CdS量子点敏化ZnO纳米棒阵列电极的制备和光电化学性能

采用连续式离子层吸附与反应法制备了CdS量子点敏化的ZnO纳米棒电极.应用扫描电子显微镜(SEM)、X射线衍射(XRD)和透射电子显微镜(TEM)对CdS量子点/ZnO纳米棒电极的形貌、晶型和颗粒尺寸进行了分析和表征;采用光电流-电位曲线和光电流谱研究了不同CdS循环沉积次数及不同沉积浓度对复合电极的光电性能影响.结果表明,前驱体浓度都为0.1mol·L-1且沉积15次敏化后的ZnO纳米棒阵列电极光电性能最好.与单纯的ZnO纳米棒阵列电极和单纯的CdS量子点电极相比,其光电转换效率显著提高,单色光光子-电流转换效率(IPCE)在380nm处达到76%.这是因为CdS量子点可以拓宽光的吸收到可见光区,并且在所形成的界面上光生载流子更容易分离.荧光光谱实验进一步说明了光电增强的原因是,两者间形成的界面中表面态大大减少,有利于减少光生电子和空穴的复合.     

液相沉积法制备ZnO/CdS复合纳米棒阵列薄膜及其光电性质

采用两步化学溶液沉积法在氧化铟锡(ITO)导电玻璃衬底上制备了ZnO/CdS复合纳米棒阵列薄膜.利用X射线衍射(XRD)仪、扫描电子显微镜(SEM)、紫外-可见(UV-Vis)吸收分光光度计、荧光(PL)光谱仪及表面光电压谱(SPS)研究了不同CdS沉积时间对复合薄膜的晶体结构、形貌、光电性质的影响.研究结果表明:ZnO纳米棒阵列表面包覆CdS纳米颗粒后,其吸收光谱可拓展到可见光区;与吸收光谱相对应在可见光区出现新的光电压谱响应区,这一现象证实,通过与CdS复合可显著提高ZnO纳米棒阵列在可见光区的光电转换性能;随着CdS纳米颗粒沉积时间的延长,复合纳米棒阵列薄膜在大于383nm波长区域的光电压强度逐渐减弱,而在小于383nm波长区域的光电压强度逐渐增强.用两种不同的电荷产生和分离机制对这一截然相反的光响应过程进行了详细的讨论和解释.     

g-C_3N_4/CdS纳米棒复合光催化剂的制备及其光催化性能

采用简单的水热法制得CdS纳米棒,采用溶剂热法制得g-C_3N_4/CdS纳米棒复合光催化剂(1),其结构和性能经SEM,XRD和UV-Vis(DRS)表征。探究了1在可见光作用下光催化降解模拟有机污染物甲基橙的性能。结果表明:在可见光作用下,与纯CdS纳米棒光催化剂比较,1的催化活性明显提高,稳定性显著增强。     

单晶二氧化钛纳米棒阵列的修饰及其在量子点敏化太阳电池中的应用(英文)

使用TiCl4溶液对单晶TiO2纳米棒阵列(TNRs)进行修饰,通过在TiO2纳米棒表面合成TiO2纳米颗粒来提高TNRs的表面积,提高TNRs对量子点的吸附能力,并在此基础上研究了TiCl4修饰时间对基于单晶TNRs的CdS/CdSe量子点敏化太阳电池光伏性能的影响,同时结合强度调制光电流谱(IMPS)研究了TiO2纳米棒阵列的电子传输性能.结果表明:TiCl4修饰可以大幅提高基于单晶TNRs的CdS/CdSe量子点敏化太阳电池的光伏性能,在TiCl4修饰时间为60 h时,其短路电流密度和光电转换效率分别由修饰前的(2.93±0.07)mA·cm-2和0.36%±0.02%提高至(8.19±0.12)mA·cm-2和1.17%±0.07%.同时,IMPS测试表明电子在单晶TiO2纳米棒阵列中的传输速率高于在TiO2纳米颗粒薄膜中的传输速率,证明了单晶TiO2纳米棒阵列在电子传输方面的优越性.     

P3HT/CdS/TiO2/ZnO一维有序核壳式纳米棒阵列的构制及其在杂化太阳电池中的应用研究

采用恒电位法在铟锡氧化物导电玻璃(ITO)上制备了高度有序一维ZnO纳米棒阵列,将ZnO纳米棒阵列在TiO2溶胶中采用提拉法制备出了一维TiO2/ZnO核壳式纳米棒阵列.在一维TiO2/ZnO核壳式纳米棒阵列上电沉积CdS纳米晶得到一维CdS/TiO2/ZnO核壳式纳米棒阵列,然后在一维CdS/TiO2/ZnO核壳式纳米棒阵列上电沉积聚3-己基噻吩(P3HT)薄膜得到P3HT/CdS/TiO2/ZnO核壳式纳米结构薄膜.以该纳米结构薄膜电极为光阳极制备出新型纳米结构杂化太阳电池,研究了该类电池的光电转换性能,初步探讨了该类电池的工作机理.     

CdS/TiO2纳米管复合结构的制备与光电性能研究

利用阳极氧化法在钛金属基底表面制备一层TiO2纳米管阵列薄膜,然后通过水热反应在TiO2纳米管上负载CdS纳米粒子,形成CdS/TiO2纳米管的复合结构。利用SEM、XRD、XPS、UV-Vis等手段对其形貌和结构进行表征。进一步考察了CdS/TiO2纳米管的光电性能和光催化活性,结果表明,相比于TiO2纳米管,CdS/TiO2纳米管复合结构在紫外光和可见光下都具有更好的光催化活性及光电性能。     

P3HT修饰一维有序壳核式CdS/ZnO纳米棒阵列复合膜的光电化学性能

采用电化学方法在铟锡氧化物(ITO)导电玻璃上制备了高度有序的ZnO纳米棒阵列, 在ZnO纳米棒阵列上先后电化学沉积CdS纳米晶膜及聚3-己基噻吩(P3HT)薄膜得到P3HT修饰的一维有序壳核式CdS/ZnO纳米阵列结构, 并通过扫描电镜(SEM)、透射电镜(TEM)、X射线衍射(XRD)、能量散射X射线(EDX)等表征手段证实了该结构的形成. 以此纳米结构薄膜为光阳极组装新型半导体敏化太阳电池, 研究了CdS纳米晶膜的厚度和P3HT薄膜的沉积对电池光伏性能的影响, 初步探讨了电荷在电池结构中的传输机理, 结果表明, CdS纳米晶膜和P3HT薄膜的沉积有效地拓宽了光阳极的光吸收范围, 实验中电池的光电转换效率最高达到1.08%.     

CdS/石墨烯纳米复合物的可见光催化效率和抗光腐蚀行为

制备了一系列CdS纳米晶/石墨烯(CdS/GR)复合物,并在可见光照条件下评价了其光催化降解亚甲基蓝的光催化效率和抗光腐蚀行为. 研究表明,石墨烯的引入加速了CdS纳米晶(NCs)光生电子的迁移速率,抑制了其光生电子-空穴的复合,有效改善了其光催化降解有机污染物的性能. CdS/GR复合物中的石墨烯含量显著影响其光催化效率,其中石墨烯含量为4.6%的光催化剂效率最高,其光电流是CdS NCs的2.3倍. 利用光电化学和X射线衍射技术进一步证实,石墨烯的引入抑制了CdS NCs光腐蚀的发生,提高了CdS/GR复合物的光催化稳定性.     

单分散CdS纳米晶/PNIPAM复合水凝胶的制备及其温敏荧光特性

采用液体-固体-溶液法(LSS)制备单分散CdS纳米晶;通过自由基聚合制备单分散CdS纳米晶/聚N-异丙基丙烯酰胺(CdS/PNIPAM)复合温敏水凝胶.采用HRTEM、XRD、FTIR、DSC、PL等对CdS纳米晶、CdS/PNIPAM温敏复合凝胶的微观结构与性能进行了表征,变温荧光光谱研究了温度对凝胶荧光性能的影响.结果表明,CdS纳米晶粒径约为2.8 nm,单分散性良好;复合凝胶的荧光发射强度与环境温度存在一定的关联性,且呈可逆性.     

DNA/CdS纳米粒子复合体系的光谱和光电化学性质

在水溶液中以DNA作为模板和稳定剂, 构筑了DNA与CdS纳米粒子复合体系(DNA/CdS NPC), 研究DNA的含量, 单双链等对复合体系光电响应的影响, 并综合TEM, UV-Vis, IR和荧光光谱等对其形貌和光谱性质进行表征. 结果表明, CdS纳米粒子(CdS NPs)与DNA链之间主要通过静电作用结合; DNA模板对CdS NPs的禁带宽度没有影响; 以DNA模板合成的CdS NPs具有较高的表面态密度, 其对CdS NPs的荧光有增强作用, 而对光电流响应有抑制作用, 并且DNA在复合体系中的含量影响荧光增强和光电流减弱的程度. 该复合体系在荧光标记检测和DNA的定量分析方面可能具有应用前景.     

Cs_xH_(3-x)PW_(12)O_(40) heteropoly salts catalyzed quinoline synthesis via Friedl(a|¨)nder reaction

Various type of cesium partially substituted phosphotungstate,Cs_xH_3-xPW₁₂O₄₀（x = 1.0,2.0 and 2.5）,were synthesized and their catalytic activities were investigated in the synthesis of quinoline.It was shown that catalytic activities of these catalysts correlated to surface acidity and total number of acidic sites.Finally,a series of quinoline derivatives were synthesized with Cs_2.5H_0.5PW₁₂O₄₀ via the Friedlander reaction in high to excellent yields and the plausible mechanism was proposed.Simple experiment,catalyst reusability,short reaction time and preclusion of toxic solvent are the advantages of this method.     

杂多化合物的酸催化特性及其在有机合成反应中的应用

杂多化合物在各个研究领域中的实际应用日趋广泛。特别是在催化领域内，对杂多化合物催化性能和研究越来越引起人们的关注。本文对在均相和非均相体系中杂多化合物的酸催化的最新研究成果和应用进行了综述，对杂多化合物的酸行为进行了简要的概括，并介绍了作者在这方面的工作。     

几种方法制备的H3PW12O40/SiO2催化剂的结构和催化性能

 针对H3PW12O40(HPW)的比表面积小和不易回收利用等缺点,分别采用浸渍法、溶胶-凝胶法和以离子液体为模板剂的溶胶-凝胶法制备了HPW/SiO2催化剂,采用傅里叶变换红外光谱、 X射线衍射、 N2物理吸附和吸附氨的程序升温脱附等技术对催化剂样品进行了表征,并考察了其对苯硝化反应的催化性能. 结果表明,所制备的催化剂样品都保持了HPW原有的Keggin结构. 浸渍法制备的催化剂的比表面积(475.2 m2/g)较小,使用4次后硝基苯的收率由82.4%下降到70.7%; 溶胶-凝胶法制备的催化剂的比表面积(498.6 m2/g)居中,使用4次后硝基苯的收率由85.1%下降到79.6%; 以［emim］BF4离子液体为模板剂,采用溶胶-凝胶法制备的催化剂含有介孔结构,比表面积(558.5 m2/g)最高,使用4次后硝基苯的收率由84.7%下降到79.9%. 不同方法制备的HPW/SiO2催化剂具有较高的催化苯硝化反应活性和较好的稳定性.     

Catalytic Oxidation of Dimethyl Ether to Dimethoxymethane over Cs Modified H_3PW_(12)O_(40)/SiO_2 Catalysts

The attractive utilization route for one-step catalytic oxidation of dimethyl ether to dimethoxymethane was successfully carried out over the H_3PW_(12)O_(40)(40%)/SiO_2 catalyst,modified by Cs,K,Ni,and V.The Cs modification of H_3PW_(12)O_(40)(40%)/SiO_2 gave the most promising result of 20% dimethyl ether conversion and 34.8% dimethoxymethane selectivity.Dimethoxymethane could be synthe- sized via methoxy groups decomposed from dimethyl ether through the synergistic effect between the acid sites and the redox sites of Cs modified H_3PW_(12)O_(40)(40%)/SiO_2.     

Direct Iodination of Aromatic Compounds with Polyvinylpyrrolidone Supported Hydrogen Peroxide (PVP-H2O2) and Potassium Iodide or Molecular Iodine

Hydrogen peroxide was supported on polyvinylpyrrolidone to afford a stable and mild oxidizing reagent.Acti-vated aromatic compounds were reacted with PVP-H_2O_2 in the presence of KI or I_2 and a catalytic amount ofH_3PW_(12)O_(40)in refluxing CH_2Cl_2 to afford the corresponding iodinated arenes.     

STUDIES ON REDOX PROPERTIES OF HETEROPOLY ACIDS (SALTS) AND THEIR DERIVATIVES WITH KEGGIN AND DAWSON STRUCTURES

We have systematically studied redox properties of two series of several dozen heteropoly acids (salts) and their derivatives with vanadium and rare-earth elements with Keggin and Dawson structures, e. g. LnHSiMo_(12), SiMo_(12-n)V_n, M_(1.5)PMo_(12), PMo_(12-n)V_n, PW_(12-n_V_n, Ln(PMo_(11))_2, Sm(XMo_(11))_2 and P_2Mo_(18-n)V_n, etc., and obtained their sequence of oxidation. It was found that there is a linear relationship between the reduction potentials of heteropoly anions and the derivatives of heteropoly anions with rare-earth elements with Keggin structure and nq~2 (n and q are the principal quantum number and charge of the central ion respectively). On the basis of the electrostatic model the regularity of oxidation and reduction was rationalized.     

Fabrication of nanoreactors based on polyoxoperoxometalates and enhancement of their catalytic activity

The nanoreactors were fabricated by reacting amphiphilic quaternary ammoniums and polyoxoperoxometalates K_n[PW_12-xTi_x- O_40-x（O₂）_x]（x=1,2 and 3;n = 5,7 and 9）(K₅[PW₁₁TiO₃₉（O₂）],K₇[PW₁₀Ti₂O₃₈（O₂）₂]and K₉[PW₉Ti₃O₃₇（O₂）₃]).Fourier transform infrared spectroscopy（FT-IR）,transmission electron microscopy（TEM） were used to characterize the resulting samples. This kind of nanocatalysts could promote NH₄SCN’ degradation into simple inorganic compounds such as SO₄^2-,HCO₃^- and NO₃^- only using oxygen as an oxidant under room conditions.     

Crystal Structure and Dodecaaminium Didecavanadate Dodecahydrate

ＣｒｙｓｔａｌＳｔｒｕｃｔｕｒｅｏｆＤｏｄｅｃａａｍｉｎｉｕｍＤｉｄｅｃａｖａｎａｄａｔｅＤｏｄｅｃａｈｙｄｒａｔｅ￥ＣｈｅｎｇＣｈａｎｇ－Ｚｈａｎｇ；ＳｈａｏＳｈｉ－Ｂａｏ；ＨｕａｎｇＸｉａｏ－Ｙｉｎｇ；ＬｉｎＺｈｏｕ－Ｂｉｎ（ＦｕｊｉａｎＩｎｓｔ...     

The effect of phosphate additive on the positive electrolyte stability of vanadium redox flow battery

The electrolyte is one of the most important components of vanadium redox flow battery(VRFB),and its stability and solubility determines the energy density of a VRFB.The performance of current positive electrolyte is limited by the low stability of VO_2~+at a higher temperature.Phosphate is proved to be a very effective additive to improve the stability of VO_2~+.Even though,the stabilizing mechanism is still not clear,which hinders the further development of VRFBs.In this paper,to clarify the effect of phosphate additive on the positive electrolyte stability,the hydration structures of VO_2~+cations and the reaction mechanisms of precipitation with or without phosphate in the supporting electrolyte of H_2SO_4solutions were investigated in detail based on calculations of electronic structure.The stable configurations of complexes were optimized at the B3LYP/6-311+G(d,p)level of theory.The zero-point energies and Gibbs free energies for these complexes were further evaluated at the B3LYP/aug-cc-pVTZ level of theory.It shows that a structure of[VO_2(H_2O)_2]~+ surrounded by water molecules in H_2SO_4solution can be formed at the room temperature.With the temperature rises,[VO_2(H_2O)_2]~+ will lose a proton and form the intermediate of VO(OH)_3,and the further dehydration among VO(OH)_3molecules will create the precipitate of V_2O_5.When H_3PO_4was added into electrolytes,the V-O-P bond-containing neutral compound could be formed through interaction between VO(OH)_3and H_3PO_4,and the activation energy of forming the V-O-P bond-containing neutral compound is about 7 kcal mol~(-1) lower than that of the VO(OH)_3dehydration,which could avoid the precipitation of V_2O_5and improve the electrolyte stability.     

Hydrothermal Synthesis and Characterization of a Sandwich-type Tungstophosphate,(1,3-H2dap)8H4[Co4(H2O)2(α-B-PW9O34)2] 2·5H2O

<正>A sandwich-type tungstophosphate, (1,3-H_2dap)_8H_4[Co_4(H_2O)_2(α-B- PW_9O_(34))_2]_2·5H_2O (1,3-dap = 1,3-diaminopropane), was hydrothermally synthesized and structurally characterized by single-crystal X-ray diffraction, IR and UV spectroscopy. The title compound crystallizes in triclinic, space group P1 with a = 13.691(3), b = 17.744(4), c = 20.620(5), α =113.466(5), β = 91.184(5), γ = 104.223(5)°, V = 4414.3(17)~3, C_(24)H_(96)Co_8N_(16)O_(145)P_4W_(36), M_r = 10143.09, D_c = 3.816 g/cm~3, μ(MoKα) = 24.210 mm~(-1), F(000) = 4452, Z = 1, the final R = 0.0694 and wR = 0.1519 for 9910 observed reflections (I > 2σ(I)). The compound consists of two sets of tetra-transition metal-substituted sandwich frameworks, [Co_4(H_2O)_2(α-B-PW_9O_(34))_2]~(10-) having an inversion centre. Two lacunary α-B-[PW_9O_(34)]~(9-) Keggin units are linked by a rhomb-like Co_4O_(14)(H_2O)_2 cluster, in which the Co~(2+) ions are coordinated by one water molecule. Isolatedly protonated 1,3-H2dap~(2+) units act as counter-ions to interact with the [Co_4(H_2O)_2(α-B-PW_9O_(34))_2]~(10-) heteropolyanions via hydrogen bonds, resulting in a three-dimensional framework.