BiOX(X=Cl,Br, I)复合光催化材料降解水体中抗生素研究进展

抗生素大量使用致使其在水环境中普遍存在,对生态环境和人类健康造成一定威胁。卤氧化铋BiOX(X=Cl, Br, I)具有独特二维层状结构、适宜的禁带宽度等优点而被用作光催化剂来降解水中残留的抗生素。但单一BiOX(X=Cl, Br, I)存在可见光吸收能力偏弱、稳定性不佳等问题,往往需要对其进行复合改性(如金属负载、碳材料修饰及构建异质结)来提升去除水中抗生素的性能。本文主要介绍了用于水体中抗生素类污染物降解的BiOX(X=Cl, Br, I)复合光催化材料的设计合成、活性增强机制以及光催化反应机理。相比于金属负载及碳材料修饰,构建半导体异质结是常用且经济有效地增强BiOX(X=Cl, Br, I)光催化降解水中抗生素性能的方法。指出该领域以后的研究需要评估BiOX(X=Cl, Br, I)复合光催化材料降解水环境中不同类型抗生素的效果,同时还需揭示自然水体的背景成分(如溶解性有机质、无机离子等)对该类复合光催化剂去除水中抗生素活性和稳定性的影响。最后提出引入过氧化物来提升BiOX复合光催化体系矿化水中抗生素的效果以及构建磁性BiOX光催化材料来解决降解反应后的固-液分离问题。     

Ni(Ⅱ),Pd(Ⅱ),Pt(Ⅱ)环戊基(苯基)叔膦配合物的低频振动光谱及构型

本工作合成了下述金属配合物:MCl_2L_2(M=Pd,Pt),NiX_2L_2(X=Cl,Br,I),L=PPh_(3-x)(C_5H_9)_x(x=0-3),并研究了它们的远红外光谱和某些低频Raman光谱。对某些M-P,M-X振动谱带做出了归属,并提供结构信息。     

氯氧化铋催化剂的电子结构调控及其光催化性能研究

以不同Bi/Cl摩尔比例为原料设计合成了一系列BiOCl半导体催化材料。扫描电子显微镜、XRD衍射峰拟合等分析结果显示,Bi/Cl比例的改变对BiOCl的形貌、表面结构、微观电子结构均具有一定的调控作用。以Bi/Cl = 1 : 1为原料合成的BiOCl光催化剂具有最窄的带隙值（Eg=3.18 eV）,使得其具有较强的的光响应能力。光催化去除罗丹明B（RhB）结果表明,随着Bi/Cl摩尔比例的减小,BiOCl的催化性能呈现先增强后减弱的趋势。Bi/Cl = 1 : 1样品具有最优的催化活性,源于其较优异的光吸收性能以及特殊的表面特性。光催化机理研究表明,光催化去除RhB的过程中,起作用的活性物质主要为光生电子、空穴以及半导体表面产生的超氧自由基。     

BiOCl/NaBiO_3复合材料的原位合成及光催化性能

利用HCl与Na Bi O3反应原位制备了结构可控的Bi OCl/Na Bi O3复合光催化材料.通过X射线粉末衍射(XRD)、紫外-可见漫反射光谱(UV-Vis-DRS)和扫描电子显微镜(SEM)等技术对其晶相组成、光吸收特性和表面形貌进行了表征,并评价了样品在可见光和紫外光下的光催化性能.结果表明,尽管Bi OCl几乎没有可见光活性,但27.4%Bi OCl/Na Bi O3在可见光下却表现出明显高于纯Bi OCl和Na Bi O3的光催化活性.由于紫外光照可以有效激发Bi OCl,所有组成的复合Bi OCl/Na Bi O3都显示出高于纯Bi OCl和Na Bi O3的光催化活性,其中47.6%Bi OCl/Na Bi O3具有最大光催化活性.研究了加入不同活性物种的捕获剂对光催化效率的影响,结合荧光实验结果和样品能带结构推测了复合材料光催化过程中光生载流子的传输行为.结果表明,Bi OCl/Na Bi O3催化活性增强主要归结于2种材料之间形成了有效的异质结构,其内建电场能够促进光生载流子的传输和分离;羟基自由基在光催化降解过程中是主要的活性物种.     

Ni(II), Pd(II), Pt(II)环戊基(苯基)和膦配合物的低频振动光谱及构型

本工作合成了下述金属配合物: MCl2L2(M=Pd, Pt), NiX2L2(X=Cl, Br, I),L=PPh3-x(C5H9)x(x=0-3), 并研究了它们的远红外光谱和某些低频Raman光谱, 对某些M-P, M-X振动谱带做出了归属, 并提供结构信息。     

Ni(II), Pd(II), Pt(II)环戊基(苯基)和膦配合物的低频振动光谱及构型

本工作合成了下述金属配合物: MCl2L2(M=Pd, Pt), NiX2L2(X=Cl, Br, I),L=PPh3-x(C5H9)x(x=0-3), 并研究了它们的远红外光谱和某些低频Raman光谱, 对某些M-P, M-X振动谱带做出了归属, 并提供结构信息。     

Ag@AgX(X=Cl,Br,I)及其复合物光催化剂的研究进展

综述了具有表面等离子体共振效应的光催化剂Ag@AgX(X=Cl,Br,I)及其与TiO2、BiOX、BiVO4、ZnO等复合物的光催化机理、应用等方面的进展,并展望了Ag@AgX(X=Cl,Br,I)及其复合物未来的发展方向和研究内容。     

BiOBr的制备及其光催化性能的研究

以氧化铋为原料,采用水解法合成了溴氧化铋光催化剂,采用X射线衍射仪对溴氧化铋晶体进行表征,研究了溴氧化铋晶体降解罗丹明B溶液的光催化性能。实验结果表明,在反应温度为40℃、反应时间为90 min合成的Bi OBr光催化性能最好,具有较强的光催化活性,其催化活性优于Bi OCl催化剂,其催化降解罗丹明B反应表现为假一级动力学。     

磁性γ-Fe2O3/BiOCl/BiVO4复合材料的制备及其光催化性能研究

采用γ-Fe2O3掺杂对Bi OCl/Bi VO4进行改性。通过超声-水热法合成出粒径在1.5~2.0μm、表面附着Bi OCl纳米片和球形颗粒γ-Fe2O3的Bi VO4微米块状磁性γ-Fe2O3/Bi OCl/Bi VO4复合光催化剂。结合XRD、SEM、UV-Vis DRS等表征手段对复合材料的组成、形貌、光学性质进行表征,通过光催化降解若丹明B溶液对其光催化性能进行评价。结果表明,使用过的15%γ-Fe2O3/Bi OCl/Bi VO4复合光催化剂可以通过外磁场作用很容易地与反应溶液分离,且仍具有较高的可见光催化活性和稳定性,其重复使用4次后,对若丹明B的降解率和光催化剂的回收率变化不明显,仍达到88.6%和90.3%。     

镍(II)、钯(II)、铂(II)-环戊基苯基膦配合物的合成及表征

合成了十五种配合物MX~2[(C~5H~9)~nPPh~3-n]~2系列, 其中M=Ni, X=Cl, Br,I; M=Pd, Pt, X=Cl; 且C~5H~9代表环戊基, n=1, 2, 3。通过元素分析、远红外光谱及紫外光谱确定了这些配合物的化学组成和空间构型。讨论了不同配体对配合物结构的影响。     

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.