ZnO/ZnS Heterostructured Nanorod Arrays and Their Efficient Photocatalytic Hydrogen Evolution

Semiconducting heterostructures have been widely applied in photocatalytic hydrogen evolution due to their variable band gaps and high energy conversion efficiency. As typical semiconducting heterostructures, ZnO/ZnS heterostructured nanorod arrays (HNRAs) have been obtained through a simple anion‐exchange process in this work. Structural characterization indicates that the heterostructured nanorods (HNRs) are all composed of hexagonal wurtzite ZnO core and cubic zinc‐blende ZnS shell. As expected, the as‐obtained one‐dimensional heterostructures not only lower the energy barrier but also enhance the separation ability of photogenerated carriers in photocatalytic hydrogen evolution. Through comparisons, it is found that 1D ZnO/ZnS HNRAs exhibit much better performance in photocatalytic hydrogen evolution than 1D ZnO nanorod arrays (NRAs) and 1D ZnS NRAs. The maximum H₂ production is 19.2 mmol h^?1 for 0.05 g catalyst under solar‐simulated light irradiation at 25 °C and the corresponding quantum efficiency is 13.9 %, which goes beyond the economical threshold of photocatalytic hydrogen evolution technology.     

花状ZnO/ZnS异质结构的简易合成、结构表征及光催化活性

采用简便的两步溶液相化学方法,在较低温度下(80℃),制备出了花状的ZnO/ZnS异质结构。分别利用X射线衍射、X射线光电子能谱仪、扫描电子显微镜、透射电子显微镜、紫外-可见光谱仪等测试手段对所制备的样品进行表征,结果表明ZnO/ZnS异质结构是由花状ZnO纳米结构和ZnS纳米粒子组成。在光降解罗丹明B(RhB)的测试中,ZnO/ZnS异质结构样品体现出了比ZnO前驱物和商业P25光催化剂更高的光催化效率,这主要可归因于异质结构更有利于电子-空穴的有效分离。ZnO/ZnS光催化剂体现出良好的循环稳定性。     

One-pot hydrothermal synthesis of heterostructured ZnO/ZnS nanorod arrays with high ethanol-sensing properties

ZnO/ZnS heterostructured nanorod arrays with uniform diameter and length were synthesized from zinc substrates in a one-pot procedure by using a simple hydrothermal method. Structural characterization by HRTEM indicated that the heterostructured nanorods were composed of parallel segments of wurtzite-type ZnO and zinc-blende ZnS, with a distinct interface along the axial direction, which revealed the epitaxial relationship, ZnO (1010) and ZnS (111). The as-prepared ZnO/ZnS nanorods showed only two green emissions at around 523?nm and 576?nm. We also found that the nanorods exhibited high sensitivity to ethanol at relatively low temperatures, owing to their smaller size and structure.     

One‐Pot Hydrothermal Synthesis of Heterostructured ZnO/ZnS Nanorod Arrays with High Ethanol‐Sensing Properties

ZnO/ZnS heterostructured nanorod arrays with uniform diameter and length were synthesized from zinc substrates in a one‐pot procedure by using a simple hydrothermal method. Structural characterization by HRTEM indicated that the heterostructured nanorods were composed of parallel segments of wurtzite‐type ZnO and zinc‐blende ZnS, with a distinct interface along the axial direction, which revealed the epitaxial relationship, ZnO (10$\bar 1$ 0) and ZnS ($\bar 1$ 1$\bar 1$ ). The as‐prepared ZnO/ZnS nanorods showed only two green emissions at around 523 nm and 576 nm. We also found that the nanorods exhibited high sensitivity to ethanol at relatively low temperatures, owing to their smaller size and structure.     

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.     

Low‐density polyethylene films doped with europium(III) complex: their properties and applications

Light‐converting polyethylene film containing europium(III) complex with phenanthroline was manufactured under an extrusion process. The film was characterized first by means of time‐of‐flight secondary‐ion‐mass spectrometry (TOF‐SIMS), ultraviolet‐visible‐infrared (UV‐vis‐IR) spectroscopy, then a study of excitation and luminescence spectra, quantum yield and lifetime of luminescence. The quantum yield of luminescence was measured as 5±2%, and the lifetime of luminescence was determined about 470 μsec. TOF‐SIMS surface mapping showed the uniform distribution of europium(III) over the film. Visualization of strong picosecond UV laser beams through the use of the developed film has been demonstrated. Copyright © 2004 John Wiley & Sons, Ltd.     

A study on electrodeposited of ZnO/ZnS heterostructures

ZnO/ZnS heterostructures were synthesized by a two steps electrochemical deposition method. Firstly, ZnS layer was deposited from an aqueous solution containing Na₂S₂O₃ and ZnSO₄ onto indium-doped tin oxide (ITO) coating glass substrate at two deposition potentials. Then, ZnO nanostructures were deposited from an aqueous solution of Zn(NO₃) onto ZnS surface. The as-obtained samples were characterized by scanning electron microscopy (SEM), atomic force microscopy (AFM), X-ray diffraction (XRD), Raman and UV-visible analysis. The results indicate that the electrodeposition of ZnS layer at ?0.9 V give the best proprieties of ZnO/ZnS heterostructures. Homogeneous and uniform surface of ZnO/ZnS heterostructure was confirmed by AFM images. The XRD patterns indicates a high crystallinity of ZnO/ZnS. A high transmittance of 65% was also noted from UV-Visible spectra and band gap energy as large as 3.6?eV was found.     

One‐Pot Method for Synthesizing Spherical‐Like Metal Sulfide–Reduced Graphene Oxide Composite Powders with Superior Electrochemical Properties for Lithium‐Ion Batteries

A facile, one‐pot method for synthesizing spherical‐like metal sulfide–reduced graphene oxide (RGO) composite powders by spray pyrolysis is reported. The direct sulfidation of ZnO nanocrystals decorated on spherical‐like RGO powders resulted in ZnS–RGO composite powders. ZnS nanocrystals with a size below 20 nm were uniformly dispersed on spherical‐like RGO balls. The discharge capacities of the ZnS–RGO, ZnO–RGO, bare ZnS, and bare ZnO powders at a current density of 1000 mA g^?1 after 300 cycles were 628, 476, 230, and 168 mA h g^?1, respectively, and the corresponding capacity retentions measured after the first cycles were 93, 70, 40, and 21 %, respectively. The discharge capacity of the ZnS–RGO composite powders at a high current density of 4000 mA g^?1 after 700 cycles was 437 mA h g^?1. The structural stability of the highly conductive ZnS–RGO composite powders with ultrafine crystals during cycling resulted in excellent electrochemical properties.     

Heterointerface Engineering of ZnO/CdS Heterostructures through ZnS Layers for Photocatalytic Water Splitting

Solar-driven water splitting to produce clean and renewable hydrogen offers a green strategy to address the energy crisis and environmental pollution. Heterostructure catalysts are receiving increasing attention for photocatalytic hydrogen generation. ZnO/ZnS/CdS and ZnO/CdS heterostructures have been successfully designed and prepared according to two different strategies. By introducing a heterointerface layer of ZnS between ZnO and CdS, a Z scheme charge-transfer channel was promoted and achieved superior photocatalytic performance. A highest hydrogen generation rate of 156.7 μmol g⁻¹ h⁻¹ was achieved by precise control of the thickness of the heterointerface layer and of the CdS shell. These findings demonstrated that heterostructures are promising catalysts for solar-driven water splitting, and that heterointerface engineering is an effective way to improve the photocatalytic properties of heterostructures.     

硫化锌与硫化锌/氧化锌异质结纳米线的化学气相沉积法制备与表征

介绍一种利用石墨还原快速制备大量硫化锌纳米线的方法,并分别合成了超晶格型、双轴型、核/壳型的硫化锌/氧化锌异质结纳米线。所合成的硫化锌纳米线存在六方纤锌矿和立方闪锌矿两种晶型,纳米线长度达几十微米,直径在20-50 nm,直径均匀且产量很高。在具有双轴型的硫化锌/氧化锌异质结中,首次发现具有超结构特征的氧化锌。HRTEM分析表明,硫化锌/氧化锌超晶格异质结界面为ZB-ZnS(111)∥ZnO(0001),而核/壳型异质结界面为W-ZnS(0001)∥ZnO(0001),这三个晶面分别为各自晶体的极性面,即所合成的硫化锌/氧化锌异质结中极性面相互平行。对ZnS 和ZnS/ZnO 异质结的生长机制进行了探讨,并对硫化锌纳米线与硫化锌/氧化锌异质结的光学性质进行了分析。     

Fabrication and photoluminescent properties of heteroepitaxial ZnO/Zn0.8Mg0.2O coaxial nanorod heterostructures

ZnO/Zn0.8Mg0.2O coaxial nanorod heterostructures were prepared by employing catalyst-free metal-organic vapor-phase epitaxy, and their structural and photoluminescent (PL) properties were investigated using transmission electron microscopy (TEM) and temperature-dependent PL spectroscopy. TEM images show that ZnO/Zn0.8Mg0.2O layers were epitaxially grown on the entire surfaces of the ZnO nanorods and the ZnO nanorod diameters as a core material were as small as 9 +/- 2 nm. A dominant PL peak was observed at 3.316 eV, from room-temperature PL spectra of ZnO/Zn0.8Mg0.2O coaxial nanorod heterostructures with ZnO core diameters of 9 nm, indicating a PL blue shift of 30 meV, which resulted from a quantum confinement effect along the radial direction in ZnO nanorods. Furthermore, temperature-dependent PL properties of the coaxial nanorod heterostructures were investigated, showing much higher PL intensity for the coaxial nanorod heterostructures than that of bare ZnO nanorods at room temperature. The origin of the enhanced PL intensity and reduced thermal quenching for the coaxial nanorod heterostructures is also discussed.     

ZnO/ZnS core-shell composites for low-temperature-processed perovskite solar cells

Electron transport layers(ETLs)in perovskite solar cells(PSCs)are a key factor to determine the photovoltaic performance.Herein,we demonstrate preparation of Zn O/ZnS core-shell composites through directly synthesizing ZnS on the ZnO nanoparticles in solution.We confirmed the formation of ZnO/ZnS core-shell composites by the uses of X-ray diffraction patterns and the Fourier transform infrared spectroscopy.ZnO/ZnS composites exhibit much homogeneous surface morphology as compared with the bare Zn O as revealed in the scanning electronic microscopy.Moreover,the upper shift of conduction band level upon composition of the Zn O/Zn S film results in a better alignment of energy level,which facilitates cascade charge extraction and thus improves the current density of perovskite solar cell.The shift of conduction band also improves the voltage of the PSCs.The photoluminescence(PL)spectroscopies measured in both steady and transient states were carried out to characterize the charge extraction at the interface between CH_3NH_3PbI_3and the electron transport layers of either ZnO or ZnO/ZnS composite.The ZnO/ZnS composite can more efficiently quench the PL signal of perovskite absorber than bare Zn O resulting in enhanced photocurrent generation in PSCs.     

Synthesis,characterization, and biosensing application of ZnO/SnO2 heterostructured nanomaterials

In this work, zinc oxide/tin oxide (ZnO/SnO₂) heterostructured nanomaterials were synthesized by hydrothermal method. Transmission electron microscopy, scanning electron microscopy, energy-dispersive X-ray spectroscopy, and X-ray diffraction measurements revealed that the product was composed of ZnO nanowires and SnO₂ nanobranches. The novel ZnO/SnO₂ heterostructured nanocrystals were for the first time used as a supporting matrix to explore a novel immobilization and biosensing platform of redox proteins. UV–visible absorption investigation indicated that hemoglobin (Hb) intercalated well in the ZnO/SnO₂ heterostructured nanocrystals retained its native structure. Comparative experiments have confirmed that the ZnO/SnO₂-based biosensor not only had enhanced direct electron transfer capacity but also displayed excellent electrocatalytic properties such as higher sensitivity and wider linear range to the detection of hydrogen peroxide in comparison with the ZnO- and SnO₂-based biosensors.     

Alloyed ZnS–CuInS2 Semiconductor Nanorods and Their Nanoscale Heterostructures for Visible‐Light‐Driven Photocatalytic Hydrogen Generation

A promising photocatalytic system in the form of heterostructured nanocrystals (HNCs) is presented wherein alloyed ZnS–CuInS₂ (ZCIS) semiconductor nanorods are decorated with Pt and Pd₄S nanoparticles. This is apparently the first report on the colloidal preparation and photocatalytic behavior of ZCIS–Pt and ZCIS–Pd₄S nanoscale heterostructures. Incorporation of Pt and Pd₄S cocatalysts leads to considerable enhancement of the photocatalytic activity of ZCIS for visible‐light‐driven hydrogen production.     

Laser Assisted Catalytic Growth of ZnS/CdSe Core‐Shell and Wire‐Coil Nanowire Heterostructures

ZnS/CdSe core‐shell and wire‐coil nanowire heterostructures have been synthesized by chemical vapor deposition assisted with pulsed laser ablation. Measurements from high‐resolution transmission electron microscopy and selected area electron diffraction have revealed that both ZnS/CdSe core‐shell and wire‐coil nanowires are of single‐crystalline hexagonal wurtzite structures and grow along the [0001] direction. While the lattice parameters of ZnS and CdSe in the core‐shell nanowires are nearly equal to those of bulk ZnS and CdSe, change of the lattice parameters in the CdSe‐coil is attributed to the doping of Zn into CdSe, resulting in the relaxation of compressive strain at the interface between CdSe‐coil and ZnS‐wire. Composition variation across the interfacial regions in the ZnS/CdSe nanowire heterostructures ranges only 10–15 nm despite the pronounced lattice mismatch between ZnS and CdSe by ?11%. Growth mechanisms of the ZnS/CdSe nanowire heterostructures are discussed.     

ZnO/ZnS大面积单晶异质结及其光电性能研究

ZnO和ZnS是重要的Ⅱ-Ⅵ族宽禁带半导体材料,二者之间形成的异质结具有Ⅱ型能带结构,可以促使受激载流子实现空间分离,延长受激载流子的寿命,从而提高材料的光催化和光电探测性能。本文利用物理气相沉积方法,首次在ZnO块状单晶衬底上生长了一层ZnS单晶薄膜,薄膜由厚约4nm、边长几百纳米,取向一致的等边三角形纳米片组成。X射线衍射和透射电子显微镜的表征结果显示,ZnS薄膜与ZnO衬底具有单一外延取向关系。阴极射线荧光光谱表明ZnS薄膜的制备显著提高了ZnO单晶片可见光荧光发光峰的强度。此外,对ZnO/ZnS异质结的紫外光电探测性能的研究结果显示,异质结对不同波长的紫外光均有响应,光响应的上升弛豫时间和下降弛豫时间分别为200ms和1050ms,展示了较好的光电应用潜力。     

SIMS depth profiling of semiconductor interfaces: Experimental study of depth resolution function

Reconstruction of original element distribution at semiconductor interfaces using experimental SIMS profiles encounters considerable difficulties because of the matrix effect, sputtering rate change at the interface, and also a sputtering‐induced broadening of original distributions. We performed a detailed depth profiling analysis of the Al step‐function distribution in GaAs/Al_xGa_1?xAs heterostructures by using Cs⁺ primary ion beam sputtering and CsM⁺ cluster ion monitoring (where M is the element of interest) to suppress the matrix effect. The experimental Depth Resolution Function (DRF) was obtained by differentiation of the Al step‐function profile and compared with the ‘reference’ DRF found from depth profiling of an Al delta layer. The difference between two experimental DRFs was explained by the sputtering rate change during the interface profiling. We experimentally studied the sputtering rate dependence on the Al_xGa_1?xAs layer composition and applied it for a reconstruction of the DRF found by differentiating the Al step‐function distribution: the ‘reconstructed’ and ‘reference’ DRFs were found to be in good agreement. This confirmed the correctness of the treatment elaborated. Copyright © 2010 John Wiley & Sons, Ltd.     

Highly Luminescent Heterostructured Copper‐Doped Zinc Sulfide Nanocrystals for Application in Cancer Cell Labeling

The structural characteristics of the seed‐mediated synthesis of heterostructured CuS–ZnS nanocrystals (NCs) and Cu‐doped ZnS (ZnS:Cu) NCs synthesized by two different protocols are compared and analyzed. At high Cu dopant concentrations, segregated subclusters of ZnS and CuS are observed. The photoluminescence quantum yield of ZnS:Cu NCs is about 50–80 %; a value much higher than that of ZnS NCs (6 %). Finally, these NCs are coated with a thin silica shell by using (3‐mercaptopropyl)triethoxysilane in a reverse microemulsion to make them water soluble. Cytotoxicity experiments show that these silica‐coated NCs have greatly reduced toxicity on both cancerous HeLa and noncancerous Chinese hamster ovary cells. The labeling of cancerous HeLa cells is also demonstrated.     

Solution-chemical synthesis of carbon nanotube/ZnS nanoparticle core/shell heterostructures

A facile solution-chemical method has been developed to be capable of encapsulating a multiwalled carbon nanotube (MWCNT) with ZnS nanocrystals without using any bridging species. The thickness of the ZnS shell can be tuned easily by controlling the experimental conditions. The optical properties of the MWCNT/ZnS heterostructures were investigated using UV-vis absorption and photoluminescence spectroscopy. The optical absorption spectrum indicates that the band gap of ZnS nanocrystallites is 4.2 eV. On the basis of the photoluminescence spectrum, charge transfer is thought to proceed from ZnS nanocrystals to the nanotube in the ZnS-carbon nanotube system. These special heterostructures are very easily encapsulated within a uniform silica layer by a modified-St?ber process and still show better stability even after heat treatment at 400 degrees C, which makes them appealing for practical applications in biochemistry and biodiagnostics.     

Three-dimensional hierarchical CeO<Subscript>2</Subscript> nanowalls/TiO<Subscript>2</Subscript> nanofibers heterostructure and its high photocatalytic performance

Combining the versatility of electrospinning technique and hydrothermal growth of nanostructures enabled the fabrication of hierarchical CeO₂/TiO₂ nanofibrous mat. The as-prepared hierarchical heterostructure consisted of CeO₂ nanowalls growing on the primary TiO₂ nanofibers. Interestingly, not only were secondary CeO₂ nanowalls successfully grown on TiO₂ nanofibers substrates, but also the CeO₂ nanowalls were uniformly distributed without aggregation on TiO₂ nanofibers. The photocatalytic studies suggested that the CeO₂/TiO₂ heterostructures showed enhanced photocatalytic efficiency compared with bare TiO₂ nanofibers under UV light irradiation.