Cross-linking of cellulose and poly(ethylene glycol) with citric acid

A novel approach to modifying native cellulosic fibres with poly(ethylene glycol) (PEG) impregnation and simultaneous cross-linking by citric acid (CA) was investigated. To understand the contributions of different components in the system, control references with just CA and cellulosic fibres (filter paper) were studied. The effect of sodium hypophosphite as a catalyst was also assessed. The results revealed that ester bonds are indeed formed in the cellulose–PEG–CA reaction system, as indicated by weight percentage gain (WPG) and FTIR analysis. The best results were achieved by using 5% CA and 10% PEG (calculated as weight-% from cellulose). In the reaction, the environmentally friendly CA prevents PEG from being leached out of cellulose during washing, resulting in promising future applications in dimensionally stabilized products based on cellulosic fibres.     

催化裂化催化剂制备过程中水资源的综合利用

在催化裂化催化剂制备过程中会产生大量废水,这些废水来源于分子筛和催化剂的交换、过滤、洗涤及后改性过程中引入的铵盐、新鲜水及或酸碱等交换介质的残存液。通过分析过程中废水产生的原因及性质,将废水按不同性质分类收集,并采用不同的处理方法,重新回用于制备体系中,提高水资源循环利用率,降低外排废水量。     

High temperature Ir segregation in Ir–B ceramics: effect of oxygen presence on stability of IrB2 and other Ir–B phases

The formation of IrB₂, IrB_1.35, IrB_1.1 and IrB monoboride phases in the Ir–B ceramic nanopowder was confirmed during mechanochemical reaction between metallic Ir and elemental B powders. The Ir–B phases were analysed after 90 h of high energy ball milling and after annealing of the powder for 72 h at 1050°C in vacuo. The iridium monoboride (IrB) orthorhombic phase was synthesised experimentally for the first time and identified by powder X-ray diffraction. Additionally, the ReB₂ type IrB₂ hexagonal phase was also produced for the first time and identified by high resolution transmission electron microscope. Ir segregation along disordered domains of the boron lattice was found to occur during high temperature annealing. These nanodomains may have useful catalytic properties.     

Synthesis,characterization, rheological and thermal behavior of metallocene ethylene − norbornene copolymers with low norbornene content using pentafluorophenol modified methylaluminoxane

Ethylene ? norbornene copolymers were synthesized using rac‐ethylene bis(indenyl) zirconium dichloride/pentafluorophenol modified methylaluminoxane. First, the effect of using a modifier in combination with a low ratio of Al/Zr on the catalyst activity and co‐monomer incorporation was studied. The results of copolymerization reveal a 20% co‐monomer incorporation improvement and a rise of activity by 2‐fold in the presence of the modifier. Rheological measurements show a higher molecular weight in copolymers synthesized using modified methylaluminoxane. The alternative and dyad block microstructures of copolymers become possible in the case of a norbornene content of more than 14 mol%. Second, the effect of co‐monomer content on the rheological and thermal behavior of the synthesized copolymers was investigated. The results of the rheological study indicate a lower molecular weight in samples containing a higher norbornene content. Dynamic mechanical thermal analysis confirms the influence of different microstructures on the glass transition temperature. The crystal structure of copolymers having a higher molecular weight is emphasized using wide angle X‐ray scattering and DSC even with a greater incorporation of norbornene. © 2015 Society of Chemical Industry     

Reverse iodine transfer polymerization of vinyl acetate and vinyl benzoate: synthesis and characterization of homo‐ and copolymers

Homo‐ and copolymers of vinyl esters including vinyl acetate (VAc) and vinyl benzoate (VBz) were synthesized via the reverse iodine transfer radical polymerization technique. Polymerization was carried out in the presence of iodine as the in situ generator of the transfer agent and 2,2′‐azobis(isobutyronitrile) as the initiator at 70 °C. Reverse iodine transfer radical homopolymerization of VAc and VBz led to conversions of 76 and 57%, number‐average molecular weights of 8266 and 9814 g mol^?1 and molecular weight distributions of 1.58 and 1.49, respectively. The microstructure of the synthesized polymers was investigated in detail using gel permeation chromatography, ¹H NMR, ¹³C NMR and distortionless enhancement of polarization transfer (135° decoupler pulse) techniques. Relatively narrow molecular weight distribution and controlled and predictable trend of molecular weight versus conversion were observed for the synthesized polymers, showing that reverse iodine transfer radical homo‐ and copolymerization of VAc and VBz proceeded with controlled characteristics. Results of molecular weight and its distribution along with the ¹H NMR spectra recorded for homo‐ and copolymers indicated that side reactions can occur during the course of polymerization with a significant contribution when VAc, even in a small amount, was present in the reaction mixture. This can result in polymer chains with aldehyde dead end and broadening of the molecular weight distribution. © 2015 Society of Chemical Industry     

中空碳基材料在电解水中的研究进展

氢能所具有的清洁、高能量密度特点，使其成为一种未来的理想能源。相较于石油、天然气等的热解制氢技术，利用可再生清洁能源进行电催化分解水制氢具有高效和清洁无污染的特点，且获得氢气产物纯度高，具备大规模发展的潜力。而在大规模水电解过程中，电催化剂是不可或缺的元素之一。它能有效地加速电解水在阴阳两极反应的动力学过程。传统的贵金属基催化剂具有良好的电催化析氢、析氧活性，但成本高昂、储量稀缺，从而限制了其规模化地推广及应用。开发新型高效廉价的非贵金属基电催化剂已成为时下研究热点。中空碳基纳米材料集成了中空材料和碳基材料的优势，作为电催化剂，在电解水方面有着潜在的应用价值。本文总结了近年来微纳米结构碳基中空材料作为新型电解水催化剂的研究进展，介绍了高效碳基中空析氧/析氢催化剂的设计原则和相应的设计策略，并对开发持久高效的中空碳基电解水催化剂进行了总结和展望。     

阴离子种类及浓度对RCT催化剂催化湿式氧化处理头孢废水的影响

采用催化湿式氧化法处理头孢类废水,以RCT为催化剂,考察了阴离子对污染物降解效果的影响。结果表明,不加阴离子时,RCT催化剂能有效催化污染物的降解,TOC和TN去除率分别为78.3%和85.9%;投加不同阴离子对反应的影响不同。RCT催化剂可将头孢氨苄废水中的有机N转化为$N_{2}$,少部分以$NO_{3}-N$形式存在;阴离子F^-、Cl^-、Br^-、I-及$S^{2-}_{4}$对TN的降解影响不大,而$N^{-}_{3}$、$P^{3-}_4$、$CO^{2-}_{3}$、$Si^{2-}_{3}$及$B_{4}O^{2-}_{7}$则明显抑制了对TN的去除。投加F^-、Cl^-、Br^-、I-及$NO^{-}_{3}$对TOC的降解有促进作用(I^-> F^-> Cl^-> Br^-> $NO^{-}_{3}$),TOC的降解率提高了3.1~18.6个百分点;而投加$S^{2-}_{4}$、P,$P^{3-}_4$、$CO^{2-}_{3}$、$SiO^{2-}_{3}$及$B_{4}O^{2-}_{7}$对TOC的降解有抑制作用($SiO^{2-}_{3}$> ,$P^{3-}_4$> $CO^{2-}_{3}$> $B_{4}O^{2-}_{7}$> $S^{2-}_{4}$),TOC的降解率降低了2.0~46.9个百分点。研究Cl-浓度对RCT催化剂降解效果的影响,当Cl-为0.1 mol·L-1时,对TOC的去除有抑制作用,而较高的Cl-浓度(≥0.3 mol·L-1)对TOC的去除却有促进作用,投加Cl-对TN的去除有促进作用,但随着Cl-浓度的增加[(0.1~0.8) mol·L-1],TN的去除率变化不明显(约为88%)。     

Selective Hydrogenation of Biomass-Derived Succinic Acid: Reaction Network and Kinetics

The conversion of bio-based succinic acid (SA) to the value-added chemicals 1,4-butanediol (BDO), γ-butyrolactone (GBL), and tetrahydrofuran (THF) can replace the corresponding petrochemical production routes to achieve a sustainable process. The reaction network for aqueous-phase catalytic hydrogenation of succinic acid over a supported Re-Pd catalyst was identified and the reaction kinetics was determined. With the developed kinetic model, the composition of the product mixture regarding the desired products (BDO, GBL, THF) can be described as a function of educt concentration, temperature, and pressure. The maximum BDO yield was achieved at high pressure and low temperature, while low pressure and high temperature favored GBL and THF production.     

四氢呋喃对M-1催化剂性能的影响

结合乙烯气相流化床反应工艺的特点,深入探讨分析四氢呋喃对M-1催化剂的作用和影响,结果表明,四氢呋喃的含量直接影响M-1催化剂的活性和催化乙烯与丁烯-1共聚生产的树脂产品性能。为了生产性能优良的乙烯与丁烯-1共聚产品,需要将四氢呋喃的含量严格控制在较窄的范围。     

Effects of molecular modifications for water splitting enhancement of BiVO4

Combined organic (molecular adsorption) and inorganic (TiO₂ passivation) modifications for enhancing water splitting efficiency of porous bismuth vanadate electrodes are tested. The catalytic activity of BiVO₄ is increased after adsorption of a newly prepared ruthenium catalyst. TiO₂ passivation and sensitization with RuP dye does not show straightforward improvements to the complex photocatalytic behaviour depending on the configuration of the (two- or three-electrode) photoelectrochemical cell, type of the experiment and sample aging. The time constant for electron transport in BiVO₄ electrodes (in the range of seconds, revealed by electrochemical impedance measurements) was found to correlate with the stable photocurrent of the cells. The femtosecond transient absorption studies confirm the negligible effects of RuP on the population of the photoexcited carriers in BiVO₄. The transient absorption studies also show that the processes responsible for the differences in photocurrents of the modified BiVO₄ samples occur on a time scale longer than the first nanoseconds.