氮掺杂纳米多孔TiO2∶EDTA-Na2辅助水热合成及光催化性能

利用螯合剂乙二胺四乙酸二钠(EDTA-Na₂)作为致孔剂,以三氯化钛(TiCl₃)为前驱体,利用水热法直接合成了氮掺杂的纳米多孔TiO₂。通过 SEM、XRD、IR、低温N2吸附-脱附、XPS、热重分析(TG)和紫外可见(UV)光谱对样品进行了表征与分析。结果表明所合成TiO₂以锐钛矿相形式存在,氮掺在TiO₂晶面之间,具有典型的介孔结构和较高的比表面积,通过改变EDTA-Na₂的浓度,比表面积可控制在95~216 m²·g^-1之间。这种纳米多孔TiO₂在光降解甲基橙的实验中表现出很好的光催化活性,且随着EDTA-Na₂的浓度增大而逐渐增加。     

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.     

等离子体修饰磁载TiO2光催化剂性能研究

以化学共沉法制备的CoFe₂O₄纳米粒子为磁核,采用TiCl₄水解包覆技术制备磁载二氧化钛纳米复合粒子CoFe₂O₄ /TiO_x(TCF),利用低温等离子体技术修饰TCF制备了CoFe₂O₄/TiO₂(PTCF)纳米复合光催化剂。运用VSM(振动样品磁强计)技术对样品磁性能进行研究,结果表明：等离子体修饰后的复合材料仍具有较高的饱和磁化强度,可在外加磁场作用下实现催化剂在水中的分离与回收;样品的XRD、TEM和UV-Vis分析测试结果表明：等离子体修饰后的复合材料有锐钛矿型TiO₂存在;TEM谱图显示磁核CoFe₂O₄的平均粒径约为20 nm,TCF复合粒子的粒径约为30~40 nm,TiO₂包覆层的厚度为10~20 nm。与纯TiO₂相比PTCF样品对光的吸收拓展到整个紫外-可见区,扩大了光谱响应范围;对甲基橙溶液降解的光催化活性评价研究表明：TCF复合粒子等离子体修饰后的PTCF纳米复合光催剂的光催化活性明显提高。     

晶相组成可调的高活性可见光应答型二氧化钛纳米复合光催化材料的制备

采用新的化学溶液法,通过不同体积的钛酸四异丙酯的2-乙二醇单乙醚溶液与一定浓度的H₂O₂水溶液直接反应并对生成的钛过氧化配合物进行焙烧,制备了一系列TiO₂光催化剂. 表征发现,所得TiO₂样品为金红石和锐钛矿的纳米复合晶体,改变2-乙二醇单乙醚的体积可实现金红石相比例在0~96%广范围的调变.与商业二氧化钛P-25相比,所得的TiO₂紫外-可见光吸收谱出现明显红移,间隙能降低, 在可见光照射下,该样品对亚甲基蓝有良好的降解活性. 当2-乙二醇单乙醚的添加量为5 ml时,所得样品体相中金红石相比例接近50%,其光催化活性和吸附性能最好,可分别是P-25的3倍和5倍. 拉曼光谱结合X射线衍射等表征结果表明,该样品的表面仅含少量的金红石相. TiO₂纳米复合晶表面晶相的组成和分布对其光催化降解亚甲基蓝的活性及其吸附能力有直接的影响. 另外,TiO₂纳米复合晶的缺陷浓度也是增强其光吸收能力,提高其可见光光催化活性的原因之一.     

纳米TiO2固相光催化降解固体废弃塑料

以纳米TiO₂作光催化剂,制备出环境友好的可光催化降解的纳米复合塑料是解决“白色污染”行之有效的方法之一。本文综述了近年来纳米TiO₂固相光催化降解固体废弃塑料的研究进展,探讨了TiO₂-聚合物复合膜的固相光催化反应机理及光催化降解情况,从对纳米TiO₂表面改性以改善其在聚合物中的分散性,对纳米TiO₂进行修饰处理以提高其对可见光的吸收,从而提高其光催化效率等方面探讨了可光降解塑料研究存在的问题及应用前景。     

中空Ta2O5/TiO2复合光催化剂的可控氧化制备及性能

以钛粉、钽粉为原料,炭黑作为反应性模板,通过熔盐法在炭黑表面原位生长了TaTiC₂纳米碳化物涂层,并以所得TaTiC₂/C复合物为碳化物前驱体,再经可控氧化制备出中空Ta₂O₅/TiO₂复合光催化剂。采用X射线粉末衍射（XRD）、扫描电子显微镜（SEM）、透射电子显微镜（TEM）、紫外-可见（UV-Vis）漫反射（DRS）及N₂物理吸附等手段对所制备的光催化剂进行形貌、显微结构及孔结构表征。以高压汞灯为紫外光源,以亚甲基蓝为目标降解物,通过光催化降解实验评价中空Ta₂O₅/TiO₂复合光催化剂的光催化活性。结果表明,熔盐法生长碳化物涂层厚度均匀（20~30 nm）,碳化物主要以TaTiC₂晶相存在且具有纳米级的颗粒尺寸。中空Ta₂O₅/TiO₂复合光催化剂同时具有200 nm左右的中空大孔结构及壳层10 nm左右的介孔结构。中空大孔和介孔的存在提高了所制备催化剂对亚甲基蓝的吸附能力。此外,TiO₂与Ta₂O₅通过电子能带结构的耦合,有效提高了光生电子和空穴的分离效率,从而显著提高了光催化活性。n_Ti∶n_Ta=2.5∶1.5时,相应的中空Ta₂O₅/TiO₂复合光催化剂表现出最佳的光催化活性,对亚甲基蓝的紫外光催化降解率高达97%。     

玻璃微珠/Ag/TiO2可见光催化剂的制备与表征

通过离子交换法将Ag纳米颗粒负载于玻璃微珠的表面及浅表层,并以钛酸四丁酯的乙醇溶液为前驱体,将TiO₂负载于包含银的玻璃微珠表面,制得一种玻璃微珠/Ag/TiO₂复合光催化剂。由于纳米银的表面等离子体吸收效应,该复合光催化剂具有一定的可见光响应特性。利用XRD、SEM对样品进行表征,可发现玻璃微珠表面形成一层均匀多孔的锐钛矿TiO₂,其粒径均在50 nm左右。由漫反射光谱可得出该催化剂具有较强的可见光吸收,并在降解甲基橙溶液的试验中表现出较好的可见光催化活性。     

g-C3N4-BiOBr复合材料制备及可见光催化性能

利用原位沉积法将BiOBr纳米片生长到g-C₃N₄表面,制得g-C₃N₄-BiOBr p-n型异质结复合光催化剂。采用X射线衍射(XRD)、红外光谱(FTIR)、场发射扫描电子显微镜(FE-SEM)、透射电子显微镜(TEM)、紫外可见漫反射(UV-Vis-DRS)和荧光光谱(PL)等测试对光催化剂结构和性能进行表征。通过可见光辐照降解甲基橙水溶液检测评估复合光催化剂光催化活性。研究结果表明:复合光催化剂由BiOBr和g-C₃N₄两相组成,BiOBr纳米片在片状g-C₃N₄表面快速形核生长形成面-面复合结构。相比于纯相g-C₃N₄和BiOBr,g-C₃N₄-BiOBr复合材料具有更强可见光吸收能力,吸收带边红移。在可见光辐照100 min后,性能最佳的2:8 g-C₃N₄-BiOBr复合光催化剂光催化活性分别是纯相g-C₃N₄和BiOBr的1.8和1.2倍,经过4次循环实验后,其降解率仍达84%,说明复合结构光催化剂催化性能和稳定性增强。复合光催化剂的荧光强度显著降低,说明光生载流子复合得到了有效抑制。复合光催化剂催化性能的提高归因于p-n型异质结促进电荷有效分离、抑制电子-空穴复合和吸收光波长范围的扩展,相比单一成分材料具有更好的催化活性和稳定性。自由基捕获实验证明,可见光降解甲基橙光催化过程中的主要活性成分为空穴,并据此提出了可能的光催化机理。     

具有丰富(001)面的锐钛矿TiO2晶体的无氟合成

采用一种全新的方法实现了无氟、在阳离子聚合物参与下合成具有丰富(001)面的锐钛矿TiO₂晶体(TiO₂-P), 并通过X射线衍射、扫描电镜、透射电镜、紫外-可见光谱等手段对样品进行了表征. 光催化测试显示, 该样品对甲基橙的降解具有比常规锐钛矿TiO₂和商业P25更好的活性, 这可归因于TiO₂-P具有大量的暴露(001)晶面.     

溶胶-凝胶法低温制备N掺杂TiO2可见光光催化剂

为了满足低温制备可见光光催化材料的需要,采用溶胶-凝胶法制备TiO₂纳米晶溶胶,再与聚乙烯基吡咯烷酮(PVP)直接反应制备N掺杂TiO₂可见光光催化剂。通过XPS分析,说明N取代了部分晶格中的O,UV-Vis漫反射吸收光谱显示,光催化剂具有明显的可见光响应,这是由于N原子的2p轨道位于O原子的2p轨道之上,从而使得价带和导带间的能量带隙变窄,引起吸收带红移,产生明显的可见光吸收。依靠亚甲基兰(MB)的可见光降解实验证明,N掺杂光催化剂具有良好的可见光光催化活性,16 h MB降解率接近25％。     

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.