功能性纳米零价铁的构筑及其对环境放射性核素铀的富集应用研究进展

随着核能的广泛应用和核技术的快速发展,环境中放射性核素铀的污染日益严峻.纳米零价铁（Nanoscale Zero Valent Iron：nZVI）因其具有廉价、制备简便、高表面活性及对铀高效的吸附性能等特性而逐渐成为环境中铀污染处理的良好材料.采用可行的方法制备纳米零价铁复合材料,借助单体材料之间的协同效应可进一步提高材料对铀酰的吸附性能.因此,纳米零价铁复合材料的制备以及应用成为近期环境科学领域的研究热点之一.针对纳米零价铁及其复合材料对环境中铀酰的去除研究进行了概述和展望,包括纳米零价铁及其复合材料的制备方法、去除效果及去除机理,并且简要探讨了纳米零价铁及其复合材料在环境放射性污染治理的应用前景,以期为今后的深入研究和实际应用提供参考依据.     

纳米铁及铁基纳米复合粒子在环境修复中的研究进展

由于纳米零价铁及铁基纳米复合粒子对大多数常见的环境污染物,如重金属离子、卤代有机物等均具有转化和降低毒性的作用,因此,在环境修复领域,它们已成为研究的热点之一。 纳米零价铁及铁基纳米复合粒子的比表面积大,反应活性高,应用灵活,为大多数具有挑战性的环境污染问题提供了一个有效的解决方法。 本文主要阐述了近些年来纳米零价铁及铁基纳米复合粒子在环境修复中的具体应用,同时也评估了其对环境微生物的潜在毒理效应,为以后进一步研究工作奠定一定的理论基础。     

修饰型纳米零价铁降解有机卤化物的研究

纳米零价铁技术由于其独特的性质,已成为国内外研究的热点。对纳米零价铁进行改性,可有效提高其降解效率,解决纳米零价铁易团聚等问题,是解决卤代有机物污染问题行之有效的方法之一,特别适合于土壤和地下水的原位修复。本文从修饰型纳米零价铁的合成方法、制备原理、降解效果、应用范围、降解机理、修饰因素的影响等几方面进行了分析,着重介绍了国内外运用修饰型纳米零价铁降解卤代有机物的研究成果和现状,讨论分析了该技术存在的问题,并对该技术的发展前景进行了展望。     

纳米零价铁去除水中重金属离子的研究进展

重金属离子危害严重.本文综述了近几年纳米零价铁去除水中重金属离子的研究,总结了纳米零价铁去除水中重金属离子的机理,主要包括:纳米零价铁的表面吸附-配合、还原、吸附-还原,并对纳米零价铁在这一领域的应用进行了展望.     

硫化纳米零价铁研究进展: 合成、性质及环境应用

纳米零价铁(nanoscale Zero-Valent Iron, nZVI)是水环境修复领域研究最广泛的材料之一, 但易团聚和氧化、电子选择性差等缺点制约了其实际应用. 对nZVI表面进行硫化制备成硫化纳米零价铁(Sulfidated nanoscale Zero-Valent Iron, S-nZVI), 能够提高纳米颗粒的分散性能、增强稳定性, 提高电子选择性, 已成为目前研究热点. 本综述以“合成方法—理化性质—应用性能”为主线展开论述, 首先总结了不同的硫化方法对S-nZVI理化性质的影响, 重点阐释通过调控合成条件(硫化顺序、硫化剂种类、硫铁比等)以调节S-nZVI的微观结构和界面元素化学形态(实际S/Fe、硫分布、FeS_x形态等), 从而改变其宏观性质(亲疏水、析氢、导电性等), 最终实现对有机污染物与金属污染物的定向去除. 此外, 详细综述了S-nZVI用于去除卤代有机物、硝基苯有机物和重金属等污染物方面的研究进展, 并对未来的研究方向进行了展望.     

还原氧化石墨烯负载零价铁的合成及对TNT废水处理

选取比表面积大且导电性能优良的还原氧化石墨烯（rGO）作为支撑材料,负载还原性强但极易团聚的纳米零价铁（nZVI）,制得还原氧化石墨烯负载零价铁（nZVI/rGO）复合材料.通过X射线衍射（XRD）、傅里叶变换红外光谱（FTIR）、扫描电子显微镜（SEM）与X射线光电子能谱（XPS）等测试手段对零价铁的负载情况、材料表面微观形貌与反应前后nZVI/rGO材料表面铁元素的含量与组成进行表征.考察了溶液初始pH值、材料投加量和理论零价铁负载量等因素对nZVI/rGO去除2,4,6-三硝基甲苯（TNT）的影响,研究了nZVI/rGO材料去除TNT的反应机理.通过正交实验可知,nZVI/rGO对含TNT废水的处理在较宽的反应条件范围内都可达到处理要求,在理论零价铁的负载量为3.0 g/g rGO,溶液初始pH为6,材料投加量为40 g/L时效果最佳,可将废水中TNT处理到检出限0.1 mg/L以下.     

纳米复合材料固定化酶的研究进展

载体材料的选择对固定化酶的性能有着至关重要的影响。纳米复合材料不仅具有纳米尺寸的特性,而且可以克服单一材料的不足,在固定化酶领域引起了广泛关注。本文就目前在固定化酶领域使用的纳米复合载体分类进行了系统的阐述,重点介绍了目前在固定化酶研究领域运用较为广泛的硅基纳米复合材料、碳基纳米复合材料和纳米纤维复合材料等材料的制备方法及不同材料对酶学性能的影响,并对这些纳米复合材料固定化酶发展前景进行了展望。     

纳米零价铁与重金属的反应:“核-壳”结构在重金属去除中的作用

重金属是一类毒性较高、处理难度较大的环境污染物.纳米零价铁因为具有高效分离、固定重金属的潜能而受到广泛关注.其独特的纳米级核壳结构和表面性质使纳米零价铁能够通过吸附、还原和沉淀等多种作用高效去除重金属.现代仪器分析手段的进步,特别是高分辨电子显微成像技术的发展,为深入研究纳米零价铁的微观结构以及纳米零价铁与重金属的作用机理开辟了新的视角.本文重点讨论了纳米零价铁的结构、性质及其在重金属去除中的作用.研究借助高分辨率的球差校正扫描透射电镜(Cs-STEM)成像,配合高灵敏度的X射线能谱仪(XEDS)进行化学分析,旨在更好地了解纳米零价铁的精细结构及其与重金属的界面反应过程和机理.在深入理论研究的同时,通过"小试—中试—工程"逐级放大的方法,系统论证了纳米零价铁处理重金属废水的可行性.结果表明,纳米零价铁可有效、同步去除实际废水中铜、砷、铅、锌等多种重金属,并具有较高的去除负荷.     

纳米复合材料固定化酶的研究进展

载体材料的选择对固定化酶的性能有着至关重要的影响。纳米复合材料不仅具有纳米尺寸的特性,而且可以克服单一材料的不足,在固定化酶领域引起了广泛关注。本文就目前在固定化酶领域使用的纳米复合载体分类进行了系统的阐述,重点介绍了目前在固定化酶研究领域运用较为广泛的硅基纳米复合材料、碳基纳米复合材料和纳米纤维复合材料等材料的制备方法及不同材料对酶学性能的影响,并对这些纳米复合材料固定化酶发展前景进行了展望。     

纳米零价铁在水相反应中的表面化学和晶相转化

纳米零价铁在水相中的表面化学特性和晶相等性质变化,将影响其反应活性及环境归趋等.总结近期课题组关于纳米零价铁在水相中表面化学和晶相转化的研究进展,为纳米零价铁污染控制化学提供基础理论.重点探讨水中有无溶解氧、不同水力学条件复氧（静态和扰动）、重金属共存、无机阴离子共存对纳米零价铁颗粒表面化学特性和晶相转变的影响.同时也研究高分子电解质表面修饰后,颗粒在水相中表面及晶相的演变及对重金属去除性能的影响.研究表明,纳米零价铁与水相中的水分子、溶解氧、重金属离子及无机阴离子反应,零价铁失去电子演变为氧化铁、羟基氧化铁等;环境条件对颗粒结构性能产生影响,从而影响污染物去除效率及其在环境中的归趋.未来研究将重点探讨结构性能动态变化与不同污染物之间反应性能的影响,建立纳米颗粒的结构与性能之间关系模型,为纳米零价铁材料的环境应用提供理论依据.     

二氧化碳和丙烯直接合成甲基丙烯酸的NiPMo/TiO2催化剂的研究

用溶胶-凝胶法以磷钼酸(MPA)的镍盐溶液水解钛酸四丁酯制备了NiPMo/TiO2催化剂.使用ICP、 XRD、 TG-DTA、 IR、 TPD-MS和微反应技术研究了催化剂的化学组成、热稳定性、化学吸附性质和催化反应性能.杂多钼酸盐与TiO2通过O2-在TiO2表面发生了键合.在623 K下,杂多阴离子仍保持原有的Keggin结构.CO2在Lewis酸位Ni(Ⅱ)和Lewis碱位Ni-O-Mo的桥氧协同作用下生成CO2卧式吸附态Ni(Ⅱ)←O-(CO)←(O--Ni).丙烯有多种吸附态在催化剂上吸附.在563 K、 1 MPa和空速1500 h-1的反应条件下,丙烯的摩尔转化率为3.2%,产物MAA选择性为95%.     

CoFe2O4自形成磁性液体场致结构化对磁化的影响

The Langevin paramagnetic theory can’t describe the relation between magnetization of ferrofluids and applied magnetic field. The structuralization of ferrofluids, which is considered the main influence factor of the magnetization, is regarded. The part of magnetization works is deposited when the structure is forming. This action influences the magnetization of ferrofluids directly or indirectly. On the base of the “compressing” model, the Langevin function that usually describes the magnetization of ferrofluid is modified, and a well-fitted curve is obtained. An equation of the relation between the equivalent volume fraction after being “compressed” and the intensity of magnetic field is discovered, which approximately describes the process of magnetization. The relation between the approximate initial susceptibility and the volume fraction can be obtained from modified formula.     

Highly regioselective Buchwald–Hartwig amination at C-2 of 2,4-dichloropyridine enabling a novel approach to 2,4-bisanilinopyridine (BAPyd) libraries

The highly regioselective Buchwald–Hartwig amination at C-2 of the cheap and readily accessible reagent, 2,4-dichloropyridine with a range of anilines and heterocyclic amines is described. This new methodology is robust and provides a facile access to 4-chloro-N-phenylpyridin-2-amines on 0.25 mol scale. These intermediates undergo a further Buchwald–Hartwig amination at higher temperature to enable rapid exploration of the chemical space at C-4 and to provide a library of 2,4-bisaminopyridines.     

Sulfur-directed metal-free and regiospecific methyl C(sp3)–H imidation of thioanisoles

Regiospecific and direct imidation of the methyl C(sp³)–H bond of thioanisoles is realized under mild and metal-free conditions with N-fluorobis(benzenesulfonyl)imide as an oxidant and nitrogen source. Proposed mechanism suggests that thionium ion intermediates and a Pummerer-type reaction are involved. The imidation has advantages such as high step-economy, excellent functionality tolerance, and regiospecificity, giving structurally diverse imidation products.     

Selective syntheses of 2H-1,3-oxazines and 1H-pyrrol-3(2H)-ones via temperature-dependent Rh(II)-carbenoid-mediated 2H-azirine-ring expansion

The Rh(II)-catalyzed reaction of 2-carbonyl-substituted 2H-azirines with ethyl 2-cyano-2-diazoacetate or 2-diazo-3,3,3-trifluoropropionate provides an easy access to 2H-1,3-oxazines and 1H-pyrrol-3(2H)-ones. These compounds can be selectively prepared from the same starting material using temperature as the only varied parameter. The 2-azabuta-1,3-diene intermediate, a common precursor for both heterocyclic products, isomerizes into 2H-1,3-oxazine under kinetic control, while 1H-pyrrol-3(2H)-one is the sole product of the reaction at elevated temperatures. According to DFT-calculations a one-atom oxazine ring contraction involving ring-opening to a 2-azabuta-1,3-diene intermediate, followed by a 1,5- and 1,2-prototropic shift leads to the consecutive formation of imidoylketene and azomethine ylide, which then further undergo cyclization to the pyrrole derivative.     

Copper catalyzed/mediated synthetic methodology for ebselen and related isoselenazolones

Scope of the copper catalyzed/mediated selenium-nitrogen coupling reaction has been studied for the synthesis of isoselenazolones. It is noticed that the 2-chloro, 2-bromo-, and 2-iodo-aryl amides substrates can be exploited in the selenium-nitrogen coupling reaction by employing 25-100 mol % of CuI/1,10-phenanthroline (L) and potassium carbonate as a base in DMF. Furthermore, electron rich 2-chloro-arylamides also underwent selenium-nitrogen coupling reaction to give biologically important selenium-nitrogen heterocycles. Also, copper-catalyzed selenium-nitrogen coupling reaction has been meticulously applied for the synthesis of diaryl diselenides having methoxy, amine, and amide functionality from respective aryl iodides in the presence of stoichiometric amount of succinimide as an external Se-N coupling partner.     

Knoevenagel condensation catalyzed by novel Nmm-based ionic liquids in water

A series of novel N-methyl morpholine (Nmm) based ionic liquids with 1,2-propanediol group were synthesized and used as catalysts for Knoevenagel condensation at room temperature in water. Under the effect of the catalyst, various aldehydes or aliphatic ketones could react with a wide range of activated methylene compounds well, including malononitrile, alkyl cyanoacetate, cyanoacetamide, β-diketone, barbituric acid, 2-arylacetonitrile and thiazolidinedione. Furthermore, most of the products could be separated just by filtrating and washing with water. Additionally, the catalyst is recyclable and applicable for the large-scale synthesis.     

Construction of polyheterocyclic spirotetrahydrothiophene derivatives via sulfa-Michael/aldol cascade reaction

A series of polyheterocyclic spirotetrahydrothiophene derivatives were obtained in moderate to excellent yields via a catalyst-free sulfa-Michael/aldol cascade reaction of chalcones 1 and commercially available 1,4-dithiane-2,5-diol 2 under mild conditions. We also present the first asymmetric sulfa-Michael/aldol cascade reaction of chalcones 1 and commercially available 1,4-dithiane-2,5-diol 2 with moderate to good enantioselectivities catalyzed by readily available chiral phase-transfer catalysts (PTCs).     

Suzuki-Miyaura reactions of the soluble guanylate cyclase inhibitor NS2028: a non-product specific route to C-8 substituted analogues

Both soluble guanylate cyclase (sGC) inhibitors ODQ 1 and NS2028 2 are synthesized via improved protocols. In the former case treating 3,4-dihydroquinoxalin-2(1H)-one oxime 8, which can be prepared in two steps from 1,2-benzenediamine, with 1,1′-carbonyldiimidazole (CDI) gives the dihydro-ODQ 10 that in the presence of KMnO₄ oxidises to give ODQ 1 in an overall yield of 46% starting from 1,2-benzenediamine. In the latter case, the synthesis affords NS2028 2 from 2-amino-4-bromophenol 3 in three steps with an overall yield of 85% and avoids the need for chromatography. Furthermore, Suzuki-Miyaura reaction conditions are described that enable the preparation of 8-aryl and 8-heteroaryl derivatives of NS2028 directly from NS2028 2. Finally, demethylation of the 8-(methoxyphenyl) substituted analogues afforded the 8-(hydroxyphenyl) derivatives 40-42. All new products are fully characterised.