木质素催化降解液化的研究进展

木质素是自然界中含量仅次于纤维素的天然有机高分子,它是以3种苯丙烷(芥子醇、松柏醇和香豆醇)为结构单元,通过C-C和C-O-C键连接形成的无定形网状大分子,是自然界唯一可再生的芳香类物质原料。木质素在生产大宗化学品和精细化学品方面有着巨大潜力。但是,木质素复杂的结构导致其难以高效、高选择性转化而被有效利用。近年来,有关木质素催化降解液化的研究成为一个备受关注的热点。概述了木质素催化降解液化的研究现状,基于溶液状态下木质素分子尺度和形态分析,设计与之匹配的负载酸和金属粒子的介孔催化剂,可实现木质素在有限孔道内催化降解以及抑制降解片段重聚,最后对其未来发展趋势进行了展望。

木质纤维素快速热化学液化催化制氢研究的现状

氢能作为一种洁净的可再生能源,从长远看,它的发展可能带来能源结构的重大改变,是一种很有潜力的低污染或零污染的车用替代能源。加快木质纤维素深度化学降解液化理论与技术的研究步伐,在温和的条件下,高效地获得稳定的和高质量的液态氢源燃料,并研制与该新型液态氢源燃料相匹配的高活性、高选择性制氢催化剂和高效氢燃料电池,是推动我国氢能经济发展的当务之急。

Improved visible light photocatalytic activity of mesoporous FeVO_4 nanorods synthesized using a reactable ionic liquid

Mesoporous FeVO4 nanorods were successfully synthesized by calcining the precursor Fe- VO4·1.1H2O nanorods, which were obtained via a simple hydrothermal method in the presence of a reactable metal-ion-containing ionic liquid, 1-octyl-3-methylimidazolium tetrachloride ferrate(III)([Omim]FeCl4). The structure and morphology of the prepared samples were examined using various characterization techniques. During the synthetic process,[Omim]FeCl4 acted as the solvent, reactant, and capping agent simultaneously. Moreover, the porous FeVO4 nanorods as the heterogeneous photo-Fenton-like semiconductor catalyst for the degradation of tetracycline and rhodamine B under visible light irradiation exhibited excellent photocatalytic activity. This excellent photocatalytic activity of the porous FeVO4 nanorods can be attributed to the synergistic effect of their high electron-hole pair separation rate, suitable band gap structure, and large specific surface area. The possible photocatalytic degradation mechanism of FeVO4/H2O2 photocatalytic systems was also discussed in detail.

Preparation of amphiphilic TiO_2 Janus particles with highly enhanced photocatalytic activity

Stearic-acid-modified TiO2 (STA-TiO2) particles were prepared via the impregnation approach and used as a precursor for preparing TiO2 Janus particles. The morphology, structure, and properties of the TiO2 Janus particles were characterized using Fourier-transform infrared spectroscopy, ultraviolet- visible diffuse reflectance spectroscopy, thermogravimetric analysis, fluorescence microscopy, high-resolution transmission electron microscopy, contact angle analysis, dynamic light scattering, biological microscopy, X-ray photoelectron spectroscopy, and electrochemical impedance spectroscopy measurements. The results show that TiO2 Janus particles can be successfully prepared via toposelective surface modification. STA grafted on the surface of TiO2 enhances its hydrophobicity, promotes charge separation, and improves its adsorption capacity for organic compounds. The TiO2 Janus particles strongly adsorb on an oil-water interface to form a stable Pickering emulsion. The degradation rates of high-concentration kerosene and nitrobenzene wastewaters when the photocatalyst is pure TiO2, STA-TiO2, or TiO2 Janus particles are discussed and compared. The degradation rates were determined using an ultraviolet-visible spectrophotometer. It was found that the Pickering emulsion stabilized by the TiO2 Janus particles exhibited the best photocatalytic performance;these Janus particles show promising potential for catalytic application.

Passivity Degradation of Alloy 800 in Simulated Crevice Chemistries

Passivity degradation of Alloy 800 in simulated crevice chemistries was systematically investigated using cyclic polarization curve, electrochemical impedance spectroscopy(EIS), Mott-Schottky analysis, Auger electron spectroscopy(AES)and atomic absorption spectrometry(AAS). Cyclic polarization showed that the pitting potential in a thiosulfate solution was much lower than in either a chloride solution or a sulfate-chloride solution. Mott-Schottky results revealed that passive films showed n-type semiconductivity, and the presence of thiosulfate in chloride solution led to an increased donor density in the passive film. EIS spectra indicated that thiosulfate enhanced the film dissolution rate in chloride solutions. Moreover, thiosulfate enhanced the pitting propagation rate in chloride solution by stabilizing the metastable pits and forming sulfide within the pits.

Effect of Dispersity and Porous Structure of TiO2 Nanopowders on Photocatalytic Destruction of Azodyes in Aqueous Solutions

Photocatalytic activity of TiO2 nanopowders of anatase modification with various particle sizes and specific surface areas has been studied in the process of photocatalytic decolorization of aqueous solutions of methylene blue and direct blue 2C azodyes. By means of scanning electron microscopy and low-temperature N2 adsorption method, it was found that TiO2 nanopowders have the particles size of 5-120 nm with the specific surface area of 15-120 m2·g^-1. The used TiO2 samples are characterized by mesoporous structures with average pore size of 4.3-14.9 nm. The photocatalytic activity of TiO2 was evaluated via decolorization of azodyes solutions. It was shown that the efficiency of decolorization symbatically changes with the dye adsorption value on TiO2 surface and the degree of decolorization rises when the surface area of TiO2 nanopowders increases. It was found that TiO2 photocatalytic activity essentially depends on adsorption interactions between the dye molecules and catalytic active centers on TiO2 surface, and these interactions, in turn, are greatly affected by pH of the solution.

Catalytic ozonation of thymol in reverse osmosis concentrate with core/shell Fe_3O_4@SiO_2@Yb_2O_3 catalyst:Parameter optimization and degradation pathway

In this work, a novel catalyst of Fe_3O_4@SiO_2@Yb_2O_3 was prepared and the degradation of thymol in reverse osmosis concentrate using ozonation was explored. The operational parameters, such as ozone dosage(8–48 mg·min^(-1)),initial thymol concentration(20–100 mg·L^(-1)), initial pH value(3–11), and catalyst Fe_3O_4@SiO_2@Yb_2O_3dosage(0.2–1.0 g), were studied focusing on the thymol degradation and COD removal. The results indicated that the increase in ozone dosage, initial p H value, and Fe_3O_4@SiO_2@Yb_2O_3dosage accelerated the thymol degradation and COD removal, while the increase in initial thymol concentration hampered the effect of ozonation. A pathway of thymol degradation by catalytic ozonation was proposed based on the intermediates detected by gas chromatography-mass spectrometer and ion chromatography. This paper can provide basic data and technical alternative for pollutant removal from reverse osmosis concentrate by ozonation.

Photo Degradation of Dyes from Their Aqueous Solutions of Their Binary Mixture, Using TiO2 as the Oxidant with Different Sources of Energy

The photodegradation has been widely used in water and waste water treatment of all the methods like froth flotation coagulation etc., photodegradation appears to offer the best prospects for overall treatment of dyestuff effulent. Photodegradation of aniline blue and crystal violet dyes from aqueous solutions of their binary mixture was carried out using TiO2 as photocatalyst. By carrying out photodegradation, varying the experimental parameters, the optimum conditions required for maximum degradation was found out. The photodegradation of dye was carried out using different sources of energy like solar radiation and microwave radiation. The degradation studies were carried out at temperatures 25 ℃, 35 ℃ and 45 ℃ so as to calculate the rate constant and activation parameters. Both energy sources are equivalent in causing degradation in all respects except time and dose of photo catalyst. Time required is less for microwave than solar radiation, but dose of photo catalyst needed was high for microwave radiation. These results will be helpful in designing effluent treatment plants in industries.

Radiation-Chemical Degradation of Oxalic Acid in Water Solutions

Co60 gamma ray radiolysis of aqueous oxalic acid solution （1 × 10-2 M） was investigated within the dose range up to 80 kGy. The value of pH increases from 2.0 to 4.0 and approximately 90% of oxalic acid and its derivatives are degraded at the dose of 80 kGy. Dissolved O2 affects to the degradation of oxalic acid at the initial stage due to total consumption of O2 at the dose of 2 kGy. Formation of CO2 occurs at a higher rate at the initial stage until the dissolved 02 is fully consumed. The kinetic model of oxalic acid degradation in aqueous solution under the gamma irradiation was tested. The suggested mechanism complies with the experimental data both of our own and of that reported earlier.

Photochemical Degradation of Phenols in Water Using Flavin-based Photosensitizers

A slightly modified method for 10-ethyl flavin was developed in the present study. The synthetic product was characterized by nuclear magnetic resonance(NMR) and mass spectrometry, and used to catalyze the photocatalytic degradation of phenol, 2, 4-dichlorophenoxyacetic acid, p-nitrophenol, 4-chlorophenol, 4-methoxyphenol, 4-chloro-2-methyl-phenoxyacetic acid and2, 4, 5-trichloro-phenoxyacetic acid. Both HPLC(high performance liquid chromatography) and GC-MS data suggested that all phenols were degraded in the presence of either flavin at micromolar concentrations under direct sun light. A rapid breakdown of the phenols was observed. The degradation efficiency was clearly dependent on phenol type. In a decreasing order of degradation efficiency over a 2-h period, the phenols were 4-chlorophenol and 4-methoxyphenol(-80%) > phenoxyacetic acids(60%-65%) > nitrophenol and phenol(-35%).

Which is the determinant for cellulose degradation in cooperative ionic liquid pairs: dissolution or catalysis?

Catalytic conversion of sustainable cellulose to the value-added chemicals and high quality biofuel has been recognized as a perfect approach for the alleviation of the dependence on the non-renewable fossil resources. Previously, we successfully de- signed and explored novel and efficient cooperative ionic liquid pairs for this renewable material, which has advantages of high reactor efficiency than current technologies because of the dissolution and in situ catalytic decomposition mechanism. Here, the determinant of this process is further studied by the intensive investigation on the relationship between the cellulose conversion and the properties of ionic liquid catalyst and solvent. Scanning electron microscope （SEM）, thermogravimetric analysis （TG） and elemental analysis were used for the comparative characterization of raw cellulose and the residues. The re- suits demonstrate that this consecutive dissolution and in situ catalysis process is much more dependent on the dissolution ca- pability of ionic liquid solvent, while comparatively, the effect of in situ acid catalysis is relatively insignificant.