Metal‐Cluster‐Decorated TiO2 Nanotube Arrays: A Composite Heterostructure toward Versatile Photocatalytic and Photoelectrochemical Applications

Recent years have witnessed increasing interest in the solution‐phase synthesis of atomically precise thiolate‐protected gold clusters (Au_x); nonetheless, research on the photocatalytic properties of Au_x–semiconductor nanocomposites is still in its infancy. In this work, recently developed glutathione‐capped gold clusters and highly ordered nanoporous layer‐covered TiO₂ nanotube arrays (NP‐TNTAs) are employed as nanobuilding blocks for the construction of a well‐defined Au_x/NP‐TNTA heterostructure via a facile electrostatic self‐assembly strategy. Versatile photocatalytic performances of the Au_x/NP‐TNTA heterostructure which acts as a model catalyst, including photocatalytic oxidation of organic pollutant, photocatalytic reduction of aromatic nitro compounds and photoelectrochemical (PEC) water splitting under simulated solar light irradiation, are systematically exploited. It is found that synergistic interaction stemming from monodisperse coverage of Au_x clusters on NP‐TNTAs in combination with hierarchical nanostructure of NP‐TNTAs reinforce light absorption of Au_x/NP‐TNTA heterostructure especially within visible region, hence contributing to the significantly enhanced photocatalytic and PEC water splitting performances. Moreover, photocatalytic and PEC mechanisms over Au_x/NP‐TNTA heterostructure are elucidated and corresponding reaction models were presented. It is anticipated that this work could boost new insight for photocatalytic properties of metal‐cluster‐sensitized semiconductor nanocomposites.     

Morphology-dependent photocatalytic activities of hierarchical microstructures of ZnO

A range of hierarchical microstructures of ZnO were prepared using a hydrothermal method with Zn(NO₃)₂ and N,N-dimethyl ethylenediamine (DMEDA) in the presence of sodium 1-undecanesulfonate. The resulting ZnO products exhibited rod-, peanut-, dumbbell-, and notched spherical-like shapes. With increasing sodium 1-undecanesulfonate concentration, the morphology of the ZnO products evolved from rod-like, through to peanut- and dumbbell-like, then to notched spheres with higher hierarchy. The photocatalytic activities of the ZnO products for the decomposition of Rhodamine 6G were examined. The morphology of ZnO products had a significant effect on the photocatalytic activity. The mechanism of the morphology-controlled synthesis of ZnO and their morphology-dependent photocatalytic activity are discussed.     

Enhanced photocatalytic activity of Fe-doped ZnO nanoparticles synthesized via a two-step sol–gel method

A series of Zn_1–x Fe _x O (x = 0, 1, 2, 3, 4 %) powders via a two-step sol–gel method in open system were successfully fabricated. Influence of Fe doping concentration on the structure, morphology, optical properties and photo catalysis properties were investigated by means of X-ray diffraction, scanning electron microscopy, UV–Vis spectrophotometer and photochemical reaction instrument. The results showed that the ZnO powders were hexagonal wurtzite structures and their crystalline sizes and particle diameters decreased with the increase of Fe doping concentration. An increase of visible light absorption value and a decrease in band gap from 3.219 to 3.167 eV were found with the increase of Fe doping concentration, which enable the sample harvest more photons to excite the electron from the valence. Enhanced visible light induced photocatalytic activity has been found in Fe doped ZnO and the ultraviolet light induced photocatalytic properties of the Fe-doped ZnO have been improved greatly compared with undoped ZnO and commercially available TiO₂ (P25). The photocatalytic activities were not significantly affected by the particle size, and the best Fe doping concentration is 1 %.     

Photocatalytic behaviors of porous ZnO hierarchical structures fabricated via a precursor-pyrolyzing route

It is of significance to develop porous ZnO photocatalysts with high activity. In this paper, three kinds of hierarchical ZnO porous structures were fabricated by a precursor transformation of hierarchical Zn₅(CO₃)₂(OH)₆ structures synthesized in the zinc salts and urea aqueous solution. The microstructure characterization demonstrates that the obtained ZnO materials are porous structure and quasi-single-crystal nature. The solid UV–vis and PL spectra indicate that the porous ZnO with different morphologies have similar photoabsorption ability but different ratioes of green-to-UV emission, respectively. These porous ZnO samples with different structures exhibit different photocatalytic efficiency. More importantly, the photocatalytic activity of porous ZnO fabricated by the precursor-pyrolyzing method is inversely proportional to the content of surface defects under other influence factors comparable. This result inconsistent with references was also discussed.     

ZnO/GaN heterostructure for LED applications

White electroluminescence (EL) from ZnO/GaN structures fabricated by pulsed laser deposition of Zn:In onto GaN:Mg/GaN structures MOCVD-grown on Al₂O₃ substrates has been observed. The white light is produced by superposition of two strongest emission lines, narrow blue and broad yellow, peaked at 440 and 550 nm, respectively. The intensity ratio of different EL lines from ZnO/GaN/Al₂O₃ structures depends on the ZnO film quality and drive current. The white EL is due to the high density of structural defects at the n-ZnO/p-GaN interface. A band diagram of the n-ZnO/p-GaN/n-GaN is constructed and a qualitative explanation of the EL is given. Conditions of ZnO deposition strongly affects the properties of the recombination emission and predetermines the EL spectrum of the LED structure if it does not have high quantum efficiency (more than 1%) such as in commercial LEDs.     

Capillary Force‐Driven,Hierarchical Co‐Assembly of Dandelion‐Like Peptide Microstructures

The wetting and drying of drops on flexible fibers occurs ubiquitously in nature, and the capillary force underlying this phenomenon has motivated our great interest in learning how to direct supramolecular self‐assembly. Here, the hierarchical co‐assembly of two aromatic peptides, diphenylalanine (FF) and ferrocene‐diphenylalanine (Fc‐FF), is reported via sequential, combinatorial assembly. The resulting dandelion‐like microstructures have highly complex architectures, where FF microtube arrays serve as the scapes and the Fc‐FF nanofibers serve as the flower heads. Homogeneous FF microtubes with diameters tailored between 1 and 9 μm and wall thickness ranging from 70 to 950 nm are initially formed by controlling the degree of supersaturation of the FF and the water content. Once the FF microtubes are formed, the growth of the dandelion‐like microstructures is then driven by the capillary force, derived from the wetting and drying of the Fc‐FF solution on the FF microtubes. This simple and ingenious strategy offers many opportunities to develop new and creative methods for controlling the hierarchical self‐assembly of peptides and thus building highly complex nano and microstructures.     

Hierarchical nanostructures of ZnO obtained by spray pyrolysis

A two step spray pyrolysis deposition method was applied in order to grow ZnO nanorod core/ZnO shell hierarchical nanostructures with various surface morphologies, such as a highly organised platelet network on the side facets of the ZnO rod and bundles of nanoneedles on the top plane of the rod. First, well-shaped ZnO nanorods with lengths of ca. 1 μm and average diameters of 150–300 nm were deposited from zinc chloride (ZnCl₂·2H₂O) aqueous solutions onto TCO/glass substrates. Then, zinc acetate (Zn(CH₃COO)₂·2H₂O) solution was pulverised over the surface of the sprayed ZnO nanorods at a growth temperature of approximately 330 °C within 6–10 min. The obtained structures were characterised by high resolution SEM, UV–VIS and XRD. To estimate the surface areas and photocatalytic ability of the bare rods and hierarchical structures, their adsorption ability and activity of photocatalytic oxidation of doxycycline were measured. It was found that the surface area of hierarchical structures comprised of a network of platelets is at least 4 times larger than that of a bare rod. The structural and morphological properties of sprayed hierarchical structures largely depend on the spraying rate of the zinc acetate solution and on the ZnO nanorod top plane shape.     

Microstructures and mechanical properties of as‐cast titanium–zirconium–molybdenum ternary alloys

In this study titanium–zirconium–molybdenum alloys (Ti₅₀Zr₅₀)_100‐xMo_x (xMo; x = 0 at.%, 1 at.%, 3 at.%, 5 at.% or 7 at.%) were investigated, focusing on the effect of molybdenum addition on their microstructures and mechanical properties. Transmission electron microscopy observations revealed that the binary Ti₅₀Zr₅₀ alloy was composed entirely of an acicular hexagonal structure of the α’ phase. When the molybdenum content was 1 at.%, the alloy was composed of β and ω phases. However, when 3 at.% or more molybdenum was added, only the equiaxed, retained β phase was observed. Tensile tests at room temperature indicated that the mechanical properties of the 1Mo alloy were inferior owing to the embrittlement effects of the ω phase and the difficulty of dislocation motion through the ω phase. Our research suggested that the 5Mo alloy had excellent ductility (16.5 %) as well as adequate strength (780 MPa). The improved mechanical properties were attributed to the enhanced stability of the β phase and the disappearance of the ω phase.     

Influence of phase composition and textural features of ZnMoO<Subscript>4</Subscript>–MoO<Subscript>3</Subscript> systems on the photocatalytic degradation of methyl red

The studied samples ZnMoO₄–MoO₃, have been prepared by immersing an amount of molybdenum oxide in zinc acetate solution according to the appropriate molar ratio x = ZnO/MoO₃ = 0, 0.2, 0.4, 0.6, 0.8 and 1. These samples were then heated at temperature of 500°C for 3 hours. Prepared samples were characterized using different techniques such as: X-ray diffraction, Fourier spectroscopy, Raman spectroscopy, differential thermal analysis and nitrogen adsorption-desorption measurements. The Photocatalytic activity was studied via degradation of methyl red in aqueous solution when subjected to UV radiation. The results of this work revealed some variations, by increasing ZnO quantity, in phase composition and textural characteristics of ZnMoO₄–MoO₃ samples. It was found that these changes affect the photocatalytic activity by enhancing the degradation rate of Methyl red during the UV irradiation process.     

Fabrication of novel hierarchical ZnO via ultrasonic assisted hydrothermal route and their gas sensing property

Novel hierarchical ZnO nanomaterials with castellated and turriform morphologies were successfully synthesized by ultrasonic assisted hydrothermal route. The morphology and structure of products were characterized by scanning electron microscopy and X-ray diffraction, respectively. The results show that as-prepared castellated ZnO microrods have six-equal axis symmetry features with the length of 2–4 μm and the diameter of about 1 μm, and ZnO with turriform morphology has radical branch structure with the diameter ranging from 500 to 700 nm. It is found that initial alkaline concentration of the solution plays a crucial role in determining two kinds of hierarchical morphologies by etching ZnO crystal during hydrothermal process. A possible formation mechanism of castellated and turriform ZnO microstructures is also proposed. Gas sensing of hierarchical ZnO to different gases was also examined. The result indicates turriform ZnO sensor has fast response properties and excellent selective resolution capability to C₂H₅OH gas.     

Preparation of helical TiO2/CMC microtubes and pure helical TiO2 microtubes

Helical TiO₂/CMC (carbon microcoils) microtubes and helical TiO₂ microtubes were obtained by making TiO₂ layer coatings on the surface of CMC templates using a sol-gel and chemical vapor deposition (CVD) processes. The preparation conditions, morphologies and some properties were examined. Uniform TiO₂ (anatase) layers were obtained on the CMC templates by a CVD process using vapor phase hydrolysis of titanium tetra-isopropoxide at 300°C followed by heat treatment in N₂ or by calcination in air at 500–;650°C. The helical TiO₂/CMC microtubes showed good photocatalytic activity. It was considered that the helical structure activated and enhanced the photocatalytic activity of TiO₂, probably caused by the generation of inductive microelectric current induced by the irradiation of UV light, resulting in the generation of micromagnetic fields around the tubes.     

Synthesis and optical properties of MgO-doped ZnO microtubes using microwave heating

The Zn_1−xMg_xO (x = 0%, 2% and 5%) microtubes have been successfully synthesized via a microwave heating method. The as synthesized microtubes were carefully investigated. Field emission scanning electron microscope (FE-SEM) showed that all the microtubes exhibit an exact hexagonal hollow structure with smooth surfaces and straight characteristics throughout their whole lengths. UV–Vis measurement indicates that the absorption peak for ZnO microtube was shifted from 378.88 nm (3.27 eV) to 369.91 nm (3.35 eV) for Zn_0.95Mg_0.05O microtube. Room temperature photoluminescence (PL) spectra showed that the intensity of UV emission peak decreased with increase of MgO concentration and the visible emission band showed a blue shift from 538.06812 nm for ZnO microtube to 529.54114 nm for Zn_0.95Mg_0.05O microtube. Energy-dispersive spectrometer (EDS) analysis revealed the presence of Zn and O as the only elementary components with the absence of MgO as a doping material.     

GaN/ZnO复合体的制备及光催化性能

首先用聚乙烯吡咯烷酮(PVP)作为表面活性剂, 硝酸镓[Ga(NO₃)₃]作为镓源, 采用溶胶-凝胶法制备了GaN粉末。然后通过固相法将GaN粉末和ZnO粉末按不同配比机械混合, 制备成GaN/ZnO复合体。采用X射线粉末衍射(XRD)、扫描电镜(SEM)、X射线能谱 (EDS)、高分辨透射电子显微镜(HRTEM)和发致光谱(PL)表征GaN/ZnO复合体的微结构、形貌、成分和发光特性, 并将其作为催化剂进行降解亚甲基蓝水溶液的光催化性能测试。结果表明: GaN/ZnO复合体对比未经复合的GaN和ZnO粉末, 光催化性能有明显的增强。基于一级动力学方程分析, 当GaN/ZnO复合体中GaN粉末和ZnO粉末含量配比为1: 2时, 光催化性能达到最佳, 其速率常数k值为0.11 min^-1。     

Effect of ZnO on the microstructure and electrical properties of (K<Subscript>0.5</Subscript>Na<Subscript>0.5</Subscript>)NbO<Subscript>3</Subscript> lead-free piezoelectric ceramics

K_0.5Na_0.5NbO₃–x ZnO (KNN–xZn) lead-free ceramics have been prepared using the conventional sintering technique and the effects of ZnO addition on the phase structure and piezoelectric properties of the ceramics have been studied. Our results reveal that a small amount of ZnO can improve the density of the ceramics effectively. Because of the high density and ZnO doping effects, the piezoelectric and dielectric properties of the ceramics are improved considerably. The good piezoelectric and dielectric properties of d ₃₃ = 114 pC/N, k _p = 0.36, ε _r = 395, and Q _m = 68 were obtained for the KNN ceramics doped with 1 mol% ZnO. Therefore, the KNN-1.0 mol%Zn ceramics is a good candidate for lead-free piezoelectric application.     

Microstructure,mechanical properties and shape memory effect of Cu–Hf–Al–Ni alloys

The influence of hafnium element’s incorporation on a Cu–xHf–13.0Al–4.0Ni (wt-%) (x?=?0.5, 1.0 and 2.0) high-temperature shape memory alloy was investigated systematically. The results show that the matrix of Cu–xHf–13.0Al–4.0Ni (x?=?0.5, 1.0 and 2.0) alloys is 18R martensite, and an orthorhombic-structured Cu₈Hf₃ phase is formed and distributed at the grain boundaries. The grain size is significantly reduced with increasing Hf content. The mechanical properties of Cu–xHf–13.0Al–4.0Ni (x?=?0.5, 1.0 and 2.0) alloys are improved by Hf doping due to the combination of refinement strengthening, solid solution strengthening and second phase strengthening. After heating under pre-strain of 10%, the shape memory effect of the Cu–1.0Hf–13.0Al–4.0Ni alloy reaches 5.6%, which is obviously higher than that of the Cu–13.0Al–4.0Ni alloy.     

Sol–gel assisted hydrothermal synthesis of ZnO microstructures: Morphology control and photocatalytic activity

ZnO microstructures of different morphologies were synthesized by the sol–gel assisted hydrothermal method using Zn(NO₃)₂, citric acid and NaOH as raw materials. Twining-hexagonal prism, twining-hexagonal disk, sphere and flower-like ZnO microstructures could be synthesized only through controlling the pH of the hydrothermal reaction mixture at 11, 12, 13 and 14, respectively. The as-synthesized samples were characterized by X-ray diffraction (XRD), scanning electron microscope (SEM). Optical properties were examined by UV–Vis absorption/diffuse reflectance spectroscopy and room-temperature photoluminescence measurements (PL). Photocatalytic activities of the samples were evaluated by degradation of Reactive Blue 14 (KGL). The results indicated that the flower-like ZnO composed of nanosheets possessed superior photocatalytic activity to other ZnO microstructures and commercial ZnO, which could be attributed to the morphology, surface defects, band gap and surface area. The formation mechanisms of different ZnO morphologies were also investigated based on the experimental results.     

Effect of two-step sintering on rare earth (RE = Y2O3, Pr6O11) doped ZnO–Bi2O3 varistors processed from ‘nano-precursor’ powders

Nano size ZnO–Bi₂O₃ varistor precursor powders containing Y₂O₃ and Pr₆O₁₁ rare earth dopants were prepared by low temperature refluxing at 80 °C. Effect of rare earth dopants, densification by two-step sintering, evolution of microstructures and their influence on varistor properties were investigated. Chemically synthesized nano- precursor varistor powders produced controlled grain size in two-step sintering in which the average sintered ZnO grain size was reduced to at least half compared to the conventionally processed ZnO–Bi₂O₃ varistors. The study revealed that such grain size reduction is highly beneficial to attain enhanced varistor properties.     

Formation of transition-metal sulfide microspheres or microtubes

Cu_xS (x = 1, 2) microtubes, and a series of transition-metal sulfide (CdS, ZnS, NiS, CoS, CuS and Cu₂S) compounds microspheres were successfully synthesized through a facile hydrothermal reaction. These compounds have been characterized by X-ray powder diffraction (XRD), transmission electron microscopy (TEM) and scanning electron microscopy (SEM). The optical properties of ZnS and CdS have also been investigated by UV–vis absorption and fluorescence spectroscopy. The possible formation mechanism of these microspheres or microtubes was discussed based on the experimental results.     

The processing of optically active functional hierarchical nanoparticles

Global climate changes and the aroused environmentally-energy problems categorically moved the research efforts towards programmed processing of a novel class of hierarchical materials having well defined phase, compositional and morphological features. The synthesis based on the principles of the molecular design and integrative chemistry which includes the innovative aerosol and hydro(solvo)thermal nanotechnology routes, the building block assembling and hybridization, represent intelligent platform for the creation of advanced functional materials. Due to exceptional optical properties and a diverse application in electronics, optoelectronics, energy conversion/storage and biomedicine, the examples from some wide band gap oxides for light harvesting and photocatalytic applications as well as both down and up-conversion energy-saving luminescent materials for photonic and biological applications are considered. With the help of various analyzing techniques like XRPD (X-ray powder diffraction), field emission scanning electron microscopy (FE-SEM), energy dispersive spectroscopy (EDS), analytical and high resolution transmission electron microscopy (TEM, HR-TEM), selected area electron diffraction (SAED), scanning tunneling electron microscopy (STEM), Fourier transform infrared (FTIR) and Raman spectroscopy, photocatalytic and fluorescence measurements, the opportunities of the aerosol and hydro(solvo)thermal routes for the synthesis of novel hierarchically and hybrid assembled structures and nanocomposites are reviewed highlighting the recent research activities realized in the Institute of Technical Sciences of SASA, Belgrade, Serbia and University Carlos III, Madrid, Spain. The morphological, structural and functional aspects of the following systems: ZnO, TiO₂, Y₂O₃:Eu,Yb/Er/T/Hm, Y₂O₃:Eu@Ag, (Y_1?xGd_x)₂O₃:Eu, (NaYF4:Yb/Er)@EDTA/PEG/PVP, are discussed from the state-of-the art and literature contexts. Controlled growth of 1D and 3D hierarchical structures based on the single-source processing methodology in combination with the homogeneous precipitation of optically active intermediate precursor are especially stressed for the case of yttria based phosphor particles and phase-dependent luminescence efficiency. The obtained results offer possible routes for the synthesis of hierarchically structured nanomaterials with tunable structure, morphology and optical properties.     

Solvothermal synthesis of nanocrystalline ZnO with excellent photocatalytic performance

We reported a facile way to synthesize nanocrystalline ZnO particles with excellent photocatalytic performance. Their microstructures and optical properties were characterized by X-ray diffraction, field emission scanning electron, transmission electron microscopy, photoluminescence spectra and ultraviolet–visible (UV–Vis) spectra. Photocatalytic tests showed the as-prepared ZnO particles had a good activity for photodegradation of organic dyes under UV–Vis light irradiation, which was comparable with that of P25 TiO₂, a commercial standard photocatalyst. Furthermore, the sample could be easily sedimentary from the reaction system, which was favorable for the separation and reuse. Meanwhile, the photocatalytic performance of the samples exhibited no obvious reduction in the activity after five recycles of photodegradation, demonstrating its superior reusability. We attributed the superior performance to the efficient synergistic effect resulted from the small nano size, as well as the appropriate oxygen vacancies in the ZnO lattice. Our work might be promising for the application of ZnO-based photocatalysts due to its low cost, easy process, and good performance.