Cu／M0O3-TiO2复合半导体光催化剂的制备与表征

用溶胶-凝胶法制备了复合半导体MoO3-TiO2，并用等体积浸渍法制备了Cu／MoO3-TiO2光催化剂，利用X射线衍射、激光拉曼光谱、程序升温还原、红外光谱、透射电镜和紫外-可见漫反射光谱等技术研究了所得光催化剂的物相结构、微粒尺寸和吸光性能，结果表明，MoO3含量为10％时呈单分子层分散在TiO2上，催化剂的平均粒径为10nm．MoO3的引入使TiO2的吸收限发生明显的蓝移，MoO3负载量超过10％时，有体相MoO3生成，其光吸收性能下降．Mo-O-Ti键的形成加强了半导体之间的相互作用，有利于光生载流子在半导体间的传输，负载金属Cu可促进四面体配位Mo向八面体配位Mo转化。     

负载金属对MoO3-TiO2光催化剂结构与催化性能的影响

用溶胶-凝胶和浸渍-还原相结合的方法制得M/MoO3-TiO2 (M=Pd, Cu, Ni和Ag)光催化剂。利用X-射线衍射(XRD)、程序升温还原(TPR)、红外光谱(IR)、程序升温脱附(TPD)、紫外-可见漫反射光谱(UV-VisDRS)和光反应等技术，研究了负载金属复合半导体的物相结构、吸附性能、吸光性能和光催化反应性能。结果表明，金属M(M=Pd, Cu)负载在复合半导体上，延迟了TiO2由锐钛矿向金红石相的转化，增强了Mo与载体TiO2的相互作用，促进Mo物种由四面体配位向八面体配位转化，使TiO2光吸收限发生蓝移，对可见光部分的吸收明显增加，拓宽了催化剂的光响应范围；固体材料吸光性能强弱顺序Pd/MoO3-TiO2 >Cu/MoO3-TiO2>Ag/MoO3-TiO2>Ni/MoO3-TiO2；Pd对CO2吸附能力过强，卧式吸附态脱附温度高，光催化效率不高；金属Cu对CO2吸附能力适中，CO2与C3H6脱附温度较接近，实现了光-表面-热的协同作用，光量子效率最高。     

Cu/MoO3-TiO2/SiO2上光催化CO2和C3H8合成异丁烯醛的研究

采用表面改性法和等体积浸渍法制备了金属修饰的负载型复合半导体材料Cu/MoO3-TiO2/SiO2, 用X射线衍射、 比表面积测定、 红外光谱、 拉曼光谱和紫外-可见漫反射等技术对固体材料的结构、 吸光性能和化学吸附性能进行了表征, 研究了该材料对CO2和丙烷合成异丁烯醛的光促表面催化规律. 结果表明, 半导体活性组分MoO3和TiO2在所制备的催化剂Cu/MoO3-TiO2/SiO2表面形成化学键, 并存在多种活性吸附位; 金属Cu的修饰拓展了固体材料对光源的响应范围, 提高了反应体系的吸光能力; 固体材料对CO2和丙烷的有效吸附使其在较低温度下就能促进异丁烯醛的紫外光化学合成, 反应选择性达到85％左右. 根据实验结果对光促CO2和丙烷表面催化合成异丁烯醛的机理进行了讨论.     

Cu/MoO3-TiO2光催化CO2与C3H6反应合成甲基丙烯酸的性能

 研究了Cu/MoO3-TiO2上CO2和C3H6的吸附特性及其光催化CO2与C3H6反应合成甲基丙烯酸(MAA)的性能. 结果表明,在Cu/MoO3-TiO2催化剂表面存在金属Cu位、Lewis酸位Mo6+和Ti4+以及Lewis碱位Mo-O-Ti的桥氧和Mo=O的端氧三类活性中心. 在金属Cu位和Lewis酸位Ti4+(Mo6+)的协同作用下,CO2形成活性较高的卧式吸附态Cu-(CO)-O→Ti4+(Mo6+),C3H6的β-H和β-C分别吸附在Lewis碱位 Mo=O 与金属Cu位上形成Cu-C(CH2)(CH3)-H→O=Mo吸附态. Cu/MoO3-TiO2催化剂吸收阈值蓝移和光吸收量的提高均有利于其催化活性的提高,Cu/10%MoO3-TiO2 光催化剂的催化活性优于其它MoO3含量的催化剂,光量子产率达22.8%,在110 ℃,0.1 MPa,空速200 h-1和125 W紫外灯辐照下,C3H6转化率为8.4%,MAA选择性超过95%. 提出了催化剂光促表面催化CO2与C3H6合成MAA的反应机理.     

光促甲烷和水合成甲醇和氢催化剂的研究

用表面改性法制备TiO2/SiO2，以等体积浸渍法制备负载型复合半导体催化剂(MoO3,ZnO)-TiO2/SiO2，通过XRD、BET、TPR、IR、UV-Vis DRS和TPD等技术对材料的表面形态结构、吸光特性、化学吸附性能及光催化甲烷和水的反应性能进行了表征和分析。结果表明，MoO3-TiO2/SiO2和ZnO-TiO2/SiO2的表面物种均具有显著的量子尺寸效应，在表面分别形成Mo—O—Ti和Zn—O—Ti复合结构；MoO3和TiO2在载体表面的复合可提高对光能的利用率并可增强对甲烷的化学吸附性能， 结果使得MoO3-TiO2/SiO2的光催化反应性能明显优于ZnO-TiO2/SiO2；在固定床环隙反应器中，150℃MoO3-TiO2/SiO2光催化气相甲烷和水合成了目的产物甲醇和氢，甲醇的选择性达到87.3％。     

TiO2/Mo-TiO2 的制备、表征和光催化活性

 采用溶胶-凝胶法制备了掺 Mo 的 TiO2 粉末, 再由其制得 TiO2/Mo-TiO2 复合物光催化剂. 使用 X 射线光电子能谱、X 射线衍射、透射电镜、N2 吸附-脱附、紫外-可见漫反射光谱和荧光光谱等手段对催化剂进行了表征. 在紫外光照射下, 以甲基橙溶液降解为探针反应, 研究了 Mo 掺杂量对样品光催化活性的影响. 结果表明, Mo-TiO2 催化剂的活性不如纯 TiO2, 这是因为 Mo 离子促进了光生载流子的复合; 而带有 n-n 异质结半导体结构的 TiO2/Mo-TiO2 复合催化剂具有比纯 TiO2 和 Mo-TiO2 催化剂更高的光催化活性. 当 Mo 掺杂摩尔分数为 2%, TiO2:Mo-TiO2 质量比为 10:1 时, 活性是纯 TiO2 的 1.57 倍.     

SnO2-TiO2复合光催化剂的制备和性能

采用均匀沉淀法在超细TiO2表面包覆SnO2,制备出SnO2-TiO2复合光催化剂,并用EDS,XRD,TEM和BET比表面积测定等手段进行了表征.以活性艳红X-3B溶液为模拟废水,考察了SnO2-TiO2的光催化活性.结果表明,复合粒子由锐钛矿型TiO2和金红石型SnO2组成;与纯TiO2相比,SnO2-TiO2的光催化活性有较大提高,SnO2最佳包覆量为18.4%.复合光催化剂活性的提高归因于不同能级半导体之间光生载流子的输运和分离.     

MoO3-TiO2/SiO2上光促表面催化甲烷和水合成甲醇和氢气

用分步等体积浸渍法制备了负载型复合半导体催化剂MoO3-TiO2/SiO2,通过XRD,BET,TPR,IR,UVDRS和TPD等手段对其进行了表征,结果表明,活性组分在载体表面高度分散,并具有量子尺寸效应,吸光阈值显著蓝移;TiO2在SiO2表面分散可增强MoO3与载体的相互作用,调变吸光性能,所形成的表面活性基元能够有效地吸附活化甲烷和水.在100℃下利用固定床环隙反应器借助紫外光的激发,通过“光-表面-热”协同作用,气相甲烷和水在MoO3-TiO2/SiO2表面生成了甲醇和氢,选择性达到85.6%.     

活性炭负载Cu离子掺杂纳米TiO2颗粒的制备及光催化性能

采用溶胶-凝胶法在活性炭(AC)表面负载掺杂Cu离子的TiO2纳米颗粒, 制备负载型掺杂Cu2+-TiO2/AC复合光催化剂, 采用XRD, ESR, FS, UV-Vis和BET等手段对其进行了表征, 通过罗丹明B的光催化降解试验, 分析活性炭载体的比表面积和Cu离子掺杂量对负载型掺杂催化剂光催化活性的影响. 结果表明, Cu以+2价存在, Ti以少量的+3价存在; TiO2纳米颗粒具有量子尺寸效应, 吸光阈值显著蓝移, 并使光谱相应范围向可见光区拓展; 另外, 适量Cu离子的掺杂降低了负载型TiO2/AC的荧光强度. 负载和高温处理没有改变活性炭载体的微观结构. 以AC3为载体和质量分数为3%的Cu离子掺杂所制备的3%Cu2+-TiO2/AC3催化剂的活性最高, 并且该催化剂便于回收, 在重复使用中也表现出很高的光催化活性.     

MoO_3/V_2O_5异质结构材料的静电纺丝法制备及光催化性能

以聚乙烯吡咯烷酮(PVP)、四水合钼酸铵[(NH4)6Mo7O24·4H2O]和偏钒酸铵(NH4VO3)为原料,利用静电纺丝技术结合溶胶-凝胶法制备了在可见光区具有高光催化活性的MoO3/V2O5异质结构半导体光催化剂.采用X射线衍射光谱(XRD)、傅里叶变换红外光谱(FTIR)、场发射扫描电子显微镜(FE-SEM)、X射线光电子能谱(XPS)和紫外-可见(UV-Vis)漫反射光谱等测试手段对材料进行了表征.以光降解亚甲基蓝(MB)为模型反应,考察了MoO3/V2O5异质结构材料的光催化性能.结果表明,n(Mo)/n(V)1∶8时均能形成MoO3/V2O5异质结构且带隙明显宽于V2O5,可有效地实现光生电子和空穴的分离,增强体系的量子效率,促进光催化活性的提高,其中n(Mo)/n(V)=1∶6时光催化活性最高(达到97.24%),并分析和探讨了光催化机理.     

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%).     

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 pyrrolo[1,2-a]pyrazines and pyrazino[1,2-a]indoles by Curtius reaction in Morita-Baylis-Hillman derivatives

Synthesis of substituted pyrrolo[1,2-a]pyrazines and pyrazino[1,2-a]indoles from the Morita-Baylis-Hillman derivatives of acrylates via saponification followed by Curtius reaction is described.     

正丁胺对激光染料荧光谱影响的研究

用正丁胺作为碳源,采用射频辉光放电制备碳膜,选用激光染料R6G和聚乙二醇混合液作为蒸气源,采用单源热蒸发,在蒸发室与染料同时沉积得到混合膜,用拉曼光谱和红外光谱分析了碳膜的结构和键合方式,分析表明:碳膜中存在胺基团和氢原子.混合膜的荧光谱测量结果表明,认为正丁胺对染料荧光谱的影响是因为胺基和氢原子的存在.     

Cu0-catalysed 1,3-dipolar cycloadditions of α-amino acid derived N,N-cyclic azomethine imines to ynones

A series of 20 CuAIAC reactions between eight 4-acylamino substituted pyrazolidine-3-one-1-azomethine imines and four terminal ynones were performed using Cu⁰ as catalyst. The corresponding fluorescent cycloadducts were obtained in very high yields upon simple workup. Thus, Cu-metal turned out to be a better catalyst than Cu^I in terms of yield and ease of isolation. Availability of azomethine imines, mild reaction conditions, and simple workup enable a “click” access to libraries of densely substituted 2,3-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-ones. Reactivity of differently substituted dipoles was evaluated experimentally and by quantum chemical methods (DFT).     

Synthesis and antioxidative/anti-inflammatory activity of novel fullerene–polyamine conjugates

(E)-4-(Fullerenopyrrolidin-1-yl)-3-methylbut-2-enoic acid and its corresponding succinimidyl ester, readily obtained through Prato-type modification of C₆₀, were used for the selective N-acylation of polyamines. The thus obtained conjugates were evaluated for their antioxidative and anti-inflammatory activity and their cytotoxicity was determined. Members of this family of compounds showed interesting anti-lipid peroxidation, anti-lipoxygenase and anti-inflammatory activity and comparable cytocompatibility to spermidine.