盐酸后处理对水热合成纳米钛酸盐形貌及光限幅效应的影响

采用碱性水热合成法制备纳米钛酸盐, 研究盐酸后处理对纳米钛酸盐-二氧化钛形貌及光限幅效应的影响. 采用X射线衍射分析仪、透射电子显微镜和扫描电子显微镜对样品的晶型转变及形貌演变进行表征, 通过紫外-可见光谱与开孔Z扫描激光测试技术, 研究样品的线性光学与非线性光学效应. 结果表明, 当酸处理浓度介于0.10-0.55 mol·L^-1范围时, 水热产物由钛酸盐转变为钛酸盐/二氧化钛混合物; 当酸处理浓度高于0.78mol·L^-1时, 钛酸盐近乎完全转变为金红石型二氧化钛. 在酸处理过程中, 纳米钛酸盐晶型转变速率与盐酸的浓度直接相关. 随着盐酸浓度的增加, 钛酸盐体系中逐步分离出游离的TiO₆八面体, 进而发生TiO₆八面体重组, 使水热产物由钛酸盐纳米管转变成二氧化钛纳米片和纳米颗粒. 当盐酸浓度为0.55 mol·L^-1时, 样品表现出最强的光限幅效应.     

由钛酸盐纳米带水热制备锐钛矿型TiO2纳米带

研究了水热处理具有层状结构的钛酸钠纳米带或钛酸纳米带转化为锐钛矿型TiO₂的制备过程、难易程度和相转化机理. 实验结果表明, 当水热反应温度和时间分别在160 ℃ 和24 h以内, 钛酸钠纳米带很难完全转化为锐钛矿型TiO₂, 若升高反应温度并延长反应时间, 则可制得纯的锐钛矿型TiO₂, 但纳米带形貌被严重破坏; 当水热反应温度和时间分别为160 ℃ 和16 h时, 1次酸洗的钛酸纳米带能够完全转化为锐钛矿型TiO₂, 若钛酸纳米带经过3次强酸浸泡, 则在160 ℃下相转化时间就会缩短到12 h, 所有钛酸纳米带在转化为TiO₂后的形貌仍为纳米带, 但经3次酸浸后生成的TiO₂纳米带表面更光滑. 讨论了钛酸钠纳米带或钛酸纳米带转化为锐钛矿型TiO₂的相转化机理.     

热处理对TiO2纳米管结构相变的影响

TiO₂纳米管为无定形结构,焙烧后则由无定形转变为锐钛矿型,纳米管的管状结构被破坏,晶型转变是TiO₂纳米管的管状结构破坏的根本原因.经热处理,原来的TiO₂纳米管部分转变为长棒状的金红石型晶柱结构,而原料TiO₂在较大温度范围内焙烧均未出现长棒状晶柱结构;TiO₂由A→R的相变温差很大,TiO₂纳米管的A→R相变温度比原料约低350℃;合成的TiO₂纳米管的比表面积和孔体积很大.     

纳米管钛酸CO处理产物的结构及光催化活性

研究了在CO气流中,处理温度对纳米管钛酸(NTA)脱水产物TiO₂的结构及C₃H₆光催化氧化反应活性的影响.结果表明:NTA经CO高温处理后,样品未发生C掺杂,只有碳沉积发生;随着处理温度的升高,样品的比表面积大幅下降,与NTA在空气中焙烧处理相比,由锐钛矿向金红石TiO₂转变的温度提前;CO处理后产物对C₃H₆均未表现出可见光催化性能,但具有紫外光催化活性,随着在CO气氛中处理温度的升高,紫外光催化活性降低.     

方形锐钛矿TiO2纳米晶的合成及表征

在不添加任何模板剂或形状控制剂的条件下,以TiCl₄为前体,经氨水沉淀、乙醇洗涤和超临界干燥(AS制备法)选择性地合成了方形锐钛矿TiO₂纳米单晶.热稳定性研究结果表明,当焙烧温度不超过650℃时,方形锐钛矿TiO₂纳米晶的表面积、孔容、晶粒/颗粒尺寸基本保持不变.XRD和拉曼光谱分析表明,方形锐钛矿TiO₂纳米晶在800℃下焙烧后仍能保持晶相不变,表现出很强的抗晶相转变能力.但在1000℃焙烧后,样品可以完全转变成金红石相TiO₂.     

单一板钛矿相TiO2微晶的制备

以新鲜的无定形TiO₂沉淀为前驱体,在水热条件下得到了板钛矿型TiO₂微晶粉末,考察了前驱体制备过程中碱的种类与用量以及水热反应的温度和时间等因素对板钛矿型TiO₂的影响.XRD,TEM和Raman测试表明,所合成的样品具有单一的板钛矿型TiO₂结构,晶相纯度很高,晶粒形状相同且具有完美的内部结构,粒度分布均匀.此板钛矿型TiO₂样品在900℃时开始向金红石结构转化,1000℃时完全转变为金红石结构.     

Keggin型铬取代的磷钨杂多阴离子/二氧化钛纳米膜光催化剂的制备及可见光催化性能

以钛酸四丁酯Ti(OC₄H₉)₄为TiO₂前驱体,Keggin型铬取代的杂多阴离子PW₁₁Cr为可见光活性组分,采用溶胶-凝胶提拉法在玻片表面制备了PW₁₁Cr/TiO₂纳米膜光催化剂,并用UV-Vis DRS、IR、XRD、SEM和TEM等技术手段对催化剂的光吸收性质、化学组成、晶相和表面结构形貌等进行了表征;讨论了膜中PW₁₁Cr和TiO₂相互作用的方式;以染料模型污染物RhB的可见光催化降解为探针,评估了PW₁₁Cr/TiO₂光催化剂的可见光催化活性,讨论了光催化反应机理,并与TiO₂的光催化反应机理进行了比较;考察了焙烧温度、PW₁₁Cr剂量和溶液pH值对光催化活性的影响;最后用RhB的循环降解实验评估了催化剂的光催化稳定性。 实验结果表明,PW₁₁Cr/TiO₂光催化剂对可见光有明显吸收,较低焙烧温度(100 ℃)下得到的膜为无定形结构,而较高焙烧温度(500 ℃)为纳晶结构;前者的光催化活性较高,在200 W金卤灯照射下降解10 μmol/L RhB,120 min的降解率为95%,4 h的COD去除率为72%;羟基自由基是导致RhB降解的主要氧活性物质;低的膜处理温度,高的PW₁₁Cr负载量和溶液酸性有利于提高PW₁₁Cr/TiO₂膜的光催化活性;经循环重复使用10次,PW₁₁Cr/TiO₂膜的光催化活性仅有较少损失。     

化学沉淀法制备BaTiO3纳米粉体的研究

以正钛酸(H₄TiO₄)、硝酸钡[Ba(NO₃)₂]为原料, 以双氧水、氨水为溶剂, 采用化学沉淀法制备出晶粒尺寸约20 nm的钛酸钡粉体. 研究了原料种类、煅烧温度、加料方式、反应温度对钛酸钡粉体性能的影响, 确定了最佳的制备条件. 结果表明: 当正钛酸(g)∶双氧水(mL)∶氨水(mL)＝1∶5∶3, 且采用正钛酸的双氧水-氨水溶液缓慢滴加到硝酸钡溶液中的加料方式时, 溶解完全, 制得的BaTiO₃粉体粒径小、纯度高. 用X射线衍射(XRD)和扫描电子显微镜(SEM)表征了颗粒的晶体结构、晶型转变机理以及颗粒的形貌|结果显示: 前驱体的起始晶型转变温度为500, 800 ℃煅烧获得的粒子晶型完整, 形貌呈规则的球形, 当煅烧温度升高到900 ℃时, 粉体晶体结构由立方相转变为四方相.     

钛金属表面结构可控多层钛酸盐纳米管薄膜的制备和结构稳定性

在水热条件下, 通过控制反应温度和氢氧化钠的浓度, 在钛金属表面得到结构可控的多层钛酸盐纳米管薄膜. 根据扫描电子显微镜和高倍透射电子显微镜的观测结果, 认为钛金属表面多层钛酸盐纳米管薄膜的形成经历以下4个阶段: (1) 钛金属的水合和碱性钛酸盐水凝胶的生成; (2) 碱性钛酸盐水凝胶分解并形成层状Na₂Ti₃O₇; (3) 层状Na₂Ti₃O₇的生长; (4) 层状Na₂Ti₃O₇的劈裂和多层卷曲成轴形成纳米管. 研究了薄膜形成后机械处理对薄膜形貌和结构稳定性的影响, 并利用超声的方法实现了多层膜的层分离.     

CeO2/TiO2复合纳米纤维的制备及光催化性能研究

采用静电纺丝技术和水热合成法制备了CeO₂/TiO₂复合纳米纤维. 利用X射线衍射(XRD)、拉曼光谱(Raman)、扫描电镜(SEM)、透射电镜(TEM)和比表面积测定(BET)等分析测试手段对样品的形貌及结构进行了表征, 并以罗丹明B的脱色降解为模式反应, 考察了样品的光催化性能. 结果表明: CeO₂纳米粒子均匀地生长在TiO₂纳米纤维表面, 形成了异质结构的CeO₂/TiO₂复合纳米纤维光催化材料. 通过改变碱源, 可以得到不同形貌的CeO₂. CeO₂的存在增加了TiO₂纳米纤维的比表面积, 有效地实现TiO₂光生电子和空穴的分离, 增强了体系的量子效率, 与纯TiO₂纳米纤维相比光催化活性明显提高. 初步探讨了异质结的形成机理.     

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.