Sol-Gel法制备La~(3+)改性的TiO_2纳米粉体

在常用的半导体光催化材料中,研究较多的有TiO2、ZnO、CdS等[1-3],其中TiO2因性能稳定、催化活性高、无毒、不产生二次污染和成本低廉等优点,在光催化降解污染物领域显示出优越的应用前景[3-6].     

Co~(2+)掺杂的纳米TiO_2薄膜光催化特性及电化学阻抗谱研究

本文采用交流电沉积技术,在多孔氧化铝模板中合成出Co2+掺杂的纳米TiO2薄膜(Co2+/TiO2薄膜)。以次甲基蓝为降解物,研究了纳米Co2+/TiO2薄膜在可见光下的催化性能,考察了阳极偏压对光催化活性的影响。用电化学阻抗谱(EIS)研究了纳米Co2+/TiO2薄膜在次甲基蓝溶液中的电化学行为,给出了相应的等效电路和半导体能带结构参数-空间电荷层宽度。研究表明,适量Co2+掺杂可以提高TiO2薄膜的光催化活性。在Co2+/TiO2膜电极上施加一定阳极偏压,使空间电荷层宽度增加,因此能有效实现光生电子-空穴分离,进一步提高次甲基蓝的光催化降解效率。     

GRS大红和弱酸红R混合液的光催化降解模拟研究

近年来,利用半导体材料处理印染废水的光催化氧化技术研究日益受到重视.该技术与传统的污水处理方法相比,具有高效、稳定、无二次污染以及对各类有机污染物(包括难生物降解的有毒污染物)可深度、彻底氧化等突出优点[1-2].目前对该技术研究的关注焦点放在高催化活性的光催化剂的研制上,但近年已有人开始利用已有催化剂如TiO2对印染废水进行光催化降解模拟研究,分析确定降解影响因素,并研究降解条件的优化,从而为该技术的应用奠定基础[3-5].     

电场对TiO2纳米膜光催化性能的影响

 以泡沫镍为基材,采用溶胶-凝胶法制备了TiO2纳米膜光催化剂. 在自制外加电场光催化反应装置中,对催化剂施加一定的偏电压,研究了甲基橙溶液的光电催化降解反应,考察了偏压极性、阳极偏压和甲基橙初始溶液浓度等对降解效率的影响,并比较了光电催化与光催化、光解对甲基橙溶液降解的差异. 结果表明,外加阳极偏压形成的电场可以较大幅度提高甲基橙溶液的降解效率. 从半导体和量子力学理论出发探讨了电场促进光催化反应的作用机理.     

纳米TiO2-x光催化膜中的缺陷结构与性能关系初探

半导体TiO2由于具有较大的禁带宽度(TiO2Eg=3.2eV),常用作光化学降解反应的催化剂.利用溶胶-凝胶技术(Sol-Gel)制备薄膜型光催化剂,特别是在石英板或石英反应管壁上制备纳米级TiO2光催化剂膜已成为这一领域的研究热点[1].制备高活性光催化剂的突出问题是如何增加光生电子与空穴的产额,减少它们的复合几率,同时提高光催化膜的表面吸附能力.本实验采用溶胶-凝胶法制备出纳米级无机非整比TiO2-x膜,经过可控气氛热处理后,可在膜表面形成较多亚稳相氧空位(缺陷),为催化剂膜表面提供了更多的吸附中心和反应活性位,因此表现出较高的光催化反应活性[2].     

Sn4+掺杂对TiO2纳米颗粒膜光催化降解苯酚活性的影响

金属离子掺杂能改善TiO2纳米微粒光催化活性,在光降解大气和水污染物的研究中,已引起人们的重视[1,2].实验证明,掺杂物的浓度、掺杂离子的分布、掺杂能级与TiO2能带匹配程度、掺杂离子d电子的组态、电荷的转移和复合等因素对催化剂的光催化活性有直接影响[3].Kamat等[4]曾利用TiO2颗粒与SnO2颗粒混合制膜,使光催化剂活性得到提高.但Sn4+掺杂TiO2用于光催化剂尚少见报道.本文采用等离子体化学气相沉积法(PECVD)[5]制备了Sn4+离子掺杂的TiO2纳米颗粒膜催化剂(TiO2-Sn),考察了其对苯酚的光催化降解活性,讨论了Sn4+离子的掺杂方式及光催化活性提高的机理.     

SO2-4/TiO2固体酸催化剂的酸强度及光催化性能

SO2-4/TiO2固体酸可用于光催化降解溴代甲烷,其光催化性能明显优于TiO2光催化剂.在相同反应条件下,SO2-4/TiO2的光催化活性比TiO2提高2～10倍.当H2SO4浸渍液浓度为1mol/L时,制得的SO2-4/TiO2酸性最强(H0＜-12.14),具有超强酸性和最高的光催化活性.     

活性炭负载TiO2光催化降解1-萘胺

活性炭负载TiO2光催化降解1-萘胺;炭载TiO2光催化剂;萘胺;光催化降解     

气相苯在TiO2光催化剂上吸附常数和光催化反应常数测定

采用溶胶-凝胶法制备TiO2光催化剂以及掺杂Fe3 和Ce3 的TiO2光催化剂,进行间歇式光催化降解气相苯动力学实验,基于光催化Langmuir-Hinshelwood反应动力学模型(L-H模型),测定气相苯在3种光催化剂上的降解动力学常数和吸附平衡常数.根据光催化降解气相苯实验动力学曲线和L-H模型,估算出TiO2、Fe3 /TiO2和Ce3 /TiO2光催化剂光催化降解苯的反应速率常数k和Langmuir吸附常数K分别为0.5247g/m3·min、1.523g/m3·min、1.010g/m3·min和8.605×10-2m3/g、2.390×10-2m3/g、3.928×10-2m3/g.掺杂Fe3 和Ce3 可明显提高光催化剂光催化降解苯的反应速率常数k,其中Fe3 /TiO2,的反应速率常数k最大.     

负载型Pt-TiO2光催化剂的研究

TiO2粉末悬浮体系是一种研究比较早的光催化反应体系[1,2].由于它存在易凝聚和难回收等缺点,给实际应用带来了一定的困难.克服这一障碍的有效途径是制备负载型TiO2[3].所以,这些年来人们对负载型TiO2光催化体系颇有兴趣.从目前的文献报道来看,制备负载型TiO2的方法主要是溶胶法[4].采用溶胶法可在导体或非导体的基体上获得结合牢固、尺寸分布均匀的薄膜,但是膜的催化活性有待于提高.     

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.     

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.     

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.     

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.