Cu2O/Ag纳米复合物的表面增强拉曼光谱

用一种简单的化学还原方法制备了银纳米粒子包覆的氧化亚铜（Cu2O）纳米复合物。扫描电子显微镜显示Cu2O 为八面体型的纳米粒子,表面光滑,结构对称。包覆的Ag部分占据Cu2O粒子表面。通过比较Ag/Cu2O纳米复合物、Ag溶胶及Cu纳米粒子表面吸附的4-巯基吡啶（4-Mpy）分子表面增强拉曼光谱（SERS）发现,利用此方法得到了Cu2O粒子表面吸附分子的拉曼光谱。银纳米粒子所产生的电磁场增强又增强了吸附在Cu2O上的4-Mpy拉曼信号。这种方法为初步研究Cu2O表面吸附分子性质提供了依据,扩宽了SERS的使用范围,使SERS应用在纳米半导体材料上成为可能。     

Pd/ZnO和Ag/ZnO复合纳米粒子的制备、表征及光催化活性

 用焙烧前驱物碱式碳酸锌的方法制备了ZnO纳米粒子，采用光还原沉积贵金属的方法制备了Pd／ZnO和Ag／ZnO复合纳米粒子，并利用ICP，XRD，TEM和XPS等测试技术对样品进行了表征，初步探讨了贵金属在ZnO纳米粒子表面形成原子簇的原因．以光催化氧化气相正庚烷为模型反应，考察了样品的光催化活性以及贵金属沉积量对催化剂活性的影响．结果表明：沉积适量的贵金属，ZnO纳米粒子光催化剂的活性大幅度提高．同时，深入探讨了表面沉积贵金属的ZnO纳米粒子光催化剂活性有所提高的内在原因．     

表面修饰二氧化锡纳米微晶的制备与表征

制备了硅烷偶联剂KH-570表面修饰的SnO2纳米微晶，通过FT-IR、XPS、TEM和TG-DTA对其结构和表面特性进行表征和研究. FT-IR和XPS分析结果确证了KH-570与SnO2表面是以化学键合或物理吸附方式相结合,粒子表面存在酯基等有机官能团的红外吸收特征；观测到KH-570中Si原子的Si2s和Si2p谱线. TEM分析表明，表面修饰反应增强了SnO2纳米微晶的疏水性和分散性.由XPS和TG的实测数据探讨了纳米粒子具有较低包覆量的可能原因.     

超临界流体干燥法制备纳米TiO2－ZnO复合催化剂及其对苯酚降解的光催化性能

 以TiCl4和Zn（NO3）2·6H2O为原料，采用溶胶－凝胶法结合超临界流体干燥法制备了纳米级TiO2－ZnO（7～10nm）复合催化剂，并用XRD和TEM等手段进行了表征．以苯酚光催化降解为模型反应对所制备催化剂的催化性能进行了评价．结果表明，与单组分TiO2及普通干燥法制备的TiO2－ZnO催化剂相比较，纳米TiO2－ZnO复合粒子的光催化活性有较大提高．用超临界干燥法制备的催化剂具有粒径小、分布窄、比表面积大、分散性好和光催化活性高等特点．采用超临界流体干燥法可直接制得纳米TiO2（锐钛矿型）－ZnO（非晶态）复合催化剂，可实现干燥、晶化一步完成．复合催化剂中ZnO的最佳掺入量为x（ZnO）＝0．8％．超临界流体干燥法是制备纳米材料的一种新技术，具有产物容易收集和溶剂可回收利用等优点．     

基于ZnO-Au纳米复合物修饰的SPR传感器

Au纳米粒子具有容易制备,水溶性好,很高的化学稳定性和易发生生物偶联等特点~([1]).因此Au纳米粒子已广泛应用在分子生物学以及生物芯片中.ZnO纳米晶具有小尺寸效应、大的比表面积,独特的光学性质,因此受到了极其广泛的研究.在乙醇相制备的氧化锌纳米胶体很难在水溶液中稳定存在,而生物分子的偶联需在水溶液环境中才能够实现,为了利用纳米ZnO的光学性质作免疫分析和生物分子标记,必须对纳米ZnO表面进行包覆或修饰,使其溶于水溶液中来实现与生物分子的偶联.     

用TiO2，ZnO及Fe2O3纳米粒子光催化氧化庚烷的反应

 制备了三种n－型半导体氧化物TiO2，ZnO和Fe2O3纳米粒子，用X射线衍射和N2吸附技术分别对它们的结构及比表面积进行了表征．考察了三种氧化物粒子对庚烷的气相光催化氧化反应的催化活性．研究表明，对于同种催化剂，随着焙烧温度的升高，催化剂的粒径增大，比表 面积减小，光催化活性下降．三种催化剂纳米粒子的光催化活性顺序为TiO2（锐钛矿）＞ZnO＞Fe2O3，金红石型TiO2粒子的催化活性低于ZnO粒子．结合能带理论探讨了三种催化剂光催化活性差异的原因．     

磁性纳米包覆微球的制备和磁性表征

以胶体球形粒子为基体发展起来的纳米包覆(nano鄄coating)技术近来引起人们的极大兴趣,这种纳米包覆技术得到的产物常常被称为核壳粒子(core鄄shellparticles)。这种包覆一般是将纳米颗粒直接吸附在核微球上,或者包覆材料控制沉淀在核微球上[1,2]。这些复合微球常常展现出独特的光、电、力学、化学、催化等性质,因而具有广泛的研究和应用前景[3~7]。近十几年来,用做磁感应成像的超顺磁材料得到了深入的研究[4]。一方面,磁性颗粒的尺寸、电荷和表面成分对其应用有很大影响[8,9],另一方面,材料的磁学性质又主要取决于磁颗粒的大小[10]。Xu和Lindlar制备了含超顺磁颗粒的聚合物胶体颗粒,被用于构建超顺磁性的光子晶体[11,12]。在聚合物微粒上包覆氧化铁颗粒通常采用表面沉淀或表面改性官能团诱导反应包覆的方法。但这些方法不能很好控制复合微粒的均一性和表面平整性;Caruso的层鄄层包覆法(Layer鄄byLayer)虽然实现了磁性颗粒包覆[13],然而这种方法非常繁琐而不利于广泛应用。本文报道了一种新的合成磁性包覆颗粒的方法,即以聚合物微球为基核,通过非均相种子生长法包覆磁性纳米颗粒,并研究了...     

顺磁共振法在配位化学研究中的应用

顺磁共振又称电子顺磁共振(EPR)或电子自旋共振(ESR),它是测定未成对电子与其环境的相互作用的一种现代物理化学分析方法,现已广泛应用于物理、化学、生物、医学和地质等各个学科领域。1945年 Zavoisky 首先发现顺磁共振现     

乙醇溶液中ZnO纳米粒子的形成机理研究

半导体纳米粒子的研究是当今材料科学及物理化学的热门课题[1－3]．由于纳米粒子具有极大的比表面、尺寸量子化效应及增强的氧化和还原能力等不同于扶林的特殊性质，它被广泛地用于光催化，光电材料的制备及非线性光学材料的研究等[4－6]．ZnO作为一种重要的半导体材料，其纳米粒子的制备近年来也有报导[7－14]．由于ZnO在水中的生成自由能较正，所以一般都在醇溶液中制备，但其具体的成核机理至今并不十分清楚．本工作通过仔细的研究，阐明了ZnO纳米粒子形成过程中的成核和生长机理．1实验部分醋酸锌，氢氧化钠和乙醇均为分析纯试剂．制…     

静电显影墨粉级纳米Fe_3O_4的制备及表面改性研究

以氯化亚铁为原料,采用空气氧化法制备适合静电显影墨粉用的磁性纳米Fe_3O_4微粒,分别用三乙醇胺、月桂酸钠、有机硅化合物对产品进行表面改性处理.利用X射线衍射仪、透射电镜、红外光谱仪、EDS能谱仪、热重分析仪、振动样品磁强计分析了改性后纳米Fe_3O_4磁性粒子的形貌、表面相成分及磁性能.结果表明,三种物质都可以包覆在纳米Fe_3O_4磁性粒子表面;包覆后粒子的平均粒径没有明显变化,对纳米Fe_3O_4的磁性能影响不大;同时由于表面包覆层的空间位阻和静电作用,限制了纳米Fe_3O_4磁性粒子的团聚,提高了磁性粒子的分散性和稳定性.     

TEM,XPS and ESR Studies of Sol-gel ZnO-SiO2 Nanocomposite and ZnO/SiO2 Prepared from Impregnation

The ZnO-SiO₂ nanocomposite was obtained using the sol-gel method^[1] and the sample of ZnO/SiO₂ was prepared by conventional impregnation way. A narrow size distributed ZnO nanoparticles had been observed on silica matrix through both methods by TEM. The particle size increased slightly with zinc oxide content and treatment temperature from the particles of an average value of ca. 3-5 nm for Zn₁₀-T₄₀₀ (the treatment 400℃ and the zinc oxide content 10 wt%) sample to an average value of ca. 6-8 nm in Zn₁₀-T₇₀₀ sample. Furthermore, the ZnO crystalline transition from monocrystal to polycrystalline phase had been observed with treatment from 400℃ to 700℃ in ZnO-SiO₂ from the selected area diffraction patterns. XPS investigation indicated that the Zn 2p binding energy in samples of ZnO/SiO₂ and ZnO-SiO₂ increased greatly compared with zinc oxide, which suggested that strong interactions between nanometer-size ZnO and silica support were established. And it also suggested that the Si-O-H groups present in the surface of silica may be partially or totally substituted by Si-O-Zn bonds. Comparison of the ZnO-SiO₂,the Zn 2p binding energy in the ZnO/SiO₂ is lower, which implied that more Si-O-Zn groups existed on the former than the latter. The ESR results showed an interesting phenomena that a first-order standard differential ESR spectra (g_e=2.062) appeared in all ZnO-SiO₂ samples and no any signals in other samples. The ESR signal obtained may be due to O^-, O^2-, Zn⁺ or other ions. But the O^- ion vacancy is unstable, and if the Zn⁺ and the O^2- ions are the paramagnetic centers the g-factor should be equal to 2.0021^[2] or 2.109^[3], so the ESR signal from ZnO-SiO₂ sample does not arise from the ions above. Perhaps it comes from Zn³⁺, because the g-factor is close to d⁹ and Zn 2p binding energy in ZnO-SiO₂ is much higher than ZnO. The results showed that the interaction between microcrystlline ZnO and silica support in ZnO-SiO₂ is stronger than in the ZnO/SiO₂.     

Regenerable Fe-Mn-ZnO/SiO2 sorbents for room temperature removal of H2S from fuel reformates: performance, active sites, Operando studies

Fe- and Mn-promoted H(2)S sorbents Fe(x)-Mn(y)-Zn(1-x-y)O/SiO(2) (x, y = 0, 0.025) for desulfurization of model fuel reformates at room temperature were prepared, tested and characterized. Sulfur uptake capacity at 25 °C significantly exceeds that of both commercial unsupported ZnO sorbents and un-promoted supported ZnO/SiO(2) sorbents. Sulfur capacity and breakthrough characteristics remain satisfactory after multiple (～10) cycles of adsorption/regeneration, with regeneration performed by a simple and robust heating in air. XRD shows that both "calcined" and "spent" sorbents contain nano-dispersed ZnO, and XPS confirms conversion of ZnO to ZnS. "Calcined" sorbent contains Fe(3+) and Mn(3+) that are reduced to Mn(2+) upon reaction with H(2)S, but not with H(2). Operando ESR is used for the first time to study dynamics of reduction of Mn(3+) promoter sites simultaneously with measuring sulfidation dynamics of the Fe(x)-Mn(y)-Zn(1-x-y)O/SiO(2) sorbent. Fe cations are believed to occupy the surface of supported ZnO nanocrystallites, while Mn cations are distributed within ZnO.     

基于纳米ZnO/聚苯乙烯的复合材料光催化性能研究

通过将聚苯乙烯与纳米氧化锌前驱体共混制备了复合材料前驱体,运用TG-DTA联机分析得到了其分解温度及相关热分解数据;前驱体经适当温度煅烧后得复合材料光催化剂,运用TEM、XRD、FT-IR、UV-Vis、ESR等测试手段进行了表征。在荧光灯作用下对复合材料光催化性能进行了检测,并与相同条件下纳米氧化锌的光催化性能进行了比对分析。结果表明,该复合材料在荧光作用下对甲基橙催化降解11h后,甲基橙的降解率为35%,与纳米氧化锌催化降解甲基橙5%的降解率相比有较大程度的提高。     

Coagulation and stabilization of sterically functionalized magnetite nanoparticles in an organic solvent with different technical polymers

Single crystalline zinc tin oxide (ZTO) nanocrystallites were prepared at room temperature through association with a peptide-containing bolaamphiphile molecule. The bolaamphiphile molecules self-assembled to form spherical structures with creation of ZTO nanocrystallites inside. ZTO nanocrystallite synthesis was achieved only when the bolaamphiphile molecule was present, while a mixture of amorphous Sn and Zn precipitates was formed in the absence of the bolaamphiphile molecule. The bolaamphiphile molecule is thought to stabilize the Zn(2+) and Sn(4+) precursor ions by ligation and to induce subsequent condensation forming crystalline ZTO. The ZTO formation was achieved only at a strong acidic condition that promotes dissociation and ionization of Zn and Sn precursors and represses formation of ZnO and H(2)SnO(3). The prepared ZTO nanocrystallites had almost the same band gap energy as ZTO nanoparticles prepared by the conventional hydrothermal process. The outcomes of this study indicate that the controlled mineralization of metal precursor ions in a peptide-containing bolaamphiphile molecule suspension can be an alternative method to synthesize metal oxides at room temperature, while maintaining their crystalline structure and optoelectrical properties.     

Identification of irradiated sage tea (Salvia officinalis L.) by ESR spectroscopy

The use of electron spin resonance (ESR) spectroscopy to accurately distinguish irradiated from unirradiated sage tea was examined. Before irradiation, sage tea samples exhibit one asymmetric singlet ESR signal centered at g=2.0037. Besides this central signal, two weak satellite signals situated about 3 mT left and right to it in radiation-induced spectra. Irradiation with increasing doses caused a significant increase in radiation-induced ESR signal intensity at g=2.0265 (the left satellite signal) and this increase was found to be explained by a polynomial varying function. The stability of that radiation-induced ESR signal at room temperature was studied over a storage period of 9 months. Also, the kinetic of signal at g=2.0265 was studied in detail over a temperature range 313–353 K by annealing samples at different temperatures for various times.     

CdS nanocrystallites sensitized ZnO nanorods with plasmon enhanced photoelectrochemical performance

A novel architecture of CdS/ZnO nanorods with plasmonic silver (Ag) nanoparticles deposited at the interface of ZnO nanorods and CdS nanocrystallites, was designed as a photoanode for solar hydrogen generation, with photocurrent density achieving 4.7 mA/cm² at 1.6 V (vs. RHE), which is 8 and 1.7 times as high as those of pure ZnO and CdS/ZnO nanorod films, respectively. Additionally, with optical absorption onset extended to ～660 nm, CdS/Ag/ZnO nanorod film exhibits significantly increased incident photo-to-current efficiency (IPCE) in the whole optical absorption region, reaching 23.1% and 9.8% at 400 nm and 500 nm, respectively. The PEC enhancement can be attributed to the one-dimensional ZnO nanorod structure maintained for superior charge transfer, and the extended visible-light absorption of CdS nanocrystallites. Moreover, the incorporated plasmonic Ag nanoparticles could further promote the interfacial charge carrier transfer process and enhance the optical absorption ability, due to its excellent plasmon resonance effect.     

CdS nanocrystallites sensitized ZnO nanorods with plasmon enhanced photoelectrochemical performance

A sandwiched structure of CdS/Ag/ZnO nanorod photoanode exhibits greatly enhanced photoelectrochemical activity for solar hydrogen generation, due to synergistic effect of CdS nanocrystallites and plasmonic Ag nanoparticles for the enhanced optical absorption and the promoted charge carrier separation.     

石英的顺磁中心在电子自旋共振测年中的特性及应用

沉积物的电子自旋共振测年是利用石英矿物中的顺磁中心浓度确定总辐射能量,进而推定石英矿物的埋藏年代。石英中可用于测年的顺磁中心包括E’心、Al心、Ti心和Ge心。E’心需要经过热活化后才能测年。Al心是一种电子空穴心,在低温下可观测到较强的信号值。光照可以使Al心漂白,但有残留值存在。Ti心、Ge心都是电子中心,Ti心在低温测试中可见,信号微弱。Ge心光晒退最敏感,在常温观测中可见。不同顺磁中心的形成机理不同导致它们具有不同的特性,适用于不同沉积环境中的样品测年,在冰碛物中Ge心测年更具有可行性。电子自旋共振测试时降低温度可使信号增强,Ti心在10 K和15 K时信号强度最大;Al心在20 K时信号最强。Ge心在200 K时信号明显增强。在电子自旋共振测年中可根据不同顺磁中心信号强度的变化调整测试温度获得信号的最优值。在以后的ESR测试中可以选取信号最强时的测试温度进行测试,以增强微弱信号的信噪比,有利于对复杂的信号形态的分辨确定,提高对信号强度定量的准确性。     

Cu–ZnO nanocrystallites by aqueous thermolysis method

ZnO and different atomic percentages of Cu-doped ZnO nanocrystallites have been prepared by aqueous thermolysis method using Glycine as a fuel and encapsulating agent. Mechanism and formation of intermediate products have been given for the first time. All the findings given are for samples annealed at 800?°C. XRD of nanocrystalline ZnO and Cu?CZnO has been indexed to hexagonal wurtzite structure. Influence of temperature on thermal properties of gel precursor and Cu-doped ZnO nanoparticles have been investigated using thermogravimetric and differential thermal analysis. Accordingly, samples have been annealed at different temperatures. Infrared studies revealed formation of Cu?CZnO nanoparticles and removal of organic matter at higher temperature.     

Effect of seeded substrates on hydrothermally grown ZnO nanorods

We report a study on the effect of seeding on glass substrates with zinc oxide nanocrystallites towards the hydrothermal growth of ZnO nanorods from a zinc nitrate hexahydrate and hexamethylenetetramine solution at 95 °C. The seeding was done with pre-synthesized ZnO nanoparticles in isopropanol with diameters of about 6–7 nm as well as the direct growth of ZnO nanocrystallites on the substrates by the hydrolysis of pre-deposited zinc acetate film. The nanorods grown on ZnO nanoparticle seeds show uniform dimensions throughout the substrate but were not homogenously aligned vertically from the substrate and appeared like nanoflowers with nanorod petals. Nanorods grown from the crystallites formed in situ on the substrates displayed wide variations in dimension depending upon the preheating and annealing conditions. Annealing the seed crystals below 350 °C led to scattered growth directions whereupon preferential orientation of the nanorods perpendicular to the substrates was observed. High surface to volume ratio which is vital for gas sensing applications can be achieved by this simple hydrothermal growth of nanorods and the rod height and rod morphology can be controlled through the growth parameters.