水溶性苝醌衍生物(13-SO~2Na-DDHA)与胶体半导体(CdS)澡光 诱导电子传递过? 痰亩ρа芯?

根据非均相体系电子传递动力μ＜0(μ=E~s*/s+-E~CB)的原理,构建出相匹配的水溶性苝醌衍生物光敏剂(13-SO~2Na-DDHA)与胶体半导体(CdS)的复合体体系,? 獯忝鸱椒ǎ獬鏊侵浜捅砉劢岷铣Ｊ?K~app)为1480(mol/L)^-1。继而? τ孟孕?spincounteraction)的ESR技术,首次定量地研究了它们之间的光诱? 嫉绱莨痰亩ρВ范耸?3-SO~3Na-DDNA光敏化作用的CdS胶体半导体表? 婀饣乖ρХ匠毯退俾食Ｊ峁⑾郑诒咎逑抵蠺EMPO接受光电子的反应? 妒?,而不同于均相体系中的反应级数别虽在相同可见光照射条件下(13-SO~2Na-DDHA)复合体的光还原速率比单独CdS高约82倍,表明该水溶性光敏剂对CdS胶体半导体具有显著的敏化效果,在太阳能应用中可被用作CdS胶体半导体有效的敏化剂。     

水溶性苝醌衍生物(13-SO3Na-DDHA)与胶体半导体(CdS)间光诱导电子传递过程的动力学研究

根据非均相体系电子传递动力μ＜0(μ=Es*/s+-ECB)的原理,构建出相匹配的水溶性苝醌衍生物光敏剂(13-SO3Na-DDHA)与胶体半导体(CdS)的复合体体系,通过荧光淬灭方法,测出它们之间的表观结合常数(Kapp)为1480(mol/L)-1.继而应用消自旋(spin counteraction)的ESR技术,首次定量地研究了它们之间的光诱导电子传递过程的动力学,确定了受13-SO3Na-DDHA光敏化作用的CdS胶体半导体表面光还原动力学方程和速率常数,结果发现,在本体系中TEMPO接受光电子的反应级数为0,而不同于均相体系中的反应级数;特别是在相同可见光照射条件下,CdS-(13-SO3NA-DDHA)复合体的光还原速率比单独CdS高约82倍.表明该水溶性光敏剂对CdS胶体半导体具有显著的敏化效果,在太阳能应用中可被用作CdS胶体半导体有效的敏化剂.     

竹红菌素的13位磺化反应和反应机理

在通空气条件下,回流竹红菌甲素(HA)(或乙素,HB)和Na~2SO~3的含1%NaOH强碱性水溶性生成14-脱羟基-15-脱乙酰基竹红菌甲素-13-位磺酸钠(13-SO~3Na-DDHA)(产率30%)和另一种红色的水溶性聚合物。当这一反应在吡啶-水(1:1/V:V)混合溶剂中进行,并用CuO作氧化剂时,只得到13-SO~3Na-DDHA一种水溶性产物(70%产率)。在后一体系中,由于改变了溶剂和氧化剂,使13-SO~3Na-DDHA的制备更加便利。反应体系的ESR研究表明,这一磺化反应首先是通过竹红菌素和Na~2SO~3之间热活化的电子转移进行的。电子转移的结果产生竹红菌素半醌负离子自由基和三氧化硫负离子自由基(SO~3^-)。硝基甲烷酸式负离子猝灭实验证明,由于竹红菌素的13位能在碱性、高温下活化,磺化的关键步骤是SO~3^-对其活化了的13位的亲电进攻。氧化剂在这一反应中的作用为:将产生的竹红菌素半醌负离子自由基氧化至其母体醌,增加反应物的相对浓度,同时使竹红菌素与SO~3^2^-之间的电子转移循环进行,加速SO~3^-的产生。     

水溶性竹红菌素及电子转移中间体的光谱研究

本文详细研究了水溶性竹红菌素衍生物14-脱羟基-15-脱乙酰基-竹红菌甲素-13-磺酸钠(13-SO_3Na-DDHA)及光还原产物的吸收光谱和影响因素。通过吸收光谱随pH值的变化观察到13-SO_3Na-DDHA及两电子还原产物酚羟基的分步解离,并通过实验值与理论公式相拟合分别求出了解离的pK_a。此外,还比较了13-SO_3Na-DDHA在buffer溶液和在DMF-buffer溶液中的光还原特点。测定了13-SO_3Na-DDHA半醌负离子自由基质子化和歧化的动力学性质。     

胶体半导体表面光还原反应动力学的ESR研究──I.ZnS、CdS光还原效率的ESR研究

用电子自旋共振(ESR)法以4-氧-2,2,6,6-四甲基-哌啶酮(4-oxo-TEMPO)作为电子受体,研究了ZnS和CdS胶体表面光还原效率的差异,发现在本实验体系中胶体表面光还原对于底物是零级反应,其原因可能是由于胶体的吸附作用使得4-oxo-TEMPO在胶体表面处于饱和状态。测得的反应动力学常数能够定量地表示胶体半导体光还原效率的差异。实验结果表明,由于吸收光谱范围的限制,ZnS胶体在不同波长光照下以及ZnS和CdS胶体在同样光照下的光还原效率均不相同。     

基于原位形成p-n结的新型光电化学传感器检测Hg~(2+)

利用简单方法合成了水溶性的巯基乙酸修饰的硫化镉(CdS)量子点。通过静电吸附,用聚二甲基二烯丙基氯化铵(PDDA)将CdS修饰到氧化铟锡(ITO)电极上。在电子供体三乙醇胺(TEA)的存在下,CdS修饰的ITO电极具有稳定的阳极光电流。Hg2+原位吸附于CdS表面形成的p型半导体HgS与n型半导体CdS形成p-n结,能够促进电子-空穴的分离与电荷传输,使CdS量子点的光电流增大。研究了反应前驱体中Cd,S摩尔比、反应溶液的pH值、回流时间等条件对所合成的量子点与Hg2+相互作用的影响。此外,还研究了电解质溶液的pH值、外加电压、反应时间对Hg2+增大CdS量子点光电流的影响。基于此,构建了灵敏检测Hg2+的光电化学传感器。该传感器对Hg2+响应的线性范围为4.0×10-8~2.0×10-5mol/L,检出限为2.4×10-8mol/L,回收率为98.3%~103.5%。     

TiO2/CdS/Ru(bpy)2(NCS)2作为太阳电池光阳极的探讨

将CdS纳米粒子复合成TiO2纳米多孔膜上，用染料Ru(bpy)2(NCS)2对此复合半导体纳米膜电极进行每化，测量了不同CdS复合量的ITO／TiO2/CdS/Ru(bpy)2(NCS)2光阳极组成光电池的能量转换效率，实验证明，ITO／TiO2/CdS/Ru(bpy)2(NCS)2作为太阳电池光阳极的能量转换效率与TiO2/CdS复合半导体中CdS的含量有关，当CdS复合时间为5min的电池的短路电流为5．23A／m^2,开路电压为0．716V，能量转换效率为0．77％。     

多相光催化分解H2S中阴离子表面活性剂对半导体催化剂CdS表面的影响

研究了在H₂S碱性溶液中,CdS粉末催化剂存在时,光催化分解H₂S释氢和生成硫反应。考察了阴离子表面活性剂——十二烷基硫酸钠(SDS)对催化剂的表面性质和催化活性的影响。通过模拟该反应体系,用电化学方法测定了单晶CdS电极在上述反应体系中加入SDS(浓度低于临界胶团浓度CMC值)后的平带电位的变化。结果表明:单晶CdS电极的平带电位,由于该体系加入SDS而正移,与n型多晶半导体CdS在加入SDS的H₂S碱性溶液中,光催化分解H₂S的释氢量减少相一致。并探讨了在该体系中,由于表面活性剂的阴离子与S^2-在单晶CdS电极表面上的竞争吸附,而引起单晶CdS电极的平带电位正移。     

羰基四(对磺酸基苯基)卟啉钌(Ⅱ)的合成及光解水产氢的研究

金属卟啉在绿色植物的光合作用中起着重要的电子传递功能,在光解水产氢的研究中被用做光敏剂.在筛选金属卟啉光敏剂的研究中,通过改变卟啉环上的取代基和中心离子,将能改善其光敏性能.Okura等曾研究以羰基四苯基卟啉钌[Ru(CO)TPP]为光敏剂的光解水产氢体系,但由于Ru(CO)TPP不溶于水,故采用表面活性剂将其分散在水中,进行光敏效应的研究.我们合成了一种水溶性的钌卟啉化合物Ru(CO)TPPS,通过电子吸收光谱、红外光谱、核磁共振谱及元素分析等确定结构,并对Ru(CO)TPPS-K_2PtCl_6-TiCl_3复合光解水产氢体系进行了研究.实验结果表明,该体系的酸性水溶液在光照条件下,有较好的释氢性能和较高的转化数.     

非贵金属三元复合Ni(PO3)2-Ni2P/CdS NPs异质结的构建及可见光高效催化产氢性能

结合异质结构建与共催化剂改性, 以花球状Ni(OH)₂为前驱体, 经热磷酸化后得到Ni(PO₃)₂-Ni₂P二元助催化剂, 借助超声化学合成法, 与CdS NPs复合, 形成非贵金属CdS基三元光催化材料Ni(PO₃)₂-Ni₂P/CdS NPs. 以Na₂S-Na₂SO₃为牺牲剂, 在可见光(λ＞420 nm)照射下, 在不借助任何贵金属的情况下, 负载量为8%(质量分数)的Ni(PO₃)₂-Ni₂P/CdS NPs复合材料的光催化产氢速率达到4237 μmol·g^?1·h^?1, 为CdS NPs(217 μmol·g^?1·h^?1)的19倍. 在产氢循环实验中, 反应进行到第6次循环(18 h)后, 复合材料的产氢速率约为初始的89%, 具有较好的稳定性. 与CdS NPs相比, Ni(PO₃)₂-Ni₂P/CdS NPs的吸收边明显红移, 禁带宽度降至1.86 eV, 并降低了H⁺还原的过电位, 显示出增强的光吸收性能和适宜的带隙结构. 通过Ni(PO₃)₂-Ni₂P与CdS NPs之间的协同效应, 有效促进了光生载流子的分离, 提高了产氢活性和稳定性.     

Effect of beta-Cyclodextrin on the Photoinduced Charge Transfer in Sodium 1-Anilino-8-naphthalene Sulfate (ANS)/CdS Colloidal System

The S-center radical (ANS(.)) of sodium 1-anilino-8-naphthalene sulfate (ANS) generated by photoinduced charge transfer in ANS/CdS and ANS/CdS/beta-cyclodextrin(beta-CD) systems has been studied by using spin trapping electron spin resonance techniques, UV-visible spectroscopic methods, and fluorescence spectroscopic methods. It was found that the S-centered radical (ANS(.)) was produced by the charge transfer reaction between the ground state ANS and the positive hole h(+)(CdS) from the valence band of CdS colloids, by the charge transfer from the excited singlet state (1)ANS* to the conduction band of CdS colloids, or by both in the ANS/CdS and ANS/CdS/beta-CD systems. The ESR signal intensity of the spin adduct (5,5'-dimethyl-1-pyrroline-N-oxide (DMPO)-ANS)(.), which is formed from ANS(.) trapped by DMPO, in the latter system is 15 times stronger than that in the former system. The apparent association constants between ANS and CdS colloids in the absence and presence of beta-CD determined from fluorescence quenching experiments are 1097 and 1606 M(-1), respectively. From ESR and fluorescence results, it is estimated that the efficiency of photoinduced charge transfer from ANS to CdS colloids in the ANS/CdS/beta-CD system is 12.5 times that in the ANS/CdS system. Copyright 2001 Academic Press.     

Effect of β-Cyclodextrin on the Photoinduced Charge Transfer in Sodium 1-Anilino-8-naphthalene Sulfate (ANS)/CdS Colloidal System

The S-center radical (ANS^·) of sodium 1-anilino-8-naphthalene sulfate (ANS) generated by photoinduced charge transfer in ANS/CdS and ANS/CdS/β-cyclodextrin(β-CD) systems has been studied by using spin trapping electron spin resonance techniques, UV-visible spectroscopic methods, and fluorescence spectroscopic methods. It was found that the S-centered radical (ANS^·) was produced by the charge transfer reaction between the ground state ANS and the positive hole h⁺(CdS) from the valence band of CdS colloids, by the charge transfer from the excited singlet state ¹ANS* to the conduction band of CdS colloids, or by both in the ANS/CdS and ANS/CdS/β-CD systems. The ESR signal intensity of the spin adduct (5,5′-dimethyl-1-pyrroline-N-oxide (DMPO)–ANS)^·, which is formed from ANS^· trapped by DMPO, in the latter system is 15 times stronger than that in the former system. The apparent association constants between ANS and CdS colloids in the absence and presence of β-CD determined from fluorescence quenching experiments are 1097 and 1606 M⁻¹, respectively. From ESR and fluorescence results, it is estimated that the efficiency of photoinduced charge transfer from ANS to CdS colloids in the ANS/CdS/β-CD system is 12.5 times that in the ANS/CdS system.     

Synthesis and characterization of CdIn(2)S(4) nanorods by converting CdS nanorods via the hydrothermal route

The ternary semiconductor CdIn(2)S(4) nanorods were synthesized by a method based on CdS nanorods via the hydrothermal route, in which CdS nanorods were converted by reaction with InCl(3) and thiourea in aqueous solution. Transmission electron microscopy (TEM) images revealed that the typical sizes of the CdIn(2)S(4) nanorods were 10-30 nm in diameter and 200-1000 nm in length. X-ray photoelectron spectra (XPS) analysis of the surface stoichiometry (CdIn(2.03)S(4.15)) and room-temperature Raman spectrum (RS) were recorded. The influences of reaction temperature, time, and sulfur sources on the formation for CdIn(2)S(4) nanorods were investigated. A possible formation mechanism of the CdIn(2)S(4) nanorods was also proposed.     

Theoretical study of hydrated copper(II) interactions with guanine: a computational density functional theory study

Optimization of the hydrated Cu(II)(N7-guanine) structures revealed a number of minima on the potential energy surface. For selected structures, energy decompositions together with the determination of electronic properties (partial charges and electron spin densities) were performed. In the complexes of guanine with the bare copper cation and that with the monoaqua ligated cation, an electron transfer from guanine to Cu(II) was observed, resulting in a Cu(I)-guanine(+) type of complex. Conformers with two aqua ligands are borderline systems characterized by a Cu partial charge of +0.7e and a similar value of the spin density (0.6e) localized on guanine. When tetracoordination of copper was achieved, only then the prevailing electron spin density is unambiguously localized on copper. The energetic preference of diaqua-Cu-(N7,O6-guanine) over triaqua-Cu-(N7-guanine) was found for the four-coordinate structures. However, the energy difference between these two conformations decreases with the number of water molecules present in the systems, and in complexes with five water molecules this preference is preserved only at DeltaG level where thermal and entropy terms are included.     

Semiconductor cadmium sulphide nanoparticles as matrices for peptides and as co-matrices for the analysis of large proteins in matrix-assisted laser desorption/ionization reflectron and linear time-of-flight mass spectrometry

The use of semiconductor cadmium sulphide nanoparticles (CdS NPs) capped with 4-aminothiophenol (ATP) and 11-mercaptoundecanoic acid (MUA) is described for the first time as matrices and as co-matrices for the analysis of peptides and proteins in matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF-MS). UV-visible spectroscopy, Fourier transform infrared (FT-IR) spectroscopy, scanning electron microscopy (SEM) and transmission electron microscopy (TEM) were applied for the characterization of functionalized CdS NPs. The synthesized CdS-ATP and CdS-MUA NPs exhibit uniform size distribution with diameter of 15-25 nm and 20-30 nm, respectively. The -NH(2) (ATP) and -COOH (MUA) groups modified on the surfaces of CdS NPs provide ionizable moieties for efficient transfer of protons during the desorption/ionization of analytes. The functionalized CdS NPs have desirable properties for the analysis of peptides in reflectron MALDI-TOF-MS with suppressed background noise and increased mass resolution (4-13-fold) in linear MALDI-TOF-MS. The application of CdS-MUA NPs and SA as the co-matrices in MALDI-MS is demonstrated for the analysis of hydrophobic proteins from soybean.     

Identification and characterization of monoanionic tripodal tetradentate ligand complexes of copper(I) and copper(II) involved in halogen atom transfer reactions

The copper(I) complex of bis-(2-(2-pyridyl)-ethyl)-(2-(N-p-toluenesulfonamido)-ethyl)amine (PETAEA), a monoanionic, tripodal tetradentate ligand, was prepared, characterized, and shown to be an effective catalyst for atom transfer radical polymerization (ATRP). A model atom transfer reaction of Cu(PETAEA) with 1-phenylethyl bromide and TEMPO radical trapping agent was studied. The copper(II) complex formed in this reaction was identified by comparison of its spectroscopic data with that of Cu(PETAEA)Br prepared by an independent synthesis. Kinetic and spectroscopic data indicated that the reaction mechanism involved simple atom transfer from the alkyl halide to the Cu(PETAEA) to form the Cu(PETAEA)Br, and no other intermediates were involved. The solid-state structures of the copper(I) and (II) complexes appeared to be maintained in solution, so this system is an atom transfer reaction in which all of the reactive species are identified and characterized.     

Photoinduced interaction between fluorescein ester derivatives and CdS colloid

The photoinduced interaction of fluorescein ester derivatives, fluorescein's butyl ester (FL4) and fluorescein's anthraquinone-methyl ester (FL-AQ), and colloidal CdS was examined by absorption, fluorescence spectroscopy, and photoinduced ESR spectroscopy. It is found that FL4 and FL-AQ molecules are adsorbed on the surfaces of CdS colloid by an electrostatic interaction forming the surface complex of the type CdS-FL4 or CdS-FL-AQ. The apparent association constant (K(app)) and the degree of association (alpha) of CdS-FL4 obtained from absorption spectra are 2.25 x 10(4) M(-1) and 0.78, respectively. The values of K(app) and alpha of CdS-FL4 as determined from fluorescence spectra are 1.54 x 10(4) M(-1) and 0.82, respectively, which matches well with that determined from the absorption spectra changes. And the values of K(app) and alpha of CdS-FL-AQ obtained from absorption spectra are 4.18 x 10(4) M(-1) and 0.83, respectively. These data indicate that there is a strong interaction between the dye and the CdS particle surface. But there was no evidence for interfacial electron transfer from FL4 or FL-AQ to colloidal CdS by photoinduced ESR experiments. The fluorescence quenching is due to the formation of a nonfluorescent complex. The related phenomena are discussed in this paper.     

Optoeletronic investigation of Cu2ZnSn(S,Se)4 thin-films & Cu2ZnSn(S,Se)4/CdS interface with scanning probe microscopy

The kesterite-structured semiconductor Cu₂ZnSn(S,Se)₄ (CZTSSe) is prepared by spin coating a non-hydrazine precursor and annealing at Se atmosphere. Local electrical and optoelectronic properties of the CZTSSe thin-film are explored by Kelvin probe force microscopy and conductive atomic force microscopy. Before and after irradiation, no marked potential bending and very low current flow are observed at GBs, suggesting that GBs behave as a charge recombination site and an obstacle for charge transport. Furthermore, CdS nano-islands are synthesized via successive ionic layer adsorption and reaction (SILAR) method on the surface of CZTSSe. By comparing the work function and current flow change of CZTSSe and CdS in dark and under illumination, we demonstrate photo-induced electrons and holes are separated at the interface of p-n junction and transferred in CdS and CZTSSe, respectively.     

Near unity quantum yield of light-driven redox mediator reduction and efficient H2 generation using colloidal nanorod heterostructures

The advancement of direct solar-to-fuel conversion technologies requires the development of efficient catalysts as well as efficient materials and novel approaches for light harvesting and charge separation. We report a novel system for unprecedentedly efficient (with near-unity quantum yield) light-driven reduction of methylviologen (MV(2+)), a common redox mediator, using colloidal quasi-type II CdSe/CdS dot-in-rod nanorods as a light absorber and charge separator and mercaptopropionic acid as a sacrificial electron donor. In the presence of Pt nanoparticles, this system can efficiently convert sunlight into H(2), providing a versatile redox mediator-based approach for solar-to-fuel conversion. Compared to related CdSe seed and CdSe/CdS core/shell quantum dots and CdS nanorods, the quantum yields are significantly higher in the CdSe/CdS dot-in-rod structures. Comparison of charge separation, recombination and hole filling rates in these complexes showed that the dot-in-rod structure enables ultrafast electron transfer to methylviologen, fast hole removal by sacrificial electron donor and slow charge recombination, leading to the high quantum yield for MV(2+) photoreduction. Our finding demonstrates that by controlling the composition, size and shape of quantum-confined nanoheterostructures, the electron and hole wave functions can be tailored to produce efficient light harvesting and charge separation materials.     

Electron transfer between colloidal ZnO nanocrystals

Colloidal ZnO nanocrystals capped with dodecylamine and dissolved in toluene can be charged photochemically to give stable solutions in which electrons are present in the conduction bands of the nanocrystals. These conduction-band electrons are readily monitored by EPR spectroscopy, with g* values that correlate with the nanocrystal sizes. Mixing a solution of charged small nanocrystals (e(-)(CB):ZnO-S) with a solution of uncharged large nanocrystals (ZnO-L) caused changes in the EPR spectrum indicative of quantitative electron transfer from small to large nanocrystals. EPR spectra of the reverse reaction, e(-)(CB):ZnO-L + ZnO-S, showed that electrons do not transfer from large to small nanocrystals. Stopped-flow kinetics studies monitoring the change in the UV band-edge absorption showed that reactions of 50 μM nanocrystals were complete within the 5 ms mixing time of the instrument. Similar results were obtained for the reaction of charged nanocrystals with methyl viologen (MV(2+)). These and related results indicate that the electron-transfer reactions of these colloidal nanocrystals are quantitative and very rapid, despite the presence of ~1.5 nm long dodecylamine capping ligands. These soluble ZnO nanocrystals are thus well-defined redox reagents suitable for studies of electron transfer involving semiconductor nanostructures.