TiO2固定床光催化氧化头孢拉啶

 研究了抗生素头孢拉啶在负载型TiO2连续循环流动反应器中的降\r\n解，用红外和紫外光谱跟踪头孢拉啶的光催化降解过程．结果显示，在\r\n反应液流速4．5L／min，氧气流速1．6L／min，光照强度30W，反应温\r\n度28±2℃和反应时间120min的光催化氧化条件下，头孢拉啶能完全降\r\n解．光降解过程中头孢拉啶羧基的氧化比胺基容易．添加H2O2可以提高\r\n光催化氧化反应速率．光催化降解动力学研究表明，头孢拉啶的光催化\r\n氧化符合Langmuir－Hinshelwood一级动力学模型．     

不同催化系统降解甲基橙的效率比较及过程分析

以甲基橙模拟染料废水为降解目标,在自制的圆柱形不锈钢反应器中,比较三种不同的光催化系统:TiO2光催化、紫外光辐射及臭氧单独氧化的催化效率,检测脱色率、COD、pH值影响、臭氧及羟基自由基(·OH)的变化分析催化反应历程。研究表明:三种体系降解150 min后COD降解率分别为46.23%(UV),44.54%(O3)and 74.12%(TiO2),而120 min后脱色率达93.6%(UV),92.07%(O3)and 96.79%(TiO2)。三种体系在酸性条件下COD降解率和脱色率都最高。臭氧和羟基自由基检测显示,催化初期TiO2催化系统产生更多的臭氧,有利于后期·OH的产生。同时,利用·OH计算光催化反应速率也显示TiO2催化效率更好。     

RE/TiO2用于NO2-光催化氧化的研究

 以稀土盐和钛酸丁酯为原料,采用溶胶－凝胶法制备了掺杂稀土\r\n光催化剂RE／TiO2（RE＝La,Ce,Er,Pr,Gd,Nd,Sm）,并用XRD,\r\nDRS和IR等手段对RE／TiO2进行了表征;以NO－2为目标降解物,考察了\r\n其光催化氧化活性．结果表明,适量RE的掺入,可有效扩展TiO2的光谱\r\n响应范围,有利于NO－2的吸附,使光催化活性均有不同程度的提高．\r\n其中掺杂Gd样品的光催化活性最高．掺杂量是影响光催化活性的重要因\r\n素,一般最佳掺杂量为w（RE）≈0．5％．     

表面键联型TiO2/SiO2固定化催化剂的结构及催化性能

 采用浸渍法制备了表面键联型TiO2／SiO2固定化光催化剂．XRD\r\n,FT－IR,XPS和BET比表面积测定结果表明,TiO2通过Ti－O－Si联结\r\n负载于多孔硅胶的表面,由此提出TiO2／SiO2的结构模型．考察了多孔\r\n硅胶的粒度及氧化钛负载量对催化剂活性的影响．对活性艳红K－2G（\r\nR15）的光催化脱色反应,最佳的光催化剂30％TiO2／SiO2（Ims30）比\r\nB－TiO2粉末的催化速率快3倍．随着载体粒度的减小,催化剂的比表面\r\n积增大,催化活性升高;多孔硅胶不仅起着支持体的作用,而且具有分\r\n散的作用;多孔硅胶具有很好的透光性．经ξ－电位测定,所制备催化\r\n剂的等电点为3．0pH单位,表明催化剂表面呈酸性．     

活性炭负载TiO2-Fe3O4磁性光催化剂的制备及性能

采用溶胶-凝胶法制备了易于固液分离的活性炭（AC）负载磁性光催化剂（TiO2-Fe3O4／AC）．样品通过SEM-EDX和X射线衍射法进行表征．通过在紫外光照射下降解亚甲基蓝评价其光催化降解能力．结果表明：负载22％Fe3O4的光催化剂（含20％TiO2和58％AC）的光催化活性最强（120min时亚甲基蓝的降解率达到87％,是纯TiO2的2．7倍）;磁性光催化剂可实现磁分离回收．     

纳米复合Y2O3／TiO2的制备、表征及其光催化性能研究

采用溶胶－凝胶法制备复合半导体Y2O3／TiO2,掺入Y2O3会阻碍锐钛矿晶相的出现,掺入浓度越大,TiO2锐钛矿（101）峰强度减小越大,平均晶粒直径与颗粒直径减小,比表面积增大;Y2O3／TiO2具有高热稳定性与高比表面积,由于量子尺寸效应,掺入Y2O3使光催化剂的拉曼峰发生微小位移,在380－460nm范围内,使反射率增强,以亚甲基蓝与甲基橙溶液光 经降解为模型反应,掺入Y2O3,复合光催化剂对亚甲基蓝溶液的光催化脱色降解一级动力学常数明显低于纯TiO2的;掺入5％的10％Y2O3,复合光催化剂对甲基橙溶液的光催化脱色降解一有动力学均常数高于纯TiO2的,掺入浓度太高反而有害,讨论了掺入Y2O3后光物理性质的变化与其光催化活性的关系。     

纳米TiO2低温制备及光催化降解有毒有机污染物

通过设计不同的实验方案低温（180℃）制备得到纳米TiO2,并在紫外光（λ≤387nm）照射下利用有机染料罗丹明B（Rhodamine B,RhB）光催化降解为探针反应,以有机污染物降解活性最佳为目的,优选低温制备得到纳米TiO2最佳方案．结果表明以Ti（SO4）2为原料,在低温条件下通过蒸汽热法制得TiO2为最佳方案．对制备高催化活性的纳米TiO2利用透射电子显微镜（TEM）,X射线衍射仪（XRD）对其进行了物理特性及光化学性质的初步表征,探讨了纳米TiO2制备时反应温度和反应时间对其粒径大小、晶型转变以及光催化活性的影响．实验结果表明：在以紫外光（λ≤387nm）照射下的探针反应有良好的光催化降解效果为条件,优选低温制备得到纳米TiO2最佳反应温度为180℃,最佳反应时间为12h．通过紫外-可见光谱（UV—vis）、红外光谱（FTIR）和总有机碳（TOC）的测定分析,发现UV／TiO2体系在pH=3．00的条件下,能使RhB发生有效的降解和矿化,矿化率达到93．2％．     

环境湿度对TiO2借性炭纤维气．固光催化氧化甲苯的影响

在恒温控湿的环境舱中，以自制的TiO2／ACF（活性炭纤维）为光催化剂，研究了环境湿度对甲苯光催化降解过程的影响．通过N2吸附和扫描电子显微镜分别对TiO2／ACF光催化剂的孔径结构和形貌特征进行了表征；利用GC—MS和GC—FID对甲苯光催化过程中生成的中间产物进行了定性及定量分析．结果表明，环境舱中相对湿度增大，甲苯光催化转化率提高；不同相对湿度下，积累在光催化剂表面的中间产物种类相同，但支链氧化产物（苯甲醇、苯甲醛和苯甲酸）的积累量远多于苯环氧化产物（甲酚和对甲基苯酚）的积累量；随环境相对湿度的增大．苯甲醛在光催化剂表面的积累量减小，其余中间产物的积累量均有不同程度的增加．这说明水分子在甲苯光催化过程中起重要作用，相对湿度不仅影响甲苯的光催化转化效率，还影响其光催化转化的过程．尽管在各湿度条件下，支链氧化都是甲苯光催化降解的主要途径，但环境湿度增大更有利于苯环氧化途径的进行．讨论了水蒸气在甲苯光催化氧化过程中的作用机理．     

B2O3/TiO2-ZrO2催化环己酮肟气相Beckmann重排反应研究 Ⅰ.B2O3含量的影响

 制备了不同B2O3含量（0～20％）的B2O3／TiO2－ZrO2固体酸催\r\n化剂，用XRD，FT－IR，N2吸附及NH3－TPD等方法测定了其结构、比表\r\n面积、孔分布和表面酸性．结果表明，当B2O3含量较低（≤5％）时，\r\n催化剂呈无定形态，样品中的B2O3主要以BO4结构存在．当B2O3含量较\r\n高（≥8％）时，催化剂中的TiO2－ZrO2以ZrTiO4晶相存在，分散于Ti\r\nO2－ZrO2表面的B2O3主要以玻璃体形式和BO3结构存在．随着B2O3含量\r\n的增加，催化剂的比表面积减小，孔径增大．300℃下的环己酮肟气相\r\nBeck－mann重排反应结果表明，随着B2O3含量的增加，己内酰胺的选择\r\n性逐渐增大，而己内酰胺的收率在B2O3含量为12％时达到最大值．讨论\r\n了B2O3／TiO2－ZrO2的催化性能与其表面酸性及孔径大小的关系．     

La2O3掺杂TiO2光催化剂的制备和性能

采用溶胶-凝胶法制备了La2O3掺杂TiO2纳米光催化剂，并通过XRD、TEM、BET和XPS等手段进行了表征．掺入La2O3后，阻止了TiO2从锐钛矿晶型向金红石晶型的转变，使TiO2的粒径减小，比表面积增大．以甲基橙为光催化降解反应模型化合物，考察了光催化剂的活性．测定了甲基橙在纯TiO2和La2O3掺杂TiO2光催化剂上的吸附常数．考察了pH、H2O2对降解性能的影响．讨论了光催化活性与催化剂性质的关系．     

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.     

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.     

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.     

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.     

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.     

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.