微生物燃料电池生物阴极

微生物燃料电池(microbial fuel cells, MFCs)利用微生物处理废水的同时产电,是一种清洁可再生能源技术。近年来新兴起的生物阴极是指阴极室中的功能微生物附着在电极表面形成生物膜,电子由电极传递给微生物并发生相应的生物电化学反应;是微生物燃料电池研究的一个重要方向。本文根据厌氧、好氧操作体系的不同将生物阴极进行分类;归纳总结了微生物组成、电极和分隔材料的研究进展,探讨了生物阴极在去除污染物和生成高附加值产品中的实际应用,并提出了其将来发展的可能方向。     

用于生物电化学系统的石墨烯电极新进展

可持续社会的发展需要成本低, 并从废物或废水中提取能源或将能源转化为产品的环境友好技术. 近年兴起的生物电化学系统(BESs)利用微生物催化不同电化学反应, 是将废物或废水中能量转化为电能等多种产品的发展前景广阔的新技术. 当有关反应的吉布斯自由能小于零, 系统输出电能, 此时的BESs即为微生物燃料电池(MFCs); 相反, 若反应的吉布斯自由能为正值, 此时的BESs被称为微生物电解电池(MECs). 随着研究工作的不断深入和拓展, BESs的电极性能已成为制约其应用的瓶颈. 石墨烯以其独特的结构和优异的材料性能在BESs领域, 特别是MFCs中得以应用. 本文参考了最新的文献资料, 综述了石墨烯应用于BESs的发展现状, 包括应用于MFCs的石墨烯电极、掺杂石墨烯电极、担载石墨烯电极, 对其在MECs中可能的应用, 以及未来发展趋势予以展望.     

微生物燃料电池

微生物燃料电池 (Microbial Fuel Cells,MFCs) 是一种利用微生物作为催化剂,将燃料中的化学能直接转化为电能的装置。本文首先简要介绍了MFCs 的发展简史和基本原理,针对MFCs 产电性能低的现状,分别从产电微生物、电池结构、质子交换膜(PEM)、电极以及电解液等方面着重综述了近几年有关提高MFCs 产电性能的研究进展。最后介绍了关于MFCs 的另一些有趣的研究方向：植物MFCs,生物阴极MFCs,以及污水脱氮和有毒废水处理。     

废水生物处理过程中微生物胞外聚合物与污染物的分子间相互作用

生物处理是废水处理的主要技术手段,其中微生物在新陈代谢过程中会分泌一种复杂的高分子混合物——胞外聚合物(EPS),覆盖在微生物表面,它们是影响微生物表面特性的关键物质,在水体环境和废水处理系统中对污染物的迁移转化和去除起着至关重要的作用.研究结果表明,EPS能够利用其丰富的官能团吸附水体中的重金属和有机污染物,还可以通过氢键与氮、磷等营养元素发生相互作用.另外EPS具有一定的氧化还原特性,可以通过氧化还原反应改变污染物的存在形式.因此EPS在废水生物处理过程中具有重要的作用,可以影响重金属和有机污染物在废水生物处理过程中的去除和转化.发展高灵敏的分析方法,深入研究和理解EPS与不同污染物的分子间相互作用,对于阐明不同污染物在废水生物处理过程中的去除机制具有重要的指导意义.     

零价铁耦合厌氧微生物法在废水处理中的应用

零价铁(ZVI)与厌氧微生物的耦合是一项很有前景的技术,在难降解有机废水的去除中得到了广泛关注。该耦合技术将ZVI技术的高效性与厌氧生物技术的经济性有效融合,在多元微电场和厌氧微生物协同作用下,有效降低难降解有机物的生物抑制性和毒性。本文综述了此技术处理工业废水的潜在机理、实际应用中主要操作参数及影响条件以及处理含氯化合物、重金属、染料等生物难降解污染物的研究进展。归纳了ZVI与厌氧微生物耦合对上述污染物进行高效去除的研究现状,并对该技术在实际工程应用方面的可行策略进行了展望。     

生物阴极微生物燃料电池

传统微生物燃料电池(microbial fuel cells,MFCs)主要由生物阳极与非生物阴极组成,属于半生物燃料电池,存在化学药剂再生困难、需要铂等贵金属催化及成本高等缺陷。生物阴极则利用微生物参与阴极反应克服了这些缺陷。微生物参与MFCs阴极反应,最初在海底沉积物MFCs中被发现。为了提高空气-生物阴极的产电效率,人们进行了以铁、锰等过渡金属氧化物修饰电极材料的研究。在厌/缺氧环境中,生物阴极可将硝酸盐和硫酸盐等作为最终电子受体。对生物阴极研究的深入为MFCs工业化应用开辟了道路,此外,本文在文献综述的基础上提出了铁锰联合修饰生物阴极材料的可能性。     

铁基纳米粒子改性碳布复合材料的制备及其在微生物燃料电池阳极中的应用

微生物燃料电池(Microbial fuel cells, MFCs)可将废水中的有机物直接转化为电能,提供了可持续电能的潜在解决方案。然而,MFCs在实际应用中存在细菌负载能力低、阳极与电化学活性生物膜之间的胞外电子传递(Extracellular electron transfer, EET)效率相对较差等不足。本研究采用绿色高效的微波辅助方法和高温退火工艺,成功制备了铁基纳米粒子改性碳布(Fe₃C/Fe@CC),此复合材料具有较好的生物相容性和电催化活性,可作为MFCs的阳极材料。实验结果表明,基于Fe₃C/Fe@CC复合材料的MFCs的功率密度高达2209 mW/m²,相比基于纯碳布阳极的MFCs(1933 mW/m²)提高了17%,这主要是因为Fe₃C/Fe@CC能够有效提高微生物与电极之间的EET效率,增大电化学活性表面积,同时促进产电菌地杆菌(Geobacter)的富集。本研究采用微波辅助和高温退火方法快速制备了高导电复合阳极,为MFCs阳极的大规模制备提供了一种...     

光催化耦合微生物同步降解污染物

由于水体中新兴污染物不断增多,如何运用新型处理技术来弥补传统污水处理方法的缺陷已成为当前的研究热点。光催化耦合微生物同步降解污染物(ICPB)在保留生物法处理废水优点的同时,耦合了光催化高效、迅速的特性,可实现对多种污染物质的有效降解,节约了能源和成本,成为水体污染物有效去除的一个重要研究方向。ICPB体系主要由多孔载体、光催化材料及生物膜构成;其主要的工作原理是通过光激发载体上的光催化材料,将水体中难生物降解的污染物转化为可生物降解的物质,同时在载体内部微生物的代谢作用下,将这些污染物的中间降解产物继续矿化。本文根据光催化耦合微生物同步降解污染物体系中的关键构成,归纳总结了载体种类、光催化材料和负载生物的研究进展,探讨了该方法在去除水体污染物中的实际应用,并展望了其将来发展的方向和趋势。     

聚氨酯泡沫材料用于环境中金属离子监测及污染物去除的研究进展

聚氨酯泡沫材料具有加工成型简便、成本低廉、孔结构丰富、比表面积大、对环境中污染物吸附性能强、耐老化和抗有机溶剂浸蚀等优点,在环保与监测领域中的应用正受到广泛关注。本文重点综述了聚氨酯泡沫材料在金属离子富集与分离、固定化微生物去除废水中的重金属离子和有机污染物等环境保护领域的应用,并对其应用前景作了展望。     

生物膜电极法降解水中2-萘酚的影响因素

以2-萘酚为目标污染物,在对比电化学法和微生物法降解效果的基础上,研究了隔膜式电解体系中基体材料性质、电解池隔膜种类、温度和电流密度对生物膜电极法降解2-萘酚作用效率的影响.结果表明,生物膜电极法相比传统的电化学法和微生物法对2-萘酚类污染物的去除有一定优势,其作用效果与微生物生长状态有直接关系.以碳毡为基体的生物膜电极降解效果起始阶段优于钛网基生物膜电极,但一段时间后钛网基生物膜电极降解性能更稳定.阴离子交换隔膜电解池体系对2-萘酚的降解效果优于阳离子交换隔膜电解池体系,35℃条件下0.5 mA/cm²电流密度是最佳作用条件.     

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%.     

Synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives

Different approaches for the synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives from simple amino acids have been investigated. A library of 33 precursors for the preparation of N-hydroxy pyrazinones was obtained in moderate to good yields.     

A general and convenient synthesis of 4-(tosylmethyl)semicarbazones and their use in amidoalkylation of hydrogen,heteroatom, and carbon nucleophiles

A general synthesis of previously unknown semicarbazone-based α-amidoalkylating reagents, 4-(tosylmethyl)semicarbazones, has been developed. The synthesis involved three-component condensation of semicarbazones of aliphatic or aromatic aldehydes with the same or other aldehydes and p-toluenesulfinic acid. The scope and limitations of this reaction were investigated. The compounds obtained were demonstrated to be an efficient α-(4-semicarbazono)alkylating agents. They were reacted with H- (sodium borohydride), O- (sodium methylate), S- (sodium phenylthiolate), N- (pyrrolidine, sodium succinimide), P- (trialkyl phosphites), and C-nucleophiles (sodium diethyl malonate) to give the corresponding products of the tosyl group substitution, 4-substituted semicarbazones, including analogues of nitrofurazone. Among the prepared compounds tested in vitro for antibacterial and antifungal activity, three nitrofuryl-containing semicarbazones exhibited high biological activities with minimum inhibitory concentration (MIC) values of 8–32 μg/mL.     

Toward new camptothecins. Part 6: Synthesis of crucial ketones and their use in Friedländer reaction

In the context of the preparation of camptothecin and luotonin A analogs, the synthesis of some key keto-precursors and their use in Friedländer condensation are described. This paper also focuses on the stability of these keto intermediates and emphasizes the major differences between indolizinones and pyrroloquinazolinones series. Noteworthy is also the report of some original structures isolated as by-products of some experiments.     

Synthesis of novel chiral bidentate hydroxyalkyl-N-heterocyclic carbene ligands and their application in palladium-catalyzed Mizoroki–Heck couplings and asymmetric addition of diethylzinc to benzaldehyde

A small library of new chiral bidentate hydroxyalkyl-imidazolium salts 1 is conveniently synthesized on multi-gram scale from inexpensive and commercially available chiral pool amino acids. The corresponding carbenes, generated by deprotonation of imidazolium salts 1, in combination with palladium(II) chloride were tested in the Mizoroki–Heck coupling reaction. The most significant results in terms of yields and reactivities were achieved with low catalyst loading. The catalytic activities of these imidazolium salts were also investigated in the asymmetric addition of diethylzinc to benzaldehyde. The use of MgO nanoparticles as an additive in conjunction with these ligands played a crucial role in increasing the efficiency of these reactions.     

α-Amino acid derived enaminones and their application in the synthesis of N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates and other heterocycles

A new and simple synthesis of novel N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates, which exist in equilibrium with their 4-oxo tautomers, has been developed in two steps starting from N-protected α-amino acids. The key intermediates are enaminones, which can also be isolated, characterized, and used for the construction of other functionalized heterocycles, before they spontaneously decompose to pyrrole products. 4-Hydroxypyrroles are prone to partial aerial oxidation but can be efficiently alkylated or reduced to stable polysubstituted pyrrolidine derivatives.     

Specific intramolecular aromatic CH insertion of diazosulfonamides

The chemoselectivity in the intramolecular CH insertion of various diazosulfonamides has been experimentally studied. The results reveal that the aliphatic 1,4-, 1,5-, or 1,6-C(sp³)?H insertions of diazosulfonamides are not accessible, while the aromatic 1,5-C(sp²)?H insertion can be realized specifically by adjusting the diazo-adjacent group. In addition, the general chemoselectivities in the intramolecular CH insertions of diazosulfonyl compounds are summarized. Generally, diazosulfones undergo both aromatic 1,5-C(sp²)?H and aliphatic 1,5- and 1,6-C(sp³)?H insertions, while diazosulfonates undergo aliphatic 1,5- and 1,6-C(sp³)?H insertions. However, diazosulfonamides only undergo aromatic 1,5-C(sp²)?H insertion.     

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.     

Microwave-assisted copper-catalyzed stereoselective ring expansion of three-membered heterocycles with α-diazo-β-dicarbonyl compounds

Microwave-assisted copper-catalyzed ring expansions of three-membered heterocycles with α-diazo-β-dicarbonyl compounds were investigated. Thiiranes generated 3-acyl-5,6-dihydro-1,4-oxathiines in the presence of copper sulfate and trans-3-acyl-5,6-dihydro-1,4-oxathiines as stereospecific products for 1,2-disubstituted cis-thiiranes through an intramolecular S_N2 process. Oxiranes gave rise to 2-acyl-5,6-dihydro-1,4-dioxines under the catalysis of copper hexafluoroacetylacetonate and cis-3-acyl-5,6-dihydro-1,4-dioxines as stereospecific products for 1,2-disubstituted cis-oxiranes via an intimate ion-pair mechanism. The current method provides a direct and simple strategy in efficient preparation of 3-acyl-5,6-dihydro-1,4-oxathiines and 2-acyl-5,6-dihydro-1,4-dioxines, important agents in medicinal and agricultural chemistry, from readily available thiiranes and oxiranes, respectively.     

KMnO4-mediated oxidative CN bond cleavage of tertiary amines: Synthesis of amides and sulfonamides

KMnO₄-mediated oxidative CN bond cleavage of tertiary amines producing secondary amine was introduced, which was trapped by electrophiles (acyl chloride and sulfonyl chloride) to form amides and sulfonamides. The reaction could take place at mild condition, tolerating a wide range of function groups and affording products in moderate to excellent yields.