超细纳米TiO2/Al2O3复合体的制备及其组成分布的研究

采用溶胶－凝胶法成功制备出纳米尺寸的ＴｉＯ２／Ａｌ２Ｏ３复合体,并用ＸＲＤ、ＸＰＳ和ＩＲ等手段研究了复合体的结构组成及ＴｉＯ２和Ａｌ２Ｏ２的分布状态,进一步探讨了机械研磨法制备ＴｉＯ２／Ａｌ２Ｏ３复合体等因素对其组成的影响。ＸＲＤ分析表明,在〔Ａｌ＾＋３〕：〔Ｔｉ＾＋３〕＝１：１（或０．５）情况下,改进的溶胶－凝胶法制备纳米ＴｉＯ２／Ａｌ２Ｏ３复合体,其ＴｉＯ２主要分布在Ａｌ２Ｏ３的表面层,在含Ｔ     

二氧化钛的尺寸与光催化活性的关系

采用溶胶－凝胶法控制制备了晶粒尺寸从１０ｎｍ到８０ｎｍ的二氧化钛纳米半导体．用光催化降解苯酚作为模型反应，结合ＸＲＤ，ＤＲＳ，ＦＳ等表征手段，研究了纳米ＴｉＯ２的制备条件与其晶粒尺寸和相结构的关系，探讨了纳米ＴｉＯ２尺寸效应对其光催化活性的影响．发现当晶粒尺寸小于１６ｎｍ时，二氧化钛半导体具有了明显的尺寸量子效应．尺寸量子效应对提高ＴｉＯ２光催化降解苯酚的催化活性起了极为重要的作用．     

纳米TiO_2微胶粒的光化反应制备机理及量子尺寸效应

研究了由水相Ｔｉ３＋制备纳米极ＴｉＯ２微胶粒的光化反应机理及反应动力学，给出反应速率方程，讨论了ＴｉＯ２微胶粒的量子尺寸效应，经电镜测试ＴｉＯ２粒子的直径为１５～２５ｎｍ，反应过程中由气相色谱仪监测生成物Ｈ２。     

流动注射分析在线研究Cr（Ⅵ）在纳米TiO2表面上的吸附 …

用溶胶－凝聚法在不同的水解和热处理条件下制备了纳米尺寸的ＴｉＯ２微粉，所得的ＴｉＯ２表面性质迥异，粒径从几个纳米到数百个纳米，晶型也由低温煅烧的锐钛型转成高温地的金红石型。利用流动注射微柱富集在线分析方法对Ｃｒ离子在纳米ＴｉＯ２表面上的吸附动力学特性进行了原位表征。     

纳米TiO2微胶粒的光化应制备机理及量子尺寸效应

研究了由水相Ｔｉ＾３＋制备纳米极Ｔｉ＾Ｏ２微胶粒的光化反应机理及反应动力学，给出反应速率方程。讨论了ＴｉＯ２微胶粒的量子尺寸效应，经电镜测试ＴｉＯ２粒子的直径为１５－２５ｎｍ。反应过程中由气相色谱仪监测生成物Ｈ２。     

溶胶—凝胶法制备负载型TiO2膜的研究

本研究采用溶胶－凝胶（Ｓｏｌ－Ｇｅｌ）法制备了负载型ＴｉＯ２膜，并采用ＳＥＭ、压汞等实验手段对Ｔｉ（ＯＨ）４溶胶和ＴｉＯ２膜进行了表征。实验表明：Ｔｉ（ＯＨ）４溶胶制备过程中Ｈ２Ｏ／Ｔｉ＾４＋、Ｃ２Ｈ５ＯＨ／Ｔｉ＾４＋的比值，溶胶在支承管上浸涂的时间、次数以及凝胶煅烧升温速度和煅烧温度均是制备负载型ＴｉＯ２膜的重要因素。最终制得一种无裂纹、２０μｍ厚、孔径分布在５０￣３００ｎｍ之间的负载型ＴｉＯ２     

TiO2超微粒子的量子尺寸效应与光吸收特性

利用Ｒａｍａｎ激光光谱,ＸＲＤ,ＴＥＭ,ＳＥＭ和ＵＶ－Ｖｉｓ等手段研究了ＴｉＯ２超微粒子的量子尺寸效应与光吸收特性。结果发现：Ｔｉ（ＯＢｕ）４在较低ｐＨ值的水解条件下制得的ＴｉＯ２溶胶粒径为５～１０ｎｍ;随着热处理温度的升高,ＴｉＯ２微粒的粒径增大,经４７３～６７３Ｋ热处理得到的ＴｉＯ２超微粒子粒径为１０～２０ｎｍ,呈不规整的锐钛矿型结构。ＴｉＯ２的拉曼峰随热处理温度升高而发生红移,表现出量子尺寸     

量子尺寸二氧化钛的制备与光谱表征

本文报道了一种通过直接解胶工业粉体制备 Ti O2 溶胶的新方法。利用 AFM测定溶胶粒子的尺寸 ,发现解胶溶液的酸度可以有效地控制溶胶粒子的尺寸。它们的吸收光谱显示了显著的量子尺寸效应 ,并且分别在 2 60 nm和 3 1 0 nm处出现了两个明显的激子峰。在它们的荧光光谱中 3 40 nm处出现一个由于表面 Ti OH基电子跃迁引起的强荧光峰 ,说明在这此溶胶胶粒表面存在着丰富的表面羟基。同时 ,通过理论物理模型讨论了其价带与粒子尺寸之间的关系。     

TiO2纳米粒子膜表面性质的研究

ＴｉＯ_２纳米粒子膜在光催化降解大气和水中的污染物［１］、光电转换［２］、光致变色［３］等方面有广阔的应用前景,近年来受到了科学界的高度重视．研究表明,膜的表面性质对如上应用有着重要影响．本文采用等离子体化学气相沉积法（ＰＥＣＶＤ法）［４］制备了ＴｉＯ２的纳米粒子膜,分别采用ＴｉＣｌ４等离子体或Ｏ２等离子体处理膜表面,获得两种不同表面性质的ＴｉＯ２纳米粒子膜;并利用表面光电压谱（ＳＰＳ）和电场诱导表面光电压谱（ＥＦＩＳＰＳ）技术对膜的表面性质进行具体分析,探讨了其在光催化领域的可能应用．１实验部…     

Ru（bpy）2（NCS）2染料敏化CdS／Zn^2＋—TiO2复合半导体纳米 …

采用水热法合成了Ｚｎ＾２＋离子掺杂的ＴｉＯ２纳米粒子「Ｚｎ＾２＋掺杂量０．５％（物质的量的比）」,并用光电化学方面研究了经Ｒｕ（ｂｐｙ）２（ＮＣＳ）２（ｂｐｙ＝２,２’－ｂｉｐｙｒｉｄｉｎｅ－４,４’－ｄｉｃａｒｂｏｘｙｌｉｃ ａｃｉｄ）分别敏化的掺杂Ｚｎ＾２＋的ＴｉＯ２电极（简写为Ｚｎ＾２＋ＴｉＯ２）和ＣｄＳ／Ｚｎ＾＋－ＴｉＯ２复合半导体纳米多孔膜电极的光电化学行为。实验证明Ｒｕ（ｂｐｙ）２（Ｎ     

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%.     

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 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.     

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.     

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.     

Chemistry of heterocyclic compounds at the A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences, over 50 years (Review)

The review contains a concise historical account and information on the most significant researches undertaken by the staff at the A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences on the Chemistry of Heterocyclic Compounds. Dedicated to Academician of the Russian Academy of Sciences B. A. Trofimov on his 70th jubilee. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1443–1502, October, 2008.     

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.     

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.     

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.