饮用水中天然有机物的分析与表征方法

天然有机物(NOM)是一类分布广泛、成分复杂的有机混合物,可严重影响饮用水的处理效率,并可能对出水水质产生严重的不利影响。因此,为了改进和优化饮用水的处理过程,在研究和实际应用阶段对NOM进行表征和定量以了解其结构特性和反应性具有重要意义。文中先对NOM的富集方法进行了介绍,接着梳理了不同分离方法的依据及作用,最后总结了各类表征方法的原理及应用,以期有助于对NOM和饮用水处理的深入研究。     

有机发光材料中间体1-羟基芘的合成工艺研究

1-羟基芘是一种重要的有机电致光材料中间体,该中间体能与一些芳烃及其衍生物进一步反应得到不同性质的光电材料,具有广阔的市场前景。为获得1-羟基芘,本文以芘为原料,在二氯甲烷溶液中,在三氯化铝的催化下与乙酰氯反应得到1-乙酰芘;然后与间氯苯过甲酸或过氧硼酸发生bayer-villiger反应,得到1-乙酰氧基芘;接着在甲醇和四氢呋喃混合溶液中水解得到1-羟基芘,该合成路线短,原料易得,适应工业化生产,经1HNMR光谱鉴定,产物与1-羟基芘结构一致。     

腐解稻草DOM提取液洗脱六价铬污染土壤试验研究

工矿企业产生的铬渣、含铬废水由于管理不善导致土壤铬污染严重,迫切需要寻求低成本铬污染土壤修复技术。提出腐解稻草中溶解性有机质（Dissolved Organic Matter, DOM）提取液洗脱铬污染土壤的技术,通过实验室模拟试验,以2种铬污染土壤（总铬含量为分别为121.54、941.90 mg/kg,六价铬含量分别为119.90、856.90 mg/kg）为研究目标,采用振荡淋洗法考察了固液比、淋洗时间、淋洗次数等因素对土壤中总铬、六价铬洗脱效果的影响,并探讨了淋洗前后铬形态变化及淋洗后土壤残留六价铬的持续钝化能力。研究结果表明：稻草经35 d腐解后的DOM提取液洗脱土壤中铬效果最佳,确定为最佳淋洗剂;固液比1：15、淋洗4h/次、淋洗2次为最佳淋洗工艺条件,该条件下,2种铬污染土壤总铬分别洗脱了47.79%、85.92%,六价铬含量分别削减了51.76%、95.09%;DOM提取液呈弱碱性,包含大量羧基、羟基及酚类物质,对水溶态、弱酸提取态和残渣态铬有较好的洗脱效果,有效降低了土壤环境风险,且能持续钝化淋洗后土壤中残余的六价铬。     

Functionalized metal–organic frameworks with strong acidity and hydrophobicity as an efficient catalyst for the production of 5-hydroxymethylfurfural

In the dehydration of fructose to 5-hydroxymethyl furfural(HMF), in situ produced water weakens the acid strength of the catalyst and causes the rehydration of HMF, causing unsatisfactory catalytic activity and selectivity. In this work, a class of benzenesulfonic acid-grafted metal–organic frameworks with strong acidity and hydrophobicity is obtained by the direct sulfonation method using 4-chlorobenzenesulfonic acid as sulfonating agent. The resultant MOFs have a specific surface area of greater than 250 m~2·g~(-1), acid density above 1.0 mmol·g~(-1), and water contact angle up to 129°. The hydrophobic MOF-Ph SO_3 H exhibits both higher catalytic activity and selectivity than MOF-SO_3 H in the HMF synthesis due to its better hydrophobicity and olephilicity. Moreover, the catalyst has a high recycled stability. At last, fructose is completely converted, and 98.0% yield of HMF is obtained under 120 °C in a DMSO solvent system. The successful preparation of the hydrophobic acidic MOF provides a novel hydrophobic catalyst for the synthesis of HMF.     

Exploring the methods on improving CH4 delivery performance to surpass the Advanced Research Project Ageney-Energy target

CH_4 storage associated with adsorbed natural gas(ANG) technology is an issue attracting great concern.Following the Advanced Research Project Agency-Energy(ARPA-E) targeted deliverable capacity of 315 cm~3·cm~(-3)(STP), hundreds of thousands of materials have been experimentally or theoretically evaluated,while the best results still show a 35% gap from the target. Moreover, recent theoretical research reveals that the target is beyond the possibility that real materials can be designed. To get rid of the awkward situation, we make attempts on investigating the CH_4 delivery performance under other operation conditions. Methods of raising the discharge temperature(to infinite high) or elevating the storage pressure(to 25 MPa) have been proved to show limited effectiveness. In this work, it is found that the ARPA-E target can be achieved by using a decreasing storage temperature strategy. By taking 280 Co RE(computation-ready, experimental) COFs(covalent organic frameworks) as ANG materials, when reduce the storage temperature to 190.6 K, the highest deliverable capacity can reach 392 cm~3·cm~(-3)(STP), and16.1% Co RE COFs can surpass the target. The target is also achievable when storage at 220 K. Structure performance relationships study shows strong correlation between deliverable capacity and void fraction. Hence, 120 hypothetical COFs are generated to ascertain the optimum void fraction. In addition,the performance of 2 D-COFs can be greatly enhanced by increasing the interlayer spacings, e.g. CH_4 deliverable capacity(storage at 190.6 K) of ATFG-COF can be improved from 239 to 411 cm~3·cm~(-3)(STP) when interlayer spacing is enlarged to 1.65 nm.     

Room-Temperature Solid-State Lithium Metal Batteries Using Metal Organic Framework Composited Comb-Like Methoxy Poly(ethylene glycol) Acrylate Solid Polymer Electrolytes

Solid polymer electrolyte with good thermal stability and flexibility is an excellent candidate for solid-state lithium metal batteries, while its low ionic conductivity caused by high crystallinity limits its application at ambient temperature. Here a metal organic framework (zeolitic imidazolate framework-8, ZIF-8) composited comb-like methoxy poly(ethylene glycol) acrylate polymer electrolyte (MCPE) with high ionic conductivity (9.96 × 10⁻⁵ S cm⁻¹ at 30 °C) is prepared by an in situ UV polymerization method. The as-prepared MCPE exhibits improved mechanical property due to the introduction of porous ZIF-8 nanofillers, which is beneficial to suppress the growth of lithium dendrites. Consequently, the LiFePO₄||MCPE||Li cells show a high capacity of 116 mAh g⁻¹ at 30 °C and 0.5 C, and maintain 89.4% of initial capacity after 150 cycles with the average Coulombic efficiency of 99.9%. These results demonstrate that the MCPE shows great potential in solid-state lithium metal batteries near room temperature.     

Enzymatic Synthesis of Glucose- and Xylose Laurate Esters Using Different Acyl Donors,Higher Substrate Concentrations,and Membrane Assisted Solvent Recovery

Glucose- and xylose laurate esters are enzymatically synthesized using equimolar substrate concentrations in 2-methyl-2-butanol, comparing free lauric acid with methyl- and vinyl-laurate as acyl donors. All reactions result in ≥70% acyl donor conversions after 72 h but the activated donors are also partially hydrolyzed to lauric acid, highlighting the difficulty in controlling water presence in this particular reaction system. The esterification of xylose generates a complex product profile, with several regioisomers of monoesters and diesters. The esterification of glucose is quite selective, forming mainly the 6-O monoester (≥96%) with a small presence of two diester isomers (4%). Increasing substrate concentration up to 800 millimoles kg⁻¹ results in lower conversion values (down to 58%) but shows that the reaction proceeds successfully even in the presence of high amounts of insoluble glucose. However, the reaction is less selective and the proportion of diester increases, becoming up to 46% (molar fraction) of the final product. Solvent recovery after esterification can be achieved by organic solvent nanofiltration through a polymeric membrane able to retain ≥80% of all reaction substrates and products. Practical Applications: The use of high substrate concentrations during the enzymatic synthesis of sugar ester biosurfactants leads to product titers that are more industrially appealing, without the need to find a solvent that can solubilize all initial substrate. The sustainability of the enzymatic conversion at mild temperatures can be enhanced by recycling of the reaction solvent through organic solvent nanofiltration, an energy efficient alternative to other traditional methods like distillation.     

磁性金属有机框架材料制备及吸附性能研究

利用简单的溶剂热法合成了MIL-101（Fe）/CoFe₂O₄和MIL-101（Fe）/NiFe₂O₄磁性金属有机框架纳米复合材料。通过X射线衍射仪（XRD）、扫描电子显微镜（SEM）、振动磁强计（VSM）、热重分析仪（TGA）和紫外可见分光光度计（UV）等对复合材料的相结构、形貌、磁性能和吸附性能进行了研究。将磁性金属有机框架材料用于吸附污水中罗丹明B（RhB）,研究了罗丹明B初始质量浓度对复合材料吸附能力的影响。结果表明,制备的磁性金属有机框架复合材料的形貌均匀、结晶度高,具有高的饱和磁化强度。复合物具有金属有机框架材料和磁性材料的双重优点。MIL-101（Fe）/CoFe₂O₄对罗丹明B有较高的吸附能力（97.3 mg/g）。热力学研究发现吸附等温方程符合Langmuir模型,吸附动力学研究表明吸附机制与吸附质和吸附剂有关。磁性金属有机框架纳米复合材料作为污水处理剂将具有广阔的应用前景。     

纳米粉及添加剂对压电陶瓷材料性能的影响

采用高能球磨法研磨出PZT-5纳米粉料，添加外购的纳米有机添加剂，按照传统的固相工艺法制备出了压电陶瓷材料，研究分析纳米粉料和纳米有机添加剂对压电陶瓷性能的影响。通过测试分析可以看出，纳米压电粉料与纳米有机添加剂的综合作用，降低了材料的烧结温度、相对介电常数εr,Qm值和以d31，提高了压电应变常数d333，从而压电电压常数g33、gh、dh成倍提高，这些对制作宽带、高灵敏度的换能器是很有好处的。     

铸件内析出性气孔形成及演化的直接观察与分析

采用透明模型合金实时观察了铸件析出性气孔的形成发展,结果发现,纯物质凝固时,析出性气孔的产生发生于凝固型壳形成之后,随着凝固自型壁向中心凝固,呈现自周边向中心的气条生长。对于合金凝固,析出性气孔在凝固基本完成之后伴随着热裂及缩松的发生开始产生,呈现一定的偏聚现象。浇注前熔体过热度的提高将使析出性气孔更加密集,铸型和环境温度的降低有利于降低气孔的数量及分布范围,采用真空除气,可有效地抑制析出性气孔的产生和热裂缩松缺陷的形成。