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．     

Ce-TiO_x超细粒子的模板法制备及结构研究

利用模板法结合真空干燥技术制备出Ce-TiOx超细粒子,用XRD,TG-DSC,TEM等手段进行表征;以甲基橙溶液的光催化降解测试Ce-TiOx超细粒子的催化活性;考察初始物质的量比及热处理温度对Ce-TiOx超细粒子的结构及光催化活性的影响。结果显示:钛干凝胶经400℃热处理可得结晶度较高的锐钛矿型TiO2,800℃时TiO2转变为金红石相;Ce-Ti干凝胶经800℃热处理可得粒径约为45 nm的类球形颗粒;Ce-TiOx超细粒子中,钛以Ti3O5,Ti6O11,TiO2等多种形式存在,铈以CeO2和Ce7O12的形式存在;稀土铈影响Ce-TiOx超细粒子中钛的价态。     

活性炭负载纳米TiO2光催化降解性能研究

本文研究活性炭负载纳米TiO2的光催化降解性能和影响甲基橙废水处理的主要因素。结果表明:用溶胶-凝胶法制备的TiO2-活性炭催化剂具有比表面积大、分散性高、光催化降解性能好、可重复利用等优点;采用30W高硼紫外光灯,TiO2-活性炭光催化降解浓度为1500mg/L甲基橙废水的最优工艺条件是:催化剂活化温度为700℃、用量为1.0g/L、废水起始pH值为1、反应温度为45℃、光照时间为50m in。在此条件下,甲基橙和CODC r的去除率分别达99.8%和99.7%。     

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。     

高比表面空心球状ZnO/ZnAl2O4复合光催化剂制备及活性

以葡萄糖为模板,聚乙二醇(PEG-4000)为分散剂通过一步水热法所得前驱体,经500℃焙烧4 h得到ZnO/ZnAl2O4产物。并用XRD、SEM、TEM、BET、TG/DTA和UV-Vis DRS等技术对样品进行表征。结果表明产物为空心球状ZnO/ZnAl2O4复合光催化剂,比表面积高达158.3 m2.g-1。在模拟太阳光照射下,以甲基橙溶液的光催化降解考察样品的光催化活性,研究了焙烧温度、pH值和PEG加入量对样品光催化活性的影响。结果表明,当pH=9,PEG加入量为10%(以反应理论得到的前驱体ZnO/ZnAl2O4的质量来衡量)时,光催化活性最佳,光照60 min后,0.5 g.L-1光催化剂用量对甲基橙的脱色率达98.7%,与TiO2 Degussa P-25进行比较,相同条件下对甲基橙的脱色率提高了7.7%。     

双介孔结构的纳米TiO2/I2复合材料的制备及其可见光催化性能

以钛酸丁酯为前驱体,碘溶胶为碘源,在室温下采用水解沉淀法制备了单质碘和纳米TiO2复合的双介孔结构光催化剂(M-I2-TiO2).采用X射线衍射(XRD)、透射电子显微镜(TEM)、比表面分析(BET)、紫外-可见(UV-Vis)漫反射光谱和傅里叶变换-红外光谱(FT-IR)对M-I2-TiO2进行了表征.以次甲基蓝(MB)溶液为模拟废水,对M-I2-TiO2的光催化性能进行了评价,研究了不同热处理温度对光催化活性的影响.结果表明,M-I2-TiO2在可见光区有显著的吸收,300℃热处理得到的样品比表面积高达227.6 m2/g,600℃热处理所得样品的比表面积仍高达111.8 m2/g,而400℃热处理所得样品具有最好的光催化降解性能.双介孔结构纳米TiO2/I2复合材料的光催化降解性能显著高于相同方法制备的纯TiO2和Degussa P-25商业产品.催化剂经6次重复使用其光催化活性基本保持不变.     

纳米复合Y_2O_3/TiO_2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Y2 O3/TiO2 。掺入Y2 O3会阻碍锐钛矿晶相的出现 ,掺入浓度越大 ,TiO2 锐钛矿 (10 1)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 ;Y2 O3/TiO2 具有高热稳定性与高比表面积 ,由于量子尺寸效应 ,掺入Y2 O3使光催化剂的拉曼峰发生微小位移 ,在 3 80～ 460nm范围内 ,使反射率增强。以亚甲基蓝与甲基橙溶液光催化降解为模型反应 ,掺入Y2 O3,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 %和 10 %Y2 O3,复合光催化剂对甲基橙溶液的光催化脱色降解一级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Y2 O3后光物理性质的变化与其光催化活性的关系     

硫酸浸渍La_2O_3掺杂TiO_2光催化剂对甲基橙废水化学耗氧量的影响

采用不同浓度的硫酸溶液浸渍处理La2O3掺杂TiO2,随后经焙烧制得一系列SO24-/TiO2-La2O3光催化剂;考察了SO24-/TiO2-La2O3光催化剂对甲基橙废水溶液化学耗氧量的影响.结果表明,SO24-/TiO2-La2O3的光催化活性比TiO2-La2O3的高;H2SO4浸渍液浓度对SO24-/TiO2-La2O3的光催化活性有一定的影响,H2SO4溶液的最佳浓度为0.5mol/L.同时,催化剂的焙烧温度对其光催化活性也有一定的影响,最佳焙烧温度为500℃;而复合催化剂中La2O3的最佳掺杂量为0.3%.     

介孔TiO2的水热法制备及其光催化性能

以二钛酸钾(K2Ti2O5)经离子交换得到的无定形水合二钛酸(H2Ti2O5·xH2O)为原料, 与葡萄糖溶液在220 ℃下进行水热反应, 再在空气中520 ℃焙烧, 制备出介孔TiO2. 用扫描电子显微镜(SEM)、X射线衍射(XRD)、N2吸附、透射电子显微镜(TEM)等技术对样品进行了表征. 结果表明, 该介孔TiO2具有微米级棒状或针状形貌, 晶粒大小为12.3 nm, 比表面积为106 m2·g-1, 孔容为0.31 cm3·g-1, 孔径为8.06 nm, 焙烧处理后晶型仍是锐钛矿相. 水热生成的碳抑制了晶粒的团聚生长和晶型的转变, 提高了介孔TiO2的热稳定性. 甲基橙降解实验评价了介孔TiO2的光催化性能, 结果发现其活性与商用TiO2催化剂P25相当, 而其较大的粒径更容易回收再利用. 以碘化钾为探针反应, 表明介孔TiO2的光催化机制以光生空穴氧化为主.     

介孔TiO2的水热法制备及其光催化性能

以二钛酸钾(K2Ti2O5)经离子交换得到的无定形水合二钛酸(H2Ti2O5·xH2O)为原料,与葡萄糖溶液在220℃下进行水热反应,再在空气中520℃焙烧,制备出介孔TiO2.用扫描电子显微镜(SEM)、X射线衍射(XRD)、N2吸附、透射电子显微镜(TEM)等技术对样品进行了表征.结果表明,该介孔TiO2具有微米级棒状或针状形貌,晶粒大小为12.3 nm,比表面积为106 m2·g-1,孔容为0.31 cm3·g-1,孔径为8.06 nm,焙烧处理后晶型仍是锐钛矿相.水热生成的碳抑制了晶粒的团聚生长和晶型的转变,提高了介孔TiO2的热稳定性.甲基橙降解实验评价了介孔TiO2的光催化性能,结果发现其活性与商用TiO2催化剂P25相当,而其较大的粒径更容易回收再利用.以碘化钾为探针反应,表明介孔TiO2的光催化机制以光生空穴氧化为主.     

A carbanion induced synthesis of highly congested pyrazole and imidazole containing heterocycles

An efficient approach to the synthesis of highly congested di, penta and hexacyclic pyrazoles as well as imidazole fragment containing novel heterocyclic molecule has been developed through a carbanion induced transformation of suitably functionalized 2H-pyran-2-ones, benzo[h]chromene and thiochromeno[4,3-b]pyrans. Due to the presence of fluorescence, we report their prime application metal sensor as off/on switching in ferric ions.     

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.     

N-Heterocyclic carbene-palladacyclic complexes: synthesis,characterization and their applications in the C-N coupling and α-arylation of ketones using aryl chlorides

N-Heterocyclic carbene-palladacyclic complexes 3 were successfully achieved in a one-pot procedure under mild conditions. The structure of 3a was unambiguously confirmed by X-ray single crystal diffraction and it was an active catalyst in the Buchwald-Hartwig amination and α-arylation of ketones even at very low catalyst loadings (0.01?mol%).     

Selective synthesis of 4,5-dihydroimidazo- and imidazo[1,5-a]quinoxalines via modified Pictet–Spengler reaction

An efficient tandem approach for the selective synthesis of 4,5-dihydroimidazo[1,5-a]quinoxalines 6a–g and imidazo[1,5-a]quinoxalines 7a–h by the reaction of 2-imidazolyl anilines 4a–c with aryl aldehydes 5a–k under mild reaction conditions is described. Introduction of electron releasing alkyl groups in substrates 4a–b was found to be instrumental for the success of the reaction.     

Understanding the Diels-Alder reactivity of 1,2-azaborine analogues

The Diels-Alder reactivity of 1,2-heteroborines (H₄C₄B(H)X, X?=?NH, PH, AsH; O, S, Se) has been computationally explored by means of Density Functional Theory (DFT) calculations. The influence of the HB?=?X fragment on the reactivity of the system has been quantitatively analyzed in detail by means of the so-called Activation Strain Model (ASM) of reactivity. It is found that the interaction between these species and the dienophile is significantly stronger than that computed for their all-carbon isoelectronic counterpart, benzene. In addition, the strain energy plays a key role in the observed reactivity trends. The role of the aromaticity strength of these heteroarenes on the reactivity is also assessed.     

Synthesis of N-substituted carbazolones from α-iodo enaminones via Pd(0)-catalyzed intramolecular coupling under microwave irradiation

A variety of N-aryl and N-alkyl carbazolones were conveniently achieved in good to high yields via Pd₂(dba)₃-mediated intramolecular coupling of N-substituted α-iodo enaminones under microwave irradiation. The Pd(0)-catalyzed cyclization was found to proceed favorably with the more electron-deficient phenyl ring during the reactions involving unsymmetrical N,N-diaryl α-iodo enaminones. This unique property enables the construction of carbazolone skeleton containing nitro substituted benzenoid ring.     

Iodine-mediated oxidative Pictet-Spengler reaction using terminal alkyne as the 2-oxoaldehyde surrogate for the synthesis of 1-aroyl-β-carbolines and fused-nitrogen heterocycles

An efficient iodine-mediated oxidative Pictet-Spengler reaction in dimethyl sulphoxide (DMSO) using terminal alkynes as the 2-oxoaldehyde surrogate for the synthesis of aryl (9H-pyrido[3,4-b]indol-1-yl)methanones is described. The scope of the protocol includes the total synthesis of Fascaplysin, Eudistomins Y₁ and Y₂. The methodology is extended for preparing pyrrolo[1,2-a]-quinoxaline and indolo[1,5-a]quinoxaline derivatives. The utility of 1-aroyl-β-carbolines was demonstrated by performing palladium-catalyzed β-carboline directed ortho-C(sp2)-H functionalization of the phenyl ring with thiomethyl (SMe) group using DMSO as source and for accessing 4-aryl-canthin-6-ones.     

Facile synthesis of bicyclic 1-arylpyrazol-5-ones

In this Letter, we described a facile method for constructing fused bicyclic 1-arylpyrazol-5-one ring system. We employed various methylene-containing carboxylic acids as the substrates and proved that the pyrazolone ring closure requires activated methylene group in intermediate II. Accordingly, a series of structurally diversified, fused bicyclic 1-arylpyrazol-5-ones was prepared in moderate to high yields using the requisite substrates.     

Synthesis of substituted 2,4,5,6-tetrahydrocyclopenta[c]pyrazoles and 2,4,5,6-tetrahydropyrrolo[3,4-c]pyrazoles by intramolecular nitrilimine cycloaddition

Both substituted 2,4,5,6-tetrahydrocyclopenta[c]pyrazoles and 2,4,5,6-tetrahydropyrrolo[3,4-c]pyrazoles have been synthesized by the 3+2 intramolecular dipolar cycloaddition of nitrilimines to alkynes. This cyclization has been extended to more versatile 3-bromo derivatives by the use of alkynylbromides as dipolarophiles.