Hierarchical saw-like ZnO nanobelt/ZnS nanowire heterostructures induced by polar surfaces

Saw-like nanostructures composed of single-crystalline ZnO nanobelts and single-crystalline ZnS nanowires have been successfully synthesized by a vapor-solid process. Several techniques, including scanning electron microscope, transmission electron microscopy, and photoluminescence spectroscopy, were used to investigate the structures, morphology, and photoluminescence properties of the products. Due to the similar crystal habits of wurtzite ZnO and ZnS with chemically active Zn-terminated (0001) and chemically inactive O-terminated (or S-terminated) (000) polar surfaces, hierarchical saw-like nanostructures were considered to be formed by the initiation of a chemically active Zn-terminated ZnO (0001) polar surface. Photoluminescence properties of the heterostructures, different from pure ZnO nanobelts or ZnS nanowires, were also studied at room temperature.     

Optical and photocatalytic properties of single crystalline ZnO at the air-liquid interface by an aminolytic reaction

Crystalline flowerlike ZnO was synthesized by an aminolytic reaction at the air-liquid interface in an aqueous media at an alkaline pH. A thin visible film was formed at the air-liquid interface by self-assembly of flowerlike ZnO. Diffraction studies show rearrangement of the single crystalline units at the air-liquid interface leading to the formation of nanobelts. These nanobelts overlap systematically to form petals of the flowerlike structure; individual petals get curved with time. Each nanobelt is found to be single crystalline and can be indexed as the hexagonal ZnO phase. The organic product formed in the aminolytic reaction and dissolution-reprecipitation mechanism is the driving force for the formation of flowerlike ZnO at the air-liquid interface. A clear relationship between the surface, photocatalytic, and photoluminescent properties of ZnO is observed. The flowerlike structure exhibits a blue shift (3.56 eV) in the band emission as compared to bulk ZnO (3.37 eV). The photodegradation of methylene blue over the flowerlike ZnO catalyst formed at the air-liquid interface and in the sediments shows enhanced photocatalytic activity. The sub-bands formed due to surface defects facilitate separation of charge carriers increasing their lifetime, leading to enhanced photocatalytic activity of flowerlike ZnO.     

Synthesis of porous and nonporous ZnO nanobelt, multipod, and hierarchical nanostructure from Zn-HDS

Zn based hydroxide double salts (Zn-HDS) with an interlayer spacing of 20 Å was produced by dissolving dumbbell-like ZnO crystal. The resulting Zn-HDS with a ribbon-like shape has a suitable morphology to explore the remarkably mild procedure for synthesis of ZnO nanobelts. We found that the intercalated water molecules into the Zn-HDS could play a key role in the ZnO nanobelts porosity. The nonporous ZnO nanobelts were successfully synthesized from the Zn-HDS by soft-solution process at 95 °C through mild dehydration agent as Na₂CO₃. As-synthesized ZnO nanobelts were grown along not only the [0 1 −1 0], but also the [2 −1 −1 0]. On the other hand, the porous ZnO nanobelts were obtained from the Zn-HDS by calcinations at 200 and 400 °C. In addition, flower-like ZnO multipod and hierarchical nanostructures were produced from the Zn-HDS by using of strong dehydration agent (NaOH) through hydrothermal reaction at 150 and 230 °C.     

Surface-Polarity-Induced Spatial Charge Separation Boosts Photocatalytic Overall Water Splitting on GaN Nanorod Arrays

Photocatalytic overall water splitting has been recognized as a promising approach to convert solar energy into hydrogen. However, most of the photocatalysts suffer from low efficiencies mainly because of poor charge separation. Herein, taking a model semiconductor gallium nitride (GaN) as an example, we uncovered that photogenerated electrons and holes can be spatially separated to the nonpolar and polar surfaces of GaN nanorod arrays, which is presumably ascribed to the different surface band bending induced by the surface polarity. The photogenerated charge separation efficiency of GaN can be enhanced significantly from about 8 % to more than 80 % via co-exposing polar and nonpolar surfaces. Furthermore, spatially assembling reduction and oxidation cocatalysts on the nonpolar and polar surfaces remarkably boosts photocatalytic overall water splitting, with the quantum efficiency increased from 0.9 % for the film photocatalyst to 6.9 % for the nanorod arrays photocatalyst.     

Surface‐Polarity‐Induced Spatial Charge Separation Boosts Photocatalytic Overall Water Splitting on GaN Nanorod Arrays

Photocatalytic overall water splitting has been recognized as a promising approach to convert solar energy into hydrogen. However, most of the photocatalysts suffer from low efficiencies mainly because of poor charge separation. Herein, taking a model semiconductor gallium nitride (GaN) as an example, we uncovered that photogenerated electrons and holes can be spatially separated to the nonpolar and polar surfaces of GaN nanorod arrays, which is presumably ascribed to the different surface band bending induced by the surface polarity. The photogenerated charge separation efficiency of GaN can be enhanced significantly from about 8 % to more than 80 % via co‐exposing polar and nonpolar surfaces. Furthermore, spatially assembling reduction and oxidation cocatalysts on the nonpolar and polar surfaces remarkably boosts photocatalytic overall water splitting, with the quantum efficiency increased from 0.9 % for the film photocatalyst to 6.9 % for the nanorod arrays photocatalyst.     

图案化锥形氧化锌纳米带的原位热氧化法制备与发光性质

采用光刻技术制备出图案的锌膜,所得锌膜与纯氧在700℃氧化反应10 min,在锌膜的表面上原位生长出具有图案的锥形ZnO纳米带阵列,实现了ZnO纳米带生长位置的可控生长。锌膜上得到的锥形ZnO纳米带为单晶六方纤锌矿结构,长度在1～4μm,纳米带根部和顶部的宽度分别在300～700 nm和100～300 nm。提出了锥形ZnO纳米带的可能生长机理。在波长为300nm光的激发下,发现了锌膜上锥形ZnO纳米带具有发光峰位于395 nm弱的紫外光发光和510 nm强的蓝绿光发光,它们分别起源于ZnO宽带隙的激子发射以及表面上离子化氧空位中的电子与价带中光激发的空穴之间的复合。     

ZnO nanobelt arrays grown directly from and on zinc substrates: synthesis, characterization, and applications

In situ growth of ZnO nanobelt arrays from and on zinc substrates (foils and microparticles) has been accomplished by controlled thermal oxidation in the presence of oxygen. The nanobelts grow approximately perpendicular to the Zn substrate surface along the 110 direction of ZnO, which has a thickness of approximately 3-4 nm, a width tapering from about 50 to 300 nm, and a length of approximately 10-20 mum. On the basis of the structural analysis and kinetic studies, a tip-growth mechanism is proposed, which underlines the transport of Zn from the substrate to the growing tip. The ratio of UV to green photoluminescent emissions of the as-synthesized ZnO nanobelt arrays could be controlled by varying the reaction conditions. Sharp UV stimulated emission peak is also observed at moderate threshold excitation intensity ( approximately 0.7 mJ/cm(2)) showing the high quality of the ZnO nanobelts. The ZnO nanobelts array has also been tested for sensing NH(3) gas, and high sensitivity, reversibility, and rapid response have been demonstrated.     

ZnO Nanobelts and Hollow Microspheres Grown on Cu Foil

ZnO nanobelts, hollow microspheres, and urchins have been prepared on copper foil via a simply low temperature evaporation route. The microstructure, morphologies, and photolu-minescence of the ZnO nanostructures were studied with X-ray diffraction, Raman spectra, scanning electron microscopy and photoluminescence spectra. The width of the nanobelts was about 500 nm and the length was longer than 10μm. The diameter of the hollow microspheres was between 5 and 10μm. A possible growth mechanism of the nanobelts, microspheres and urchins was proposed. The photoluminescence spectrum exhibited strong deep level energy emissions and a weak near band edge emission. These ZnO nanostructures on a copper substrate have the advantages of naturally good adhesion and electrical connection between the ZnO nanostructures and the conductive substrate.     

Sn掺杂ZnO半导体纳米带的制备、结构和性能

在无催化剂的条件下, 利用碳热还原反应气相沉积法制备出了高产率单晶Sn掺杂ZnO纳米带. XRD和TEM研究表明纳米带为结晶完好的纤锌矿结构, 生长方向沿[0001], EDS分析表明纳米带中Sn元素含量约为1.9%. 室温光致发光谱(PL)显示掺锡氧化锌纳米带存在强的绿光发射峰和较弱的紫外发射峰, 谱峰峰位中心分别位于494.8 nm和398.4 nm处, 并对发光机制进行了分析. 这种掺杂纳米带有望作为理想的结构单元应用于纳米尺度光电器件领域.     

Morphology‐Dependent Gas‐Sensing Properties of ZnO Nanostructures for Chlorophenol

The crystal‐plane effect of ZnO nanostructures on the toxic 2‐chlorophenol gas‐sensing properties was examined. Three kinds of single‐crystalline ZnO nanostructures including nanoawls, nanorods, and nanodisks were synthesized by using different capping agents via simple hydrothermal routes. Different crystal surfaces were expected for these ZnO nanostructures. The sensing tests results showed that ZnO nanodisks exhibited the greatest sensitivity for the detection of toxic 2‐chlorophenol. The results revealed that the sensitivity of these ZnO samples was heavily dependent on their exposed surfaces. The polar (0001) planes were most reactive and could be considered as the critical factor for the gas‐sensing performance. In addition, calculations using density functional theory were employed to simulate the gas‐sensing reaction involving surface reconstruction and charge transfer both of which result in the change of electronic conductance of ZnO.     

Traps for charge carriers in molecular materials formed by dipolar species: towards light-driven molecular switch

The influence of polar species on the transport and trapping of charge carriers is discussed. Calculations performed on a model molecular lattice demonstrate that polar dopants locally modify the polarization energy thus creating traps for charge carriers in the vicinity of the dipole. The presence of polar dopants in disordered solids gives rise to a broadening of the density-of-states function. A scheme of a molecular switch has been put forward, based on electrostatic interactions between photochromic moieties and charge carriers travelling on a molecular wire (conjugated polymer chain).     

Development and investigation of the flexible hydrogen sensor based on ZnO-decorated Sb2O3 nanobelts

Hydrogen is regarded as the next-gen fuel for vehicles to avoid the emission of toxic gases, which needs a continuous monitoring of the concentration level. In the design of the H₂ sensor, especially of flexible type, a sensing layer will be blended, which affects the sensing performance of the device. Based on this concern, the present investigation is carried out to understand the effect of the bending angle toward the sensing performance of bare and ZnO (n-type)-decorated Sb₂O₃ (p-type) nanobelt–based sensors for hydrogen gas. The sensing element was prepared by the thermal chemical vapor deposition followed by the drop-casting method. Furthermore, the role of the zinc precursor (molar concentration—1 M–3 M) on the preparation of ZnO-decorated Sb₂O₃ nanobelts was studied. Various techniques were used to confirm the formation of ZnO-decorated nanobelts such as X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive X-ray analysis (EDAX), and Fourier transform infrared spectroscopy (FTIR). From these analyses, 1 M concentration of the zinc precursor shows uniform distribution of nanoparticles over the surface of Sb₂O₃ nanobelts. However, agglomeration was observed when the concentration of the zinc precursor increases from 1 M to 3 M. Later, the prepared nanobelts were deposited on the OverHead Projector (OHP) sheet by the doctor blade method for sensing hydrogen gas at 100 °C at a concentration of 1000–3000 ppm. In addition to it, the effect of the substrate bending angle (0°, 45°, 60°, and 90°) was analyzed at a fixed concentration of H₂ gas (1000 ppm). From this study, it is clear that the highest sensing response was achieved for 1 M decorated nanobelts compared with bare as well as other concentrations because of uniform distribution of nanoparticles on the surface of nanobelts. Moreover, the prepared sample demonstrates better sensing performance with the bending of substrates, which suggests that the prepared sensor could be used for flexible electronic devices. The prepared nanobelts show a good H₂ gas–sensing response even with bending of the substrates. The work suggests that the prepared sensor is applicable for flexible electronic devices.     

氧化锌纳米带的低温无催化热蒸发制备及其表征

通过纯锌粉蒸发，在600 ℃无催化条件下成功制备了高质量的不同形貌的ZnO纳米带.该制备方法中控制产物形貌和尺寸的关键是氧、氩及锌蒸气的流速及分压.扫描电镜及高分辩透射电镜观察显示，氧化锌纳米带具有规整光滑及齿状等不同形貌，且皆为单晶，其生长由固-气机理控制.室温光致发光谱表明，齿状氧化锌纳米带在390 nm附近形成紫外发射峰；在455～495 nm时，形成绿光发射峰，该处由4个次级发射峰组成.     

Elongation method with intermediate mechanical and electrostatic embedding for geometry optimizations of polymers

The elongation method with intermediate mechanical and electrostatic embedding (ELG-IMEE) is proposed. The electrostatic embedding uses atomic charges generated by a charge sensitivity analysis (CSA) method and parameterized for three different population analyses, namely, the Merz–Singh–Kollman scheme, the charge model 5, and the atomic polar tensor. The obtained CSA models were tested on two model systems. Test calculations show that the electrostatic embedding provides several times of decrease in the difference of energies of testing and reference calculations in comparison with the conventional elongation approach (ELG). The mechanical embedding is implemented in a combination of the conventional elongation method and the ONIOM approach. Moreover, it was demonstrated that the geometry optimization with the ELG-IMEE reduces the errors in the optimized structures by about one order in root-mean-square deviation, when compared to ELG.     

Interface dominated high photocatalytic properties of electrostatic self-assembled Ag(2)O/TiO(2) heterostructure

Electrostatic self-assembled Ag(2)O/TiO(2) nanobelts heterostructure was synthesized via simple physical mixing of Ag(2)O nanoparticles and TiO(2) nanobelts. The morphologies and microstructures of Ag(2)O/TiO(2) nanobelt heterostructure were characterized by high resolution transmission electron microscopy. The interface dominated high UV photocatalytic activity and degraded photoluminescence strength of composite catalyst confirmed the heterostructure effect between Ag(2)O nanoparticles and TiO(2) nanobelts. X-ray photoelectron spectroscope provided direct evidence of charge transfer on the heterostructures between them.     

Particle charging and charge screening in nonpolar dispersions with nonionic surfactants

The electrostatic stabilization of colloidal dispersions is usually considered the domain of polar media only because of the high energetic cost associated with introducing electric charge in nonpolar environments. Nevertheless, some surfactants referred to as "charge control agents" are known to raise the conductivity of liquids with low electric permittivity and to mediate charge stabilization of nonpolar dispersions. Here we study an example of the particularly counterintuitive charging and electrostatic interaction of colloidal particles in a nonpolar solvent caused by nonionic surfactants. PMMA particles in hexane solutions of nonionic sorbitan oleate (Span) surfactants are found to exhibit a field-dependent electrophoretic mobility. Extrapolation to zero field strength yields evidence for large electrostatic surface potentials that decay with increasing surfactant concentration in a fashion reminiscent of electrostatic screening caused by salt in aqueous solutions. The amount of surface charge and screening ions in the nonpolar bulk is further characterized via measurements of the particles' pair interaction energy. The latter is obtained by liquid structure analysis of quasi-2-dimensional equilibrium particle configurations studied with digital video microscopy. In contrast to the behavior reported for systems with ionic surfactants, we observe particle charging and a screened Coulomb type interaction both above and below the surfactant's critical micelle concentration.     

聚乙烯醇辅助合成ZnO纳米带及其表征

本文中以乙酸锌[Zn(CH3COO)2·2H2O]和高分子聚乙烯醇(PVA)为原料, 通过控制升温速度、调节溶液浓度, 于550 ℃合成了不同形貌和尺寸的ZnO纳米带.     

Synthetic architectures of TiO2/H2Ti5O11.H2O, ZnO/H2Ti5O11.H2O, ZnO/TiO2/H2Ti5O11.H2O, and ZnO/TiO2 nanocomposites

Although synthetic investigations of inorganic nanomaterials had been carried out extensively over the past decade, few of them have been devoted to fabrication of complex nanostructures that comprise multicomponents/phases (i.e., composite nanobuilding blocks), especially in the area of structural/morphological architecture. In this work, nanobelts of a protonated pentatitanate (H(2)Ti(5)O(11).H(2)O) were synthesized hydrothermally for the first time. Two technologically important transition-metal-oxides TiO(2) and ZnO were then grown respectively or sequentially onto the surface of the as-prepared nanobelts in aqueous mediums. With a main emphasis on organizational manipulation, the present investigation examines general issues of morphological complexity, synthetic interconvertibility, and material combinability related to fabrication of inorganic nanocomposites. Using this model material system, we demonstrate that complex binary and tertiary composite building blocks of TiO(2)/H(2)Ti(5)O(11).H(2)O, ZnO/H(2)Ti(5)O(11).H(2)O, ZnO/TiO(2)/H(2)Ti(5)O(11).H(2)O, and ZnO/TiO(2) can be architected stepwise in solution. Structural features of these nanocomposites have also been addressed.     

Adsorption of single Cu atoms at differently stabilized polar ZnO surfaces: An ab initio study

In this study, the adsorption of a single Cu atom on the polar ZnO(0001) and ZnO(0001) surfaces was investigated by means of highly accurate wave function based ab initio methods. Different modifications of the polar surfaces were investigated: unstabilized surfaces, surfaces with hydrogen and OH overlayers, and defectious surfaces. Cu is strongly bound at the unstabilized surfaces by a charge transfer mechanism which induces a stabilization of the surface. At regular adsorption sites of stabilized surfaces the binding energies are much smaller. At oxygen defects, the Cu electron is transferred to the defect and a Cu(+) ion sits on top of the defect. At the Zn terminated surface the Cu moves into the Zn defects.