第四周期过渡金属钼磷三元杂多化合物的氧化还原性质研究

研究了Keggin结构钼磷杂多化合物Na₅[PM(H₂O)Mo₁₁O₃₉]·nH₂O(M=Mn²⁺,Co²⁺,Ni²⁺,Cu²⁺,Zn²⁺在溶液中的氧化还原性质,发现环境的改变可对杂多阴离子的极谱半波电位产生影响,其影响程度的大小决定于过渡金属离子本身的性质。取代后的钼磷杂多阴离子的半波电位顺序为Ni²⁺>Co²⁺>Zn²⁺>Cu²⁺>Mn²⁺,pH值的变化影响氧化还原性质,并阐述了变价金属Cu²⁺对杂多阴离子氧化还原性质的影响.     

氧化还原活性配体的电子效应对钌催化水氧化反应的影响（英文）

水氧化(2H₂O→4e^-+4H⁺+O₂↑)是自然以及人工光合作用系统中的关键半反应,为还原过程提供反应所必需的质子和电子.但水氧化反应在热力学和动力学上的固有挑战以及对O-O键生成步骤的有限机理认识,使其成为构筑高效人工光合系统的瓶颈.为此,人们开发了大量的金属催化剂,利用金属中心活化水分子,并生成活性金属氧物种以促进O-O键的生成.其间,金属中心往往需要达到极高的氧化态,进而导致生成的高价金属氧化物具有极高的催化活性,极易诱导催化剂降解等副反应的发生,难以兼顾活性和稳定性.因此,深入认识和理解水氧化反应的催化过程及O-O键的生成机制是突破该领域瓶颈的重点.氧化还原活性配体与金属的协同作用被认为是调节电荷累积过程、平衡催化剂活性与稳定性的有效策略,受到了广泛的关注.然而,氧化还原活性配体调节金属催化中心活性的机理仍有待进一步阐明.近期,本研究组发展了一类具有氧化活性配体的单核钌水氧化催化剂[(L_H^N5-)Ru^Ⅲ-OH]⁺     

PANI-SnP复合膜电极在镍镉废水中电控离子交换性能

采用滴涂法在铂基底制备了电活性聚苯胺-磷酸锡(PANI-SnP)复合膜电极,考察了该电极在Ni²⁺、Cd²⁺溶液的电控离子交换性能. 用傅立叶变换红外光谱和扫描电镜分析观察复合膜的组成及表面形貌;在0.1 mol·L^-1 Ni(NO₃)₂、Cd(NO₃)₂溶液,通过循环伏安法比较了PANI膜、SnP膜及PANI-SnP复合膜电极的电化学性能,并结合电化学石英晶体微天平技术重点考察了PANI-SnP复合膜的离子交换机制;同时,通过循环伏安法调控复合膜电极的氧化还原电位,结合X射线能谱和X射线光电子能谱分别测定了其氧化和还原状态的元素组成. 结果表明,PANI-SnP复合膜电极在Ni²⁺、Cd²⁺溶液均有良好的氧化还原电活性和可逆离子交换性能,其Cd²⁺离子选择性优于Ni²⁺离子,通过电控离子交换可使Cd²⁺离子从镍镉废水高效分离.     

基于零价铝的氧化/还原技术在水处理中的应用

利用零价金属(ZVMs)处理环境污染物一直是环境治理领域的研究热点,其中以零价铁(ZVI)的研究最为广泛。近年来,零价铝(ZVAl)因其具有比ZVI更低的氧化还原电位(E⁰(Al³⁺/Al⁰)=-1.662 V, E⁰(Fe²⁺/Fe⁰)=-0.44 V)及其两性性质(反应pH可以拓展到碱性)而开始受到关注。目前环境领域关于ZVAl的研究主要集中于两类:以零价铝/氧/酸(ZVAl/O₂/H⁺)体系为核心的氧化体系和以零价铝/无氧(ZVAl/anaerobic)体系为核心的还原体系,其中前者因原位产生过氧化氢构成类Fenton氧化体系而备受关注。研究已发现,基于ZVAl的氧化/还原技术可有效去除酚类、偶氮染料、有机卤化物等有机污染物和Cr(Ⅵ)、As(Ⅲ)等无机污染物,且超声、微波、外加多金属氧酸盐(POM)、Fe²⁺等辅助手段对该技术有一定辅助效果。本文分别就基于ZVAl的氧化体系和还原体系,对其反应机理及去除水中污染物的国内外最新研究进展进行了综述和展望,以期促进ZVAl水处理技术的发展。铝作为地壳中最丰富的金属元素,ZVAl不存在像ZVI高pH值时产生沉淀的问题,相信随着ZVAl表面氧化膜这一制约因素的逐渐解决,其在水处理领域将有更广泛的应用。     

用于可充电器件的有机电极材料

有机化合物作为可充电器件的电极材料可以通过自身电活性部位电荷状态的变化来实现本征的氧化还原反应。除了锂离子电池外,有机电极材料还可以用于其他离子半径更大的金属离子电池(如Na⁺、K⁺、Mg²⁺、Zn²⁺等)。有机电极材料还具有诸多优势,比如结构多样、成本低廉、资源丰富和可持续性高,易于通过适当的材料设计调整其性能等,已被证明在可充电器件中具有重要的应用潜力。然而,有机电极的实际应用仍需要解决一些关键问题,例如导电性差和在常规有机电解液中溶解等。本文介绍了各种具有不同氧化还原活性中心的有机电极材料及其反应机理,包括有机硫化物、有机自由基、亚胺类化合物、偶氮化合物和羰基化合物;重点总结了有机羰基化合物电极材料在性能改善方面的策略以及近5年在可充电器件中的应用;最后,讨论了有机电极材料需要应对的挑战以及未来的机遇。     

照相明胶与化学增感剂相互作用的XPS研究

本文采用X射线光电子能谱技术研究了两种照相明胶与化学增感剂相互作用的机理.当两种照相明胶样品在HAuCl₄溶液中反应5min后,明胶中的蛋氨酸、蛋氨酸亚砜均被氧化为蛋氨酸砜.与此同时,明胶吸附的大部分Au³⁺被还原为Au⁺,并且Au⁺以络合形态存在于明胶之中.根据与AuCl₃反应之后明胶中Au³⁺与Au⁺的比例,法国明胶的还原性略高于包头明胶.添加到明胶中的Na₂S₂O₃能将明胶大分子所含的蛋氨酸亚砜全部还原为蛋氨酸.S₂O₃^2-、蛋氨酸和蛋氨酸砜可以稳定共存于明胶体系之中,外加的S₂O₃^2-的还原性高于明胶中蛋氨酸、蛋氨酸亚砜的还原性.添加Na₂S₂O₃后的两种照相明胶均可以将其溶胀吸附的Au³⁺全部还原为胶态金.此时,参与氧化还原反应的主要基团是S₂O₃^2-而非明胶中的蛋氨酸残基.由于Na₂S₂O₃的添加,照相明胶对AuCl₃的还原能力增强.     

湿法脱硫浆液中Hg2+的还原机制研究

针对燃煤电厂湿法脱硫浆液中Hg²⁺易被还原的特性,研究Hg²⁺在模拟湿法脱硫系统中的迁移机制,考察了浆液温度、pH值以及SO₃^2-、Cl^-、Ca²⁺、Mg²⁺浓度等因素对Hg²⁺还原性能的影响。结果表明,Hg²⁺还原率随着浆液中SO₃^2-浓度的增大而降低;pH值对Hg²⁺的还原呈先增加后降低的趋势,在pH值为5.5时还原率最高;温度的升高不利于浆液中稳定的二价汞盐络合物存在,导致Hg²⁺还原率增加;Ca²⁺、Mg²⁺以及Cl^-浓度的增加有利于形成稳定化合物,从而抑制Hg²⁺的还原。     

在线超声成对电合成苯甲醛和丁二酸

将间接电合成苯甲醛与电还原马来酸制备丁二酸的过程有机结合, 构建了一个新的成对电解体系, 即在隔膜电解槽中, 以纯Pb为阴极, PbO₂/Pb为阳极, 硫酸溶液为介质, 在施加超声波的条件下, 阳极氧化Ce³⁺为Ce⁴⁺, 阴极还原马来酸生成丁二酸; 同时, 在槽外采用Ce⁴⁺氧化甲苯生成苯甲醛. 实验结果表明, 阴极和阳极电解的平均电流效率分别为92.71%和87.81%, 总的电流效率高达180.52%; 且Ce⁴⁺槽外氧化甲苯为苯甲醛的收率为95.78%, 马来酸电还原为丁二酸的转化率为92.09%; 电解的槽电压与单一电解氧化Ce³⁺相比降低了0.25 V.     

铜-铈氧化还原液流电池性能

设计了一种新型Ce-Cu氧化-还原液流电池,研究了Ce³⁺/Ce⁴⁺和Cu⁰/Cu²⁺氧化还原电对的循环伏安特性,优化了电解液及电极材料,进而组装出液流电池,测试了电池的充放电性能。 结果表明,在45 mA恒电流充/放电条件下,电池放电平台电压约为1.0 V,库伦效率约100%,能量效率为75%以上,电池可稳定循环100次。     

亚铁离子氧化性实验的改进*

针对教材中验证Fe²⁺氧化性实验现象不明显的问题,改进了Fe²⁺氧化性实验。把锌片剪成细小的锌丝,通过锌丝与亚铁盐溶液反应,反应一段时间后,用磁铁吸引锌丝,锌丝能被磁铁吸引,则证明Fe²⁺被还原为铁单质,体现了Fe²⁺的氧化性。     

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.