污泥基吸附剂对亚甲基蓝和环丙沙星的吸附性能研究

亚甲基蓝和环丙沙星是水体中2种污染物, 对生态环境有潜在危害. 本文以市政剩余活性污泥为原料, 氯化锌为活化剂热解制备污泥基吸附剂, 研究盐酸酸洗浓度、氯化锌浓度、热解温度、热解时间等对污泥基吸附剂吸附水中亚甲基蓝和环丙沙星性能的影响. 结果表明 (1)污泥基吸附剂对亚甲基蓝的吸附性能随盐酸酸洗浓度的增大而增加, 对环丙沙星的吸附性能则随盐酸酸洗浓度的增大呈先降后增趋势, 两者均在1.500mol·L-1盐酸浓度下取得最优值. (2)污泥基吸附剂对亚甲基蓝和环丙沙星的吸附性能随氯化锌浓度和热解温度的增加呈先升后降趋势, 在氯化锌浓度为4.0mol·L-1、热解温度为500℃时有最优值; 随着热解时间的延长, 污泥基吸附剂对亚甲基蓝和环丙沙星的吸附性能分别在500℃热解70min和80min时有最优值. (3)污泥基吸附剂的最佳制备条件为 氯化锌4.0mol·L-1活化2h、500℃热解70min和80min、1.500mol·L-1盐酸酸洗; 以此制得的污泥基吸附剂对亚甲基蓝和环丙沙星的去除率分别为97.7%和96.4%, 平衡吸附量分别为97.9mg·g-1和3.9mg·g-1, 且污泥基吸附剂对亚甲基蓝和环丙沙星的吸附过程均符合准二级动力学方程.     

Tailoring Morphology of PVDF-HFP Membrane via One-step Reactive Vapor Induced Phase Separation for Efficient Oil-Water Separation

Poly(vinylidene fluoride-co-hexafluoropropylene)(PVDF-HFP) receives increasing attention in membrane separation field based on its advantages such as high mechanical strength, thermal and chemical stability. However, controlling the microporous structure is still challenging.In this work, we attempted to tailor the morphology of PVDF-HFP membrane via a one-step reactive vapor induced phase separation method.Namely, PVDF-HFP was dissolved in a volatile solvent and then was cast in an ammonia water vapor atmosphere. After complete evaporation of solvent, membranes with adjustable porous structure were prepared, and the microstructures of the membranes were analyzed by scanning electron microscopy, Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy and X-ray diffraction characterizations. Based on the results, a mechanism of dehydrofluorination induced cross-linking of PVDF-HFP has been suggested to understand the morphology tailoring.To our knowledge, this is the first report of one-step reactive vapor induced phase separation strategy to tailor morphology of PVDF-HFP membrane. In addition, the membranes prepared in the ammonia water vapor exhibited enhanced mechanical strength and achieved satisfactory separation efficiency for water-in-oil emulsions, suggesting promising potential.     

Generalized Jacobi spectral Galerkin method for fractional pantograph differential equation

This work is concerned with the extension of the Jacobi spectral Galerkin method to a class of nonlinear fractional pantograph differential equations. First, the fractional differential equation is converted to a nonlinear Volterra integral equation with weakly singular kernel. Second, we analyze the existence and uniqueness of solutions for the obtained integral equation. Then, the Galerkin method is used for solving the equivalent integral equation. The error estimates for the proposed method are also investigated. Finally, illustrative examples are presented to confirm our theoretical analysis.     

常压下玉米秸秆液化工艺的优化及其生物油分析

随着化石能源的日益短缺，可再生木质生物质资源的利用越来越受到重视，常压液化技术是生物质资源高效利用的主要方式之一。利用单因素方法，探讨液化温度、复配液化剂二甘醇（DEG）与1,2-丙二醇（PG）的混合比、液固比、催化剂磷酸的用量、反应时间等因素对玉米秸秆液化得率的影响，以便优化其液化工艺；然后采用热重分析仪（TGA）、气相色谱-质谱技术（GC-MS）和核磁共振（NMR）技术对此优化条件下所得生物油的挥发降解特性和主要组成成分进行了检测探讨。分析表明，玉米秸秆液化时优化工艺参数为：液化温度170 ℃，液化剂DEG与PG混合比1∶2，液固比5∶1，H₃PO₄用量10%，反应时间45 min；此时玉米秸秆液化得率高至99.50%。TGA结果表明，此条件下所得生物油含有80%以上碳数小于25的化合物，热解后最终残炭量约为15%。GC-MS表明，可以检测出此生物油中含有的39种有机物，其中，醇类有机物的含量最多，酚类有机物的含量次之，它们相对含量依次是70.70%和25.63%，其还含有一定量的有机酸（2.80%）、醚类（0.64%）、酯类（0.10%）和酮类（0.13%）等有机物；其组分十分复杂，高含氧量，稳定性较差。1H-和13C-NMR分析表明，不同化学位移δ与生物油中不同类型的质子和碳原子相对应，明确生物油中不同类型H和C的分布，有利于对其分子结构进行深入探讨。这些研究为非木材生物质高效液化条件的选择及液化产物制备化学品和生物燃油给予理论基础与应用支持，促进了生物质资源的有效转化利用及其生物质基产品的开发。     

Enhanced thermal conductivity and mechanical properties of polymeric composites through formation of covalent bonds between boron nitride and rubber chains

Hexagonal boron nitride (BN) platelets, also known as white graphite, are often used to improve the thermal conductivities of polymeric matrices. Due to the poor interfacial compatibility between BN platelets and polymeric matrices, in this study, polyrhodanine (PRd) was used to modify BN platelets and prepared functionalized BN-PRd platelets, thereby enhancing the interfacial interaction between the thermal conductive filler and polymeric matrix. Then, BN-PRd platelets were dispersed into the nitrile butadiene rubber (NBR) matrix to yield high thermally conductive composites. The presence of N? C═S groups in PRd allowed the combination of PRd and NBR chains containing stable covalent bonds via vulcanization reaction. The thermal conductivity of the as-prepared 30 vol% BN-PRd/NBR composite reached 0.40 W/mK, representing an increment of 135% over pure NBR (0.17 W/mK). In addition, the largest tensile strength of NBR composite containing 30 vol% BN-PRd platelets was 880% times of pure NBR. The 30 vol% BN-PRd/NBR composite also displayed a relatively high dielectric constant (9.35 at 100 Hz) and a low dielectric loss tangent value (0.07 at 100 Hz), indicating their usefulness as dielectric flexible materials of microelectronics. In sum, the simplicity and good efficiency of formation of covalent bonds between boron nitride and rubber chains look very promising for large-scale industrial production of high thermally conductive composites.     

Biocatalytic Feedback-Controlled Non-Newtonian Fluids

Non-Newtonian fluids are ubiquitous in daily life and industrial applications. Herein, we report an intelligent fluidic system integrating two distinct non-Newtonian rheological properties mediated by an autocatalytic enzyme reaction. Associative polyelectrolytes bearing a small amount of ionic and alkyl groups are engineered: by carefully balancing the charge density and the hydrophobic effect, the polymer solutions demonstrate a unique shear thickening property at low pH while shear thinning at high pH. The urea-urease clock reaction is utilized to program a feedback-induced pH change, leading to a strong upturn of the nonlinear viscoelastic properties. As long as the chemical fuel is supplied, two distinct non-Newtonian states can be achieved with a tunable lifetime span. As a proof of concept, we demonstrate how the physical energy-driven nonequilibrium properties can be manipulated by a chemical-fueled process.     

Redox-Active Two-Dimensional Covalent Organic Frameworks (COFs) for Selective Reductive Separation of Valence-Variable,Redox-Sensitive and Long-Lived Radionuclides

We report the first example of 2D covalent organic framework nanosheets (Redox-COF1) for the selective reduction and in situ loading of valence-variable, redox-sensitive and long-lived radionuclides (abbreviated as VRL nuclides). Compared with sorbents based on chemical adsorption and physical adsorption, the redox adsorption mechanism of Redox-COF1 can effectively reduce the impact of functional group protonation under the usual high-acidity conditions in chemisorption, and raise the adsorption efficiency from the monotonous capture by pores in physisorption. The adsorption selectivity for UO₂²⁺ reaches up to unprecedented ca. 97 % at pH 3, more than for any analogous adsorbing material.     

Iridium-Catalyzed Enantioselective Hydrogenation of Oxocarbenium Ions: A Case of Ionic Hydrogenation

Ionic hydrogenation has not been extensively explored, but is advantageous for challenging substrates such as unsaturated intermediates. Reported here is an iridium-catalyzed hydrogenation of oxocarbenium ions to afford chiral isochromans with high enantioselectivities. A variety of functionalities are compatible with this catalytic system. In the presence of a catalytic amount of the Brønsted acid HCl, an α-chloroether is generated in situ and subsequentially reduced. Kinetic studies suggest first-order kinetics in the substrate and half-order kinetics in the catalyst. A positive nonlinear effect, together with the half kinetic order, revealed a dimerization of the catalyst. Possible reaction pathways based on the monomeric iridium catalyst were proposed and DFT computational studies revealed an ionic hydrogenation pathway. Chloride abstraction and the cleavage of dihydrogen occur in the same step.     

Origins of Boosted Charge Storage on Heteroatom-Doped Carbons

Although tremendous efforts have been devoted to understanding the origin of boosted charge storage on heteroatom-doped carbons, none of the present studies has shown a whole landscape. Herein, by both experimental evidence and theoretical simulation, it is demonstrated that heteroatom doping not only results in a broadened operating voltage, but also successfully promotes the specific capacitance in aqueous supercapacitors. In particular, the electrolyte cations adsorbed on heteroatom-doped carbon can effectively inhibit hydrogen evolution reaction, a key step of water decomposition during the charging process, which broadens the voltage window of aqueous electrolytes even beyond the thermodynamic limit of water (1.23 V). Furthermore, the reduced adsorption energy of heteroatom-doped carbon consequently leads to more stored cations on the heteroatom-doped carbon surface, thus yielding a boosted charge storage performance.     

Noise-induced phenomena in a versatile class of prototype dynamical system with time delay

Nonlinear Dynamics - This work presents a general class of prototype birhythmic dynamical systems, which can be extensively used to study the generation of complex bifurcation of limit cycles....