26 nitroaromatic compounds to guppy ( Poecilia reticulata ), carp ( Cyprinus carpio), Scenedesmus obliguus, Daphnia carinata were studied based on equations we established. Results showed that observed toxicity of chemicals could be estimated by the parameters of halfwave reduction potential ( E 1 2 ) and bioconcentration factor (BCF). The toxicity data of nitroaromatic compounds to four aquatic organisms were estimated by these parameters. Compared with octanol/water partition coefficient method, the LC 50 values predicted by the two parameters are close to observed LC 50 values. Regression results also showed that the highest occupied molecular orbital energy (E HOMO ), the lowest unoccupied molecular orbital energy (E LUMO ) and octanol/water partition coefficient (K OW ) were ideal parameters instead of the reaction equilibrium constant of target molecule-organic chemical in target cells (K) and bioconcentration factor. Relationships between the toxicity data of guppy, carp, Scenedesmus obliguus, Daphnia carinata and the parameters of E HOMO , E LUMO and K OW were analyzed. Predicted and observed LC 50 values are in good agreement. The observed toxicity data of 2,4-dinitrotoluene and 2,6-dinitrotoluene may be lower than the expected toxicity data because the photolysis of the two chemicals is rapid during the course of experiments.

A novel electrochemical method to evaluate the cytotoxicity of heavy metals

There is an ongoing search to develop techniques for detection of heavy metals which are highly toxic and can cause damaging effects even at very low concentrations. In this present study, we report a label-free electrochemical method based on the direct voltammetric response of human cervical carcinoma (HeLa) cells on a highly sensitive graphene modified electrode. Five heavy metals were tested with the method and the results were validated by the traditional methyl tetrazolium (MTT) assay. The results revealed that the most toxic metal was Cr, followed by Cd, Cu, Pb and Zn. A good correlation between the two methods was observed. This work will be beneficial in providing a novel monitoring method to detect hazardous pollutants in the field of environmental toxicology.

Adsorption and photocatalytic degradation of bisphenol A by low-cost carbon nanotubes synthesized using fallen leaves of poplar

Bisphenol A (BPA) is an endocrine disruptor and the removal of it from contaminated water is a primary environmental issue. Here, carbon nanotubes (CNTs) were synthesized by heating leaves of poplar to 450 °C in air. The outer and inner diameters of CNTs were about 77.5 nm and 40.1 nm, which contained C, O, Na, Zn, Cu, Ca, K, Cl, and S. The effects of adsorption and photocatalysis on BPA (initial concentration was 10 mg L−1) by CNTs (10 mg CNTs were added into 1 L BPA solution) synthesized using leaves of poplar were studied. The results show that without CNTs, the degradation of BPA was about 24.5 ± 4.7% in 180 min with solar light irradiation. The complete equilibration time of adsorption/desorption of BPA onto the surface of CNTs was within 30 min, and approximately 19.7 ± 0.9% BPA was adsorbed by CNTs. Afterwards, the photodegradation efficiency of BPA was increased to 74.8 ± 3.9% with the combination of CNTs and solar light irradiation for 180 min. The photocatalytic property on BPA was caused by CNTs and the metal oxide on the surface of them. The methods have positive effects on solving environmental and ecological problems as well as the problem of high cost for preparation of photocatalyst.