Ce3+掺杂对纳米TiO2/SiO2镀膜玻璃性能的影响

在TiO2/SiO2溶胶中按不同比例掺杂Ce3+得到复合溶胶,将溶胶喷涂在浮法玻璃原片上,105～300 ℃烘干得到镀有纳米TiO2膜的透明玻璃.AFM图像表明 掺杂Ce3+的TiO2/SiO2镀膜玻璃表面的颗粒小于没有掺杂Ce3+的TiO2/SiO2镀膜玻璃表面颗粒.掺杂Ce3+与TiO2 摩尔比为0.01∶1时,镀膜玻璃可见光透射比为85.3%,紫外线透射比39.7%、可见光反射比7.3%、太阳光直接透射比83.5%、太阳光直接反射比6.6%; 水接触角θ为0°; 在可见光照射下,分解甲基橙的时间为48 h; 膜表面电阻率为5.9×107 Ω·cm.在400～700 ℃对镀膜玻璃进行高温处理,其光学性能明显提高,可见光透射比为91.7%,紫外线透射比39.1%、可见光反射比6.4%、太阳光直接透射比92.0%、太阳光直接反射比5.9%; θ角为0°,亲水性明显提高; 在可见光照射下,甲基橙分解时间为28 h; 膜表面电阻率为5.5×107 Ω·cm,玻璃在可见光条件下就具有自清洁能力.     

染料敏化La~(3+)掺杂的TiO_2纳晶薄膜制备及其光电性能

采用溶胶-凝胶法制备出La3+掺杂的TiO2纳米粉体材料,通过料浆喷涂工艺制得掺杂La3+的TiO2薄膜并将其以N719染料敏化制成染料敏化太阳能电池(DSSC)。以X射线衍射(XRD)、扫描电镜(SEM)和DSSC测试系统对制得的La3+掺杂的TiO2纳米粉体材料、相应的La3+掺杂的TiO2薄膜以及制成的DSSC分别进行测试表征,研究了La3+掺杂对TiO2晶型和染料敏化太阳能电池性能的影响。XRD测试结果表明,La3+的掺杂改善了TiO2的颗粒分布;电池的测试结果说明,La3+掺杂量为0.5%,煅烧温度为450℃时制备的纳米TiO2膜DSSC电池性能最佳,光电转换效率达1.926%。     

钇掺杂有序大孔TiO_2微球的制备与光催化性能研究

采用溶胶-凝胶法、胶体晶体模板法制备了钇掺杂有序多孔TiO2微球,利用FTIR,SEM,XRD,XPS,UV-V is分析对其进行表征,并研究钇掺杂前后材料的光催化性能。结果表明:钇掺杂有序多孔TiO2微球规整致密,但局部有孔洞的塌陷。钇掺杂前后有序多孔TiO2微球的晶型没有改变,仍为锐钛矿型。XPS分析发现钇掺杂有序多孔TiO2微球是可行的,材料中含有钇元素含量约为1.0%。UV-V is分析表明钇掺杂使得TiO2吸收光红移至可见光区,甲基橙降解实验显示掺钇有序多孔TiO2微球的光催化性能好于未掺钇TiO2的光催化性能。     

掺杂TiO2纳米粉的合成、表征及催化性能研究

 考察了制备方法对掺杂Fe2O3,ZrO2或SnO2的TiO2纳米粉的XRD谱及催化性能的影响．结果表明,用共沉淀法制备的Fe2O3·TiO2对其XRD谱强度的影响较大,而负载法制备Fe2O3／TiO2对其XRD谱的强度无影响;两种方法制备的掺杂ZrO2或SnO2的TiO2样品对XRD谱均无影响．TEM结果表明,TiO2纳米粉的晶粒均匀,粒径为14～18nm．苯酚水溶液的光催化氧化分解反应结果表明,与TiO2样品相比,负载型Fe2O3／TiO2的催化活性明显较高,但ZrO2／TiO2,SnO2／TiO2和共沉淀型Fe2O3·TiO2的催化活性变化不大．可以认为,对掺杂Fe2O3的TiO2催化剂,负载法是较好的制备方法．     

控制胶体合成法制备掺铁TiO_2粉末及光催化降解甲基橙

分别采用控制胶体合成法和溶胶-凝胶法制备了2种不同掺铁方式的TiO2粉末,并用XRD、TEM、BET、UV-Vis、FS等技术对样品进行了表征。在紫外光照射下,以甲基橙溶液的光催化降解反应为探针,研究了掺Fe离子浓度、包覆的次数、不同掺杂方式对样品光催化活性的影响。结果表明,以均匀掺铁TiO2(铁含量大于0.02mol%)干凝胶粉末为载体,采用控制胶体合成法制备了具有P-N结型结构的非均匀掺铁TiO2粉末,其光催化活性较均匀掺杂TiO2粉末明显提高,并且随着包覆次数(≤3次)的增加而增强,以0.04mol%掺铁TiO2粉末包覆3次后制备的样品具有最佳光催化活性,其表观速率常数是未掺杂的TiO2粉末的5.32倍,是具有相同Fe含量的均匀掺杂TiO2粉末的4.58倍。     

稀土离子掺杂对纳米TiO2光催化制氢活性的影响

采用溶胶-凝胶技术制备了纳米TiO2和一系列稀土离子掺杂的TiO2光催化剂,通过X射线衍射、透射电镜及N2吸附等技术对其进行了表征,考察了样品光催化分解水制氢的性能.结果表明,稀土离子掺杂有效抑制了TiO2粒子的生长,提高了粒子的分散性,增大了催化剂的比表面积,从而大幅度提高了其光催化分解水制氢的性能.其中,Gd3 掺杂的TiO2样品粒径最小,分散性最好,比表面积最大(是未掺杂TiO2的35倍).掺杂离子的电子构型对样品的光催化制氢活性有较大影响,具有全空电子构型的La3 和半充满电子构型的Gd3 掺杂的样品具有较高的光催化制氢活性(分别是未掺杂TiO2的3.69倍和3.72倍).     

Cu掺杂TiO_2薄膜的摩擦学性能

采用溶胶-凝胶法在普通玻璃基底上制备了纯TiO2和Cu掺杂的TiO2(Cu-TiO2)纳米结构薄膜,利用X射线光电子能谱(XPS)、原子力显微镜(AFM)、粉末X射线衍射(XRD)及UMT-3摩擦磨损试验机考察了Cu掺杂量对薄膜组成、结构、表面形貌及摩擦学性能的影响.结果表明,相比于纯TiO2薄膜,Cu掺杂TiO2纳米薄膜平整、均匀,具有较好的耐磨减摩性能.Cu掺杂量的多少直接影响Cu-TiO2薄膜的减摩抗磨性能,当Cu掺杂量为5%(摩尔分数)时,Cu-TiO2膜具有最佳的耐磨寿命和最低的摩擦系数.     

Mo掺杂TiO2/AC负载膜的制备及光催化活性

溶胶-凝胶法;Mo掺杂TiO2/AC负载膜的制备及光催化活性     

稀土掺杂的纳米TiO2分散性及光学性能研究

采用溶胶凝胶法在同一条件下制备REa+:Ti4+=0.02和0.10的稀土掺杂的纳米TiO2材料,其中REn+为Nd3+,Ce4+,La3+,Er3+四种稀土元素.通过TG-DTG,XRD,TEM,UV-Vis等测试方法对所制备的纳米TiO2进行焙烧温度、晶胞尺寸、晶粒形貌、谱学特性等方面的研究.研究表明,稀土掺杂的纳米TiO2径粒尺寸均在20 nm左右,少量稀土掺杂不但有利于TiO2颗粒的分散,而且有利于TiO2向金红石相转变.同时,由于表面修饰作用和晶场效应的影响,掺杂使纳米材料在可见光范围内有不同程度的"红移"现象,Ce4+掺杂的纳米TiO2在可见光的"红移"程度最强.稀土掺杂的纳米TiO2在农用膜和节能材料上可广泛运用.     

氮铂共掺杂纳米二氧化钛的制备及表征

采用溶胶-凝胶法制备了氮掺杂纳米TiO2(N-TiO2),并用光分解沉积法在N-TiO2表面负载上微量金属Pt形成铂-氮共掺杂纳米TiO2(Pt/N-TiO2).通过X射线衍射、光电子谱、紫外-可见吸收、扫描电镜和光电流测试对催化剂进行了表征.结果表明:Pt和N共掺杂对TiO2的晶型和形貌影响不大,但其吸收边带较纳米TiO2约红移20nm,Pt/N-TiO2电极在可见光区的光电流约为纳米TiO2电极的4倍.     

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.     

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.     

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.