超临界二氧化碳偶合超声预处理强化玉米秸秆酶水解(英)

提出了一个木质纤维素生物质预处理的全绿色加工过程.以玉米秸秆和玉米芯为原料,以超临界CO₂和超声偶合法对木质纤维素进行预处理.超临界CO₂预处理条件为:压力15-25 MPa,温度120₁70℃,含水量50%,反应时间0.5₄ h.超声场功率600W,温度80℃,作用时间2-8 h.用纤维素酶水解反应获得的还原糖总量来评价预处理效果.结果表明,单纯超临界CO₂和超临界CO₂偶合超声预处理都能够提高生物质水解反应还原糖产量.对于玉米芯,超临界CO₂预处理（170℃,20 MPa,3 0min）后,还原糖产率为62%（未预处理的为12%）.对于玉米秸秆（170℃,20 MPa,2.5 h）,还原糖产率为46.4%.对于玉米芯,超临界CO₂偶合超声预处理（600 W,80℃下超声处理6 h,然后用170℃,20 MPa超临界CO₂预处理30 min）后,还原糖产率为87%.对于玉米秸秆,超临界CO₂偶合超声预处理（600 W,80℃下超声处理8 h,然后用170℃,20 MPa超临界CO₂预处理1 h）后,还原糖产率为25.5%.与未处理生物质相比,X射线衍射结果表明玉米秸秆和玉米芯在超临界CO₂和超声预处理后其结晶度没有明显变化.扫描电镜分析则发现木质纤维素的表面积显著增加.     

Preparation of polypropylene/sepiolite nanocomposites using supercritical CO2 assisted mixing

Well dispersed polypropylene (PP)/sepiolite clay nanocomposites were prepared successfully using supercritical carbon dioxide (scCO₂) assisted mixing with and without the presence of maleic anhydride grafted polypropylene (PP-g-MA) as compatibilizer. The resulting morphology and polymorphism of nanocomposites were established using X-ray diffraction (XRD) analysis, transmission electron microscopy (TEM) and scanning electron microscopy (SEM) observations. The mechanical properties of the nanocomposites were investigated and compared with those obtained by a traditional melt compounding method. Our results showed that by using scCO₂ in the process, we were able to obtain better sepiolite dispersions and reduce breakage of sepiolite fibres. Consequently, a significant improvement in the yield stress was observed for the nanocomposites processed in scCO₂ compared to those processed by the traditional melt compounding. XRD data also indicated that the resulting nanocomposites had only α-phase crystallites of PP while the presence of sepiolite could also induce preferred orientation of these α-phase crystallites.     

Organic–inorganic polypyrrole‐surface modified SiO2 hybrid nanocomposites: a facile and green synthetic approach

Organic–inorganic hybrid nanocomposites composed of conductive polypyrrole (PPy) and surface modified silica (SiO₂) were successfully prepared through an in situ chemical oxidative polymerization in supercritical carbon dioxide (scCO₂). SiO₂ nanoparticles were surface modified using 3‐methacryloxypropyltrimethoxysilane (MPTMS) in order to disperse well in the medium. Transmission electron microscopy (TEM) and scanning electron microscopy (SEM) showed that the SiO₂ nanoparticles were encapsulated into the polymer. UV‐visible spectra of the diluted colloidal dispersions of PPy/SiO₂ hybrid nanocomposites were similar to those of PPy system. Fourier transform infrared spectroscopy (FT‐IR) suggested the strong interaction between PPy and SiO₂. Surface characterizations of nanocomposites were described by X‐ray photoelectron spectroscopy (XPS). The nanocomposites synthesized in scCO₂ have been shown to possess higher electrical conductivity and thermal stability. Copyright © 2009 John Wiley & Sons, Ltd.     

LB技术制备SnO2-TiO2无机交替纳米薄膜

采用LB技术将SnO₂纳米粒子和TiO₂纳米粒子组装进花生酸的交替多层膜，通过热处理除去膜中的有机成分后，采用红外光谱、紫外可见光谱、X-光电子能谱、低角X-射线衍射、原子力显微镜以及扫描电子显微镜等手段对处理后的膜进行了形貌、组成和结构表征，表明制得的是SnO₂纳米粒子-TiO₂纳米粒子无机-无机交替的均匀的纳米薄膜。     

傅立叶变换红外光谱技术在超临界CO2作用聚合物体系中的应用

超临界CO₂（scCO₂）作为一种物理化学性质优良、具有高扩散速率及优良溶解性能的溶剂,在科学研究及工业生产中广受青睐。将scCO₂应用于聚合物体系中,CO₂ 与聚合物间特殊的相互作用有利于CO₂分子在聚合物中的吸附与扩散。同时通过CO₂的吸附及其对聚合物的溶胀和塑化作用,聚合物所处微观化学环境以及整体结构性质会发生一定的变化。由于傅立叶变换红外光谱（FTIR）技术能够有效地考察化学环境变化对分子结构造成的影响,这一表征技术在超临界CO₂作用体系中广为应用。本文主要选取了近年来利用FTIR技术考察scCO₂作用于聚合物体系的一些实例,从CO₂-聚合物相互作用机理,scCO₂对聚合物或生物大分子的加工过程的影响两方面,阐述了利用红外光谱技术在scCO₂作用体系中的应用以及前景。     

In situ radical polymerization of methyl methacrylate in a solution of surface modified TiO2 and nanoparticles

Surface modified TiO₂ nanoparticles dissolved in toluene were encapsulated in PMMA by in situ radical polymerization of methyl methacrylate initiated by 2,2′-azobisisobutyronitrile. The surface modification of the TiO₂ nanoparticles (average diameter of 4.5 nm) was achieved by the formation of a charge transfer complex between TiO₂ nanoparticles and 6-palmitate ascorbic acid. The surface modified TiO₂/nanoparticles were characterized using UV−Vis and FTIR spectroscopy, while the obtained polymer nanocomposites were characterized using reflection and ¹H NMR spectroscopy, as well as gel permeation chromatography. The influence of the TiO₂ nanoparticles on the thermal properties of the PMMA matrix was investigated using thermo-gravimetric analysis and differential scanning calorimetry. The glass transition temperature of the polymer was not influenced by the presence of the nanoparticles while the thermal stability was significantly improved.     

纳米TiO2表面接枝聚苯乙烯及其抗紫外老化研究

利用偶联剂γ-甲基丙烯酰氧基丙基三甲氧基硅烷(KH570)对纳米TiO₂进行表面预处理, 在此基础上通过分散聚合工艺制备聚苯乙烯(PSt)接枝包覆纳米TiO₂. 运用红外光谱、热重分析及透射电镜对处理前后纳米TiO₂进行了表征, 并通过紫外人工加速老化试验比较了表面处理前后纳米TiO₂对聚丙烯/聚苯乙烯(PP/PSt)体系的抗紫外老化性能. 结果显示: KH570与纳米TiO₂表面羟基进行了缩合, PSt在粒子表面实现了接枝聚合, 接枝率约为60% (w); PSt接枝包覆纳米TiO₂呈均匀的微球形, 纳米TiO₂被包覆于微球内部; PSt接枝包覆后纳米TiO₂在PP/PSt中的分散效果较改性前有显著的改进, 其抗紫外老化性能明显优于改性前体系.     

Preparation and properties of propylene/POSS copolymer with rac-Et(Ind)2ZrCl2 catalyst

An organic-inorganic hybrid copolymer was prepared by using a C₂ symmetric ansa-metallocene catalyst in conjunction with modified methylaluminoxane (MMAO). Two kinds of monovinyl substituted polyhedral oligomeric silsesquioxane (POSS) monomers were used to copolymerize with propylene. A special experiment was carried out in order to confirm the purification of the copolymerization products. The unreacted monomer was completely removed by washing with an n-hexane/ethanol mixture. Thermal properties of the propylene/POSS copolymers exhibited improved thermal stability with higher degradation temperature and char yields, demonstrating that the inclusion of inorganic POSS nanoparticles made the organic polymer matrix more thermally robust.     

La2O3/γ-Al2O3催化剂用于二甲醚二氧化碳重整制氢

采用等体积浸渍法制备了不同负载量的La₂O₃/γ-Al₂O₃催化剂,并考察了负载量和反应温度对催化剂用于二甲醚二氧化碳重整制氢反应的性能影响。结果表明,反应温度为550℃、La₂O₃负载量为15%时,催化剂表现出最好的性能：二甲醚的转化率为100%,二氧化碳的转化率达到85.4%,产物氢气的选择性高达93.3%,一氧化碳的选择性为76.04%,副产物甲烷的选择性仅为6.3%。550 ℃时其平均积炭速率为1.387 5 mg/（g·h）。研究还利用XRD、BET、TEM、TG等方法对催化剂进行了表征。     

A facile two-step modifying process for preparation of poly(SStNa)-grafted Fe3O4/SiO2 particles

This article reports the synthesis of the poly(sodium 4-styrenesulfonate)-grafted Fe₃O₄/SiO₂ particles via two steps. The first step involved magnetite nanoparticles (Fe₃O₄) homogeneously incorporated into silica spheres using the modified Stöber method. Second, the modified silica-coated Fe₃O₄ nanoparticles were covered with the outer shell of anionic polyelectrolyte by surface-initiated atom transfer radical polymerization. The resulted composites were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), energy dispersive microscopy (EDS), Fourier transform-infrared (FT-IR), thermogravimetric analysis (TGA), X-ray photoelectron spectroscopy (XPS) and vibration sample magnetometer (VSM). The XRD results indicated that the surface modified Fe₃O₄ nanoparticles did not lead to phase change compared with the pure Fe₃O₄. TEM studies revealed nanoparticles remained monodisperse. The detection of sulfur and sodium signals was a convincing evidence that sodium 4-styrenesulfonate was grafted onto the surface of the magnetic silica in XPS analysis. Finally, super-paramagnetic properties of the composite particles, and the ease of modifying the surfaces may make the composites of important use in mild separation, enzyme immobilization, etc.     

Photocatalytic hydrogen evolution over mesoporous TiO2/metal nanocomposites

Na⁺ complex with the dibenzo-18-crown-6 ester was used as a template to synthesize mesoporous titanium dioxide with the specific surface area 130–140 m²/g, pore diameter 5–9 nm and anatase content 70–90%. The mesoporous TiO₂ samples prepared were found to have photocatalytic activity in Cu^II, Ni^II and Ag^I reduction by aliphatic alcohols. The resulting metal–semiconductor nanostructures have remarkable photocatalytic activity in hydrogen evolution from water–alcohol mixtures, their efficiency being 50–60% greater than that of the metal-containing nano-composites based on TiO₂ Degussa P25.The effects of the thermal treatment of mesoporous TiO₂ upon its photocatalytic activity in hydrogen production were studied. The anatase content and pore size were found to be the basic parameters determining the photoreaction rate. The growth of the quantum yield of hydrogen evolution from TiO₂/Ag⁰ to TiO₂/Ni⁰ to TiO₂/Cu⁰ was interpreted in terms of differences in the electronic interaction between metal nanoparticles and the semiconductor surface. It was found that there is an optimal metal concentration range where the quantum yield of hydrogen production is maximal. A decrease in the photoreaction rate at further increment in the metal content was supposed to be connected with the enlargement of metal nanoparticles and deterioration of the intimate electron interaction between the components of the metal–semiconductor nanocomposites.     

Thermal decomposition of barium oxalate hemihydrate BaC2O4·0.5H2O

The thermal behaviour of BaC₂O₄sd0.5H₂O and BaCO₃ in carbon dioxide and nitrogen atmospheres is investigated as part of a study about the thermal decomposition of barium trioxalatoaluminate. For this purpose thermogravimetry, differential thermal analysis, differential scanning calorimetry and high temperature X-ray diffraction were used. An infrared absorption spectrum of BaC₂O₄·0.5H₂O was scanned at room temperature.At increasing temperature, in dry nitrogen, the hydrate water of BaC₂O₄· 0.5H₂O is split off, followed by the oxalate decomposition. A part of the evolved carbon monoxide disproportionates, leaving carbon behind. At higher temperatures the latter reacts with barium carbonate, previously formed. Finally the residual solid barium carbonate decomposes into barium oxide and carbon dioxide.In dry carbon dioxide atmosphere an analogous dehydration occurs, followed by oxalate decomposition. Under these conditions the carbon formation is fully suppressed, and as a consequence no secondary reaction occurs. The barium carbonate decomposition is shifted to much higher temperatures, at a low rate in the solid phase, a strongly accelerated one at the onset of melting, and a moderated one when the melt is saturated with barium carbonate. The two phase transitions of BaCO₃ are detectable in both atmospheres mentioned.     

Effect of supercritical CO2 on the copolymerization behavior of cyclohexene oxide/CO2 and copolymer properties with DMC/Salen‐Co(III) catalyst system

The copolymerization of cyclohexene oxide (CHO) and carbon dioxide (CO₂) was carried out under supercritical CO₂ (scCO₂) conditions to afford poly (cyclohexene carbonate) (PCHC) in high yield. The scCO₂ provided not only the C1 feedstock but also proved to be a very efficient solvent and processing aid for this copolymerization system. Double metal cyanide (DMC) and salen‐Co(III) catalysts were employed, demonstrating excellent CO₂/CHO copolymerization with high yield and high selectivity. Surprisingly, our use of scCO₂ was found to significantly enhance the copolymerization efficiency and the quality of the final polymer product. Thermally stable and high molecular weight (MW) copolymers were successfully obtained. Optimization led to excellent catalyst yield (656 wt/wt, polymer/catalyst) and selectivity (over 96% toward polycarbonate) that were significantly beyond what could be achieved in conventional solvents. Moreover, detailed thermal analyses demonstrated that the PCHC copolymer produced in scCO₂ exhibited higher glass transition temperatures (T_g ～ 114 °C) compared to polymer formed in dense phase CO₂ (T_g ～ 77 °C), and hence good thermal stability. Additionally, residual catalyst could be removed from the final polymer using scCO₂, pointing toward a green method that avoids the use of conventional volatile organic‐based solvents for both synthesis and work‐up. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 2785–2793     

石墨相氮化碳/二氧化锡复合材料的制备及光催化性能

采用热聚合法和水热法相结合的方法制备了g-C_3N_4/SnO_2复合光催化剂。利用XRD、SEM、TEM、FT-IR和UV-Vis DRS等多种测试手段对所得样品的物相结构、微观形貌和吸光特性等进行了表征。结果表明,异质结构复合光催化剂的最大光吸收边位置相对纯相SnO_2发生了明显的红移,并且SnO_2颗粒均匀分布于g-C_3N_4表面,其中最优组分(50%-g-C_3N_4/SnO_2)光催化降解染料罗丹明B(RhB)的效率达到了纯相g-C_3N_4的3.78倍。     

The CaF2-CaCl2-CaSO4 system

The liquidus surface of the CaF₂-CaCl₂-CaSO₄ system has been investigated by differential thermal analysis. Two invariant equilibria (one eutectic and one peritectic) are realized in the system. The eutectic and peritectic melt at 597 and 703°C, and the enthalpies of phase transitions are 206 and 378.1 kJ/kg, respectively. Investigation of the ternary system formed by the natural minerals fluorite (CaF₂), anhydrite (CaSO₄), and calcium chloride (a relatively low-melting inorganic solvent) is undertaken with the goal of developing power-intensive heat-accumulating phase-transition materials and electrolytes of diversified application. Original Russian Text ? P.A. Arbukhanova, Ya.A. Dibirov, N.N. Verdiev, A.M. Amadziev, 2009, published in Zhurnal Neorganicheskoi Khimii, 2009, Vol. 54, No. 6, pp. 1043–1045.     

介孔α-Fe2O3表面配合反应平衡常数测定

采用十二胺为模板剂、氨水做沉淀剂成功制备了介孔α-Fe₂O₃, 通过粉末X射线衍射(XRD)、透射电镜(TEM)、N₂吸附/脱附技术对样品晶相、形貌和比表面积进行了表征. 根据介孔α-Fe₂O₃悬浮液的酸碱滴定数据, 使用FITEQL软件, 采用双电层恒电容模型计算得出了介孔α-Fe₂O₃的表面酸碱反应平衡常数. 在此基础上研究了Cu^2＋, Pb^2＋, Zn^2＋在介孔氧化铁表面的吸附行为, 使用WinSGW软件模拟得出了相应的表面配合反应平衡常数并讨论了其吸附机理.     

Formation of appropriate sites on nanofiltration membrane surface for binding TiO2 photo-catalyst: Performance, characterization and fouling-resistant capability

Titanium dioxide (TiO₂) nanoparticles were assembled on the surface of nanofiltration blend membrane. For settling TiO₂ on the membrane surface, two membrane categories were used: (i) unmodified polyethersulfone (PES)/polyimide (PI) blend membrane, and (ii) –OH functionalized PES/PI blend membrane with different concentrations of diethanolamine (DEA). These membranes were radiated by UV light after TiO₂ depositing with different concentrations. 15 min immersion in colloidal suspension and 15 min UV irradiation with 160 W lamps were used for modification. The modification resulted in the formation of a photo-catalytic property with enhanced membrane hydrophilicity. The self-assembly of TiO₂ nanoparticles was established through coordinance bonds with –OH functional groups on the membrane surface. A comparison between the UV irradiated TiO₂ deposited blend membrane and deposited-functionalized blend membranes showed that –OH groups originate excellent adhesion of TiO₂ nanoparticles on the membrane surface, increase reversible deposition, and diminish irreversible fouling. The membranes were characterized using SEM, FTIR, EDX, contact angle, cross flow filtration, and antifouling measurements. SEM images show that the presence of –OH groups on the DEA-modified membrane surface is the main parameter for extra uniformly settlement of TiO₂ nanoparticles on the membrane surface. This procedure is a superior technique for modification of PES/PI nanofiltration membranes to enhance water flux and minimization membrane fouling.     

Alginate-Coated Fe3O4 Hollow Microspheres for Drug Delivery

Novel hollow Fe₃O₄ nanoparticles for drug delivery were synthesized via a one-step templatefree approach. These nanoparticles were obtained by modifing the Fe₃O₄ nanoparticles with 3-aminopropyltrimethoxy silane, and then grafting alginate onto the surface of amine magnetic. The hollow structure of Fe₃O₄ spheres was characterized by TEM, XRD, and XPS. The M-H hysteresis loop indicated that the magnetic spheres exhibit superparamagnetic characteristics at room temperature. Daunorubicin acting as a model drug was loaded into the carrier, and the maximum percent of envelop and load were 28.4% and 14.2% respectively. The drug controlled releasing behaviors of the carriers were compared in different pH media.     

Preparation and characterization of poly(l-lactic acid)/TiO2 nanoparticle nanocomposite films with high transparency and efficient photodegradability

Poly(l-lactic acid)-TiO₂ nanoparticle nanocomposite films were prepared by incorporating surface modified TiO₂ nanoparticles into polymer matrices. In the process of preparing the nanocomposite films, severe aggregation of TiO₂ nanoparticles could be reduced by surface modification by using carboxylic acid and long-chain alkyl amine. As a result, the nanocomposite films with high transparency, similar to pure PLA films, were obtained without depending on the amount of added TiO₂ nanoparticles. A TEM micrograph of the nanocomposite films suggests that the TiO₂ nanoparticles of 3-6 nm in diameter were uniformly dispersed in polymer matrices. Photodegradation of PLA-TiO₂ nanoparticle nanocomposite films was also investigated. The results showed that nanocomposite films could be efficiently photodegraded by UV irradiation in comparison with pure PLA.     

Sub-nanometer-thick Al2O3 Overcoat Remarkably Enhancing Thermal Stability of Supported Gold Catalysts

Supported gold nanoparticle catalysts show extraordinarily high activity in many reactions. While the relative poor thermal stability of Au nanoparticles against sintering at elevated temperatures severely limits their practical applications. Here atomic layer deposition (ALD) of TiO₂ and Al₂O₃ was performed to deposit an Au/TiO₂ catalyst with precise thickness con-trol, and the thermal stability was investigated. We surprisingly found that sub-nanometer-thick Al₂O₃ overcoat can su ciently inhibit the aggregation of Au particles up to 600 C in oxygen. On the other hand, the enhancement of Au nanoparticle stability by TiO₂ overcoat is very limited. Di use reffectance infrared Fourier transform spectroscopy (DRIFTS) of CO chemisorption and X-ray photoelectron spectroscopy measurements both con rmed the ALD overcoat on Au particles surface and suggested that the presence of TiO₂ and Al₂O₃ ALD overcoat on Au nanoparticles does not considerably change the electronic properties of Au nanoparticles. The catalytic activities of the Al₂O₃ overcoated Au/TiO₂ catalysts in CO oxidation increased as increasing calcination temperature, which suggests that the embed-ded Au nanoparticles become more accessible for catalytic function after high temperature treatment, consistent with our DRIFTS CO chemisorption results.