钙钛矿型A位掺杂复合氧化物La1-xSrxCoO3-δ的光催化活性研究

用柠檬酸溶胶-凝胶法制备了钙钛矿型La1-xSrxCoO3-δ复合氧化物,用XRD、XPS、EDS、红外、紫外等技术进行了表征,测定了其对活性艳红等水溶性染料光催化脱色的活性.结果表明:在A位掺Sr2+,由于产生较多氧空位,表面非晶格活性氧量增加,使LaCoO3的光催化活性明显提高,其中Ia0.9Sr0.1CoO3-δ效果最佳.     

钙钛矿结构B位掺杂化合物LaCO1-xFexO3的光催化活性研究

用柠檬酸溶胶-凝胶法制备了钙钛矿型LaCo1-xFexO3系列化合物，使用XRD、XPS、红外和紫外等手段对其进行了表征和测定，并测定了其对活性艳红水溶性染料脱色的光催化活性．实验结果表明在B位掺杂Fea 后使LaCoO3光催化活性明显提高，当x=0．05时，即LaCo1-xFexO3的光催化活性最佳。     

La掺杂TiO2光催化剂的制备与表征

用共沉淀法和溶胶-凝胶法制备了La掺杂TiO2光催化剂(La3 -TiO2),并以罗丹明B为模型反应物,进行了光催化降解实验.结果发现,共沉淀法制备的La3 -TiO2具有较高的光催化活性,当掺La量为1.0%、于800℃煅烧2 h时获得的催化剂活性最佳.用X射线衍射、N2吸附、扫描电镜和电子探针等手段测定了两种方法制备的典型样品的结构和粒度分布.两种方法制备的催化剂都是含有锐钛矿和金红石型TiO2的混合晶体,但共沉淀法制备的催化剂具有较高的锐钛矿含量、较大的晶粒和大孔/介孔的多级孔结构,这是其具有较高光催化活性的主要原因.     

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．     

稀土氧化物LSCO/YSZ的XRD和XPS研究

采用常规固相反应法制备了不同Sr掺杂量的钙钛矿氧化物La1-xSrxCoO3材料。测试了该材料的XRD和XPS谱，研究了不同热处理工艺对Lz1-xSrxCoO3材料平均晶粒度的影响，研究了不同Sr掺杂量的La1-xSrxCoO3阴极材料表面的化学状态。结果表明，当热处理温度在900－1200）时，平均晶粒度较大，有利于形成多孔电极。随着Sr掺杂量的增加，La(3d5/2),Co(2p3/2)的结合能下降，氧空位浓度增加。     

La1-xSrxCoC3钙钛矿在碱性溶液中的析氧电催化

 稳态极化研究结果表明, La1-xSrxCoO3电极的析氧Tafel斜率为2303RT/F, OH-的反应级数近似为1, 在阳极析氧反应中, OH-的电化学脱附为速度控制步骤. 随着La1-xSrxCoO3中Sr含量的增加,氧化物表面的粗糙度提高,当x=02时,析氧反应的活化能最低,即La0.8Sr0.2CoO3表现有最高的析氧电催化活性.     

钙钛矿La1-xSrxCoO3的电化学电容性能

以溶胶-凝胶法制备La1-xSrxCoO3(x=0.2,0.4,0.6,0.8)电极材料,XRD表征证明所得产物属钙钛矿相.由循环伏安和充放电曲线测试了La1-xSrxCoO3在碱性介质中的电化学电容性能.结果表明,La0.6Sr0.4CoO3电极10 mA.cm-2电流密度的放电比电容为325 F.g-1,500周期循环后其比电容仍保持于315 F.g-1,比电容保持率97.0%.     

柠檬酸络合法制备La1-xPbxFeO3及其光催化性能

用柠檬酸络合法制备了钙钛矿型复合氧化物LaFeO3,并按不同比例进行掺杂,制备了La1-xPbxFeO3(x=0,0.1,0.3,0.5,0.7)。用XRD,SEM,IR,UV-vis等方法对其进行表征,其结构均为钙钛矿型。并测定了其对活性艳红X-3B水溶性染料脱色的光催化活性。实验结果表明:在A位掺杂Pb2 ,产生了较多氧空位,降低了光生电子与空穴的复合速率,使LaFeO3的光催化活性明显提高,其中La0.7Pb0.3FeO3效果最佳。     

La掺杂 BiFeO3对苯酚光催化降解性能的影响

苯酚是一种稳定、毒性大且难降解的有机物,对人类和生态环境产生很大威胁,因此急需研发出能有效移除工业废水中苯酚污染物的方法.其中,绿色、高效的光催化氧化技术得到研究人员青睐.在半导体光催化剂中, BiFeO3具有带隙窄(2.2–2.5 eV)、化学稳定性好及成本低等优点,被看作是最有潜力的光催化剂.但是, BiFeO3存在光生电子空穴对复合率高,制备过程中易形成杂质相的缺点,使得其光催化活性很差,限制了 BiFeO3在光催化领域的应用.异种离子的引入能产生杂质能级或裁剪半导体带隙,同时促进光生载流子分离,故可考虑采用离子掺杂改性 BiFeO3的手段来抑制杂质相生成,提高载流子分离,从而提高 BiFeO3的光催化性能.本文以柠檬酸为络合剂,通过一步溶胶凝胶法合成了系列样品 Bi1-xLaxFeO3(摩尔分数x =0,0.10,0.15,0.20).通过 X射线衍射(XRD)、扫描电镜(SEM)、能谱(EDS)、透射电镜(TEM)、X射线光电子能谱(XPS)、紫外可见漫反射(UV-Vis DRS)及荧光光谱(PL)等手段对不同样品的物相、形貌、表面价态和光学性能进行了表征.并通过活性物种捕获实验和羟基自由基(?OH)产生实验分析了 Bi0.85La0.15FeO3样品在苯酚降解过程中的主要活性物种和降解机理.相对于单相 BiFeO3, La改性 BiFeO3催化剂的光降解苯酚性能均有提高,其中 La最佳掺杂量为0.15.在模拟太阳光下照射180 min后, Bi0.85La0.15FeO3的光催化活性达到96%,同时 COD去除率达到81.53%,并表现出好的循环使用活性和稳定性.研究发现,该光催化过程中主要的活性物种为?OH. XRD, SEM, TEM和 EDS结果表明, La元素掺杂进 BiFeO3结构中,且各元素分布均匀,同时,适量 La元素掺杂能有效抑制杂质相 Bi25FeO40的形成,而且 La掺杂 BiFeO3样品的颗粒尺寸略有减小,有利于电子空穴转移. XPS显示, La改性 BiFeO3样品的表面有氧空位形成,将有利于有机物的吸附和降解;另外,羟基氧和吸附氧含量增大,有利于活性氧物种形成. UV-Vis DRS和 PL测试证明, La改性后的样品对可见光的响应增强,样品带隙变窄,产生杂质能级,抑制了光生载流子复合,有利于产生更多载流子来促进活性物种形成,从而提高光催化活性.氧物种捕获实验说明,在 Bi0.85La0.15FeO3参与的苯酚降解过程中的主要活性物种是?OH,同时?OH的产生实验也证明了在光照下?OH在 Bi0.85La0.15FeO3光催化剂表面持续产生,并提出了光催化降解机理.     

镧含量对La-SrTiO3催化剂的结构和光催化活性的影响（英文）

采用溶胶-凝胶方法制备了不同La含量掺杂SrTiO3催化剂,通过X射线光电子能谱(XPS)、X射线衍射(XRD)、扫描电子显微镜(SEM)、透射电子显微镜(TEM)、紫外-可见漫反射光谱(UV-Vis DRS)和BET比表面积测量对其进行了表征,用甲基橙(MO)催化降解实验评价了其光催化活性。结果表明:钛酸锶经镧掺杂后仍然保持了钙钛矿结构;与纯SrTiO3相比,0.5%La-SrTiO3样品的粒子大小和形貌没有大的区别,但它的吸收带边发生明显红移;La-SrTiO3样品的紫外和可见光催化活性随La含量增加先增加,当La含量为0.5%时分别达到最大值,然后随La含量的进一步增加而减小;与纯SrTiO3相比,0.5%La-SrTiO3样品明显具有更高的紫外和可见光催化活性,这改善的光催化活性主要归因于比表面积增加、吸附性能提高、在250~650 nm区域有较强的光吸收和较低的禁带能级。     

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.