Synthesis of gallium oxide nanomaterials on source material supply and their growth behavior

High purity and single crystalline beta-Ga2O3 nanomaterials with various morphologies were obtained through the simple thermal evaporation of metal gallium powder on a gold-coated silicon substrate in argon. In this report, the growth behavior of the beta-Ga2O3 nanomaterials as a function of synthesis time and source material supply was delicately surveyed via FESEM and HRTEM. The synthesis time and source material supply affected morphology, growth rate and growth mechanism of the grown nanomaterials. It was confirmed that the growth mechanism of the beta-Ga2O3 nanomaterials was varied in the order of VLS, combination of VLS and VS, and VS, by increasing the synthesis time without regard to the supply of the source material. When the source materials supply was increased, many beta-Ga2O3 nanomaterials with various morphologies, such as sheet, triangle, and belt-like were appeared. It was confirmed that the oxidation reaction of gallium and oxygen for the formation of gallium oxide nanomaterials carried out the precipitation of gallium at the same time due to the supersaturation of the gallium atoms in gold catalyst. The growth and formation mechanism of the beta-Ga2O3 nanomaterials are discussed herein.     

Synthesis, Growth Mechanism, and Applications of Zinc Oxide Nanomaterials

This article reviews recent progresses in growth mechanism, synthesis, and applications of zinc oxide nano-materials （mainly focusing on one-dimensional （1D） nanomaterials）. In the first part of this article, we briefly introduce the importance, the synthesis methods and growth mechanisms, the properties and applications of ZnO 1D nanomaterials. In the second part of this article, the growth mechanisms of ZnO 1D nanomaterials will be discussed in detail in the framework of vapor-liquid-solid （VLS）, vapor-solid （VS）, and aqueous solution growth （ASG） approaches. Both qualitative and quantitative information will be provided to show how a controlled synthesis of ZnO 1D nanomaterials can be achieved. In the third part of this article, we present recent progresses in our group for the synthesis of ZnO 1D nanomaterials, and the results from other groups will only be mentioned briefly. Especially, experiment designing according to theories will be elaborated to demonstrate the concept of controlled synthesis. In the fourth part of this article, the properties and potential applications of ZnO 1D nanomaterials will be treated. Finally, a summary part will be presented in the fifth section. The future trend of research for ZnO 1D nanomaterials will be pointed out and key issues to be solved will be proposed.     

Controlled growth and characterization methods of semiconductor nanomaterials

One-dimensional (1D) semiconductor nanomaterials attract much attention because they are ideal systems for investigation and studying the relationship between properties and structures and having extensive application future in the high technical field. They are expected to play an important role in fabrication of the next generation nanocircuits, nanotools, nanowires lasers, photon tunneling devices, near-field photo-waveguide devices, etc. This article described controlled growth, characterization of structures and morphologies and properties of 1D semiconductor nanomaterials based on our previous works. This article is organized into two parts: The first part is complicated nanostructures of semiconductors, which includes coaxial nanocables, heterostructure nanowires and nanowires with metal-semiconductor junction behavior, hierarchical structures, doping of the nanowires and nanobelts, porous materials and periodically twined nanowires and asymmetrical polytypic nanobelts. The second part contains semiconductor nanoarrays based on anodic alumina membrane (AAM) templates. Finally, we propose that further investigation of the influence of nanomaterial morphologies on properties and how to design the morphology of nanostructures to meet the property requirements of nanodevices are our future research directions in this field.     

Fabrication of ZnO Nanoneedle/nanocolumn Composite Films and Annealing Induced Improvement in Their Microstructural and Photoluminescence Characteristics

ZnO nanoneedle/nanocolumn （NN/NC） composite films were grown via reactive electron beam evaporation （REBE） in the NH3/H2 gaseous mixture by using polycrystalline ZnO ceramic targets as source materials. The growth was performed at low substrate temperatures （450～500℃） without employing any metallic catalysts. As-prepared samples were then rapidly annealed in 02 ambient at a higher temperature （600℃）. Electron microscopic observations revealed the typical composite-structured morphologies of NN/NC/substrate of ZnO nanomaterials grown at 500℃. Such unique morphologies should render potential applications, for instance, as an efficient microwave absorption material utilized in the fabrication of concealed aerostat. In addition, X-ray diffraction and photoluminescence measurements showed remarkable improvement in crystal and optical qualities of ZnO NN/NC composite films after annealing.     

Synthesis of nanorods and nanowires using biomolecules under conventional- and microwave-hydrothermal conditions

In this paper, we review our work on the synthesis and characterization of one-dimensional (1D) nanorods/nanowires and assemblies of inorganic materials with the assistance of several biomolecules under conventional- or microwave-hydrothermal conditions. Two classes of biomolecules have been investigated. One is sugars and their derivatives, and the other is amino acids and their polymers, peptide, and protein. With the assistance of sugars or their derivatives, different kinds of 1D elemental tellurium (Te) and selenium (Se) nanostructures with different sizes and morphologies have been obtained. With the assistance of amino acids or their polymers, 1D semiconductor sulfides and oxide nanowires and assemblies have been successfully synthesized. By providing confined spaces or serving as functional templates for site-specific nanomaterials nucleation or binding, biomolecules appear to direct the growth and/or the assembly of the nanomaterials.     

Morphology Tunable Hybrid Carbon Nanosheets with Solvatochromism

The tunable photoluminescence of carbon‐based nanomaterials has received much attention for a wide range of applications. Herein, a unique, broad‐solvatochromic hybrid carbon nanosheet (CNS) synthesized through the hydrothermal carbonization of molecular precursors exploiting graphene oxide as a template is reported, resulting in the formation of clusters of carbon nanorings on the surface of graphene‐oxide nanosheets. Under UV and visible‐light excitation, the hybrid CNS exhibits tunable emission spanning the wide range of colors in a series of solvents with different polarities. This interesting spectroscopic behavior is found to originate from hydrogen‐bonding interactions between CNS and solvents, which eventually induce the morphological transition of CNS from 2D sheets to 3D crumpled morphologies, affecting the lifetimes of emissive states. This novel soft carbon nanostructure may open up a new possibility in tailoring the photophysical properties of carbon nanomaterials.     

SnO2‐Based Nanomaterials: Synthesis and Application in Lithium‐Ion Batteries

The development of new electrode materials for lithium‐ion batteries (LIBs) has always been a focal area of materials science, as the current technology may not be able to meet the high energy demands for electronic devices with better performance. Among all the metal oxides, tin dioxide (SnO₂) is regarded as a promising candidate to serve as the anode material for LIBs due to its high theoretical capacity. Here, a thorough survey is provided of the synthesis of SnO₂‐based nanomaterials with various structures and chemical compositions, and their application as negative electrodes for LIBs. It covers SnO₂ with different morphologies ranging from 1D nanorods/nanowires/nanotubes, to 2D nanosheets, to 3D hollow nanostructures. Nanocomposites consisting of SnO₂ and different carbonaceous supports, e.g., amorphous carbon, carbon nanotubes, graphene, are also investigated. The use of Sn‐based nanomaterials as the anode material for LIBs will be briefly discussed as well. The aim of this review is to provide an in‐depth and rational understanding such that the electrochemical properties of SnO₂‐based anodes can be effectively enhanced by making proper nanostructures with optimized chemical composition. By focusing on SnO₂, the hope is that such concepts and strategies can be extended to other potential metal oxides, such as titanium dioxide or iron oxides, thus shedding some light on the future development of high‐performance metal‐oxide based negative electrodes for LIBs.     

Self-assembled materials for catalysis

The purpose of this review is to highlight developments in self-assembled nanostructured materials (i.e., mesoporous and nanoparticle-based materials) and their catalytic applications. Since there are many available reviews of metal-based nanoparticles as catalysts, this review will mainly focus on self-assembled oxide-based catalytic materials. The content includes: (1) design and synthetic strategies for self-assembled mesoporous catalysts, (2) polyoxometalate (POM)-based nanocatalysts, (3) dendrimer-based nanocatalysts, and (4) shaped nanomaterials and catalytic applications. We show that controlled assembly of molecules, crystalline seeds, and nano building blocks into organized mesoscopic structures or controlled morphologies is an effective approach for tailoring porosities of heterogeneous catalysts and controlling their catalytic activities. This article is published with open access at Springerlink.com     

Fractal‐Theory‐Based Control of the Shape and Quality of CVD‐Grown 2D Materials

The precise control of the shape and quality of 2D materials during chemical vapor deposition (CVD) processes remains a challenging task, due to a lack of understanding of their underlying growth mechanisms. The existence of a fractal‐growth‐based mechanism in the CVD synthesis of several 2D materials is revealed, to which a modified traditional fractal theory is applied in order to build a 2D diffusion‐limited aggregation (2D‐DLA) model based on an atomic‐scale growth mechanism. The strength of this model is validated by the perfect correlation between theoretically simulated data, predicted by 2D‐DLA, and experimental results obtained from the CVD synthesis of graphene, hexagonal boron nitride, and transition metal dichalcogenides. By applying the 2D‐DLA model, it is also discovered that the single‐domain net growth rate (SD‐NGR) plays a crucial factor in governing the shape and quality of 2D‐material crystals. By carefully tuning SD‐NGR, various fractal‐morphology high‐quality single‐crystal 2D materials are synthesized, achieving, for the first time, the precise control of 2D‐material CVD growth. This work lays the theoretical foundation for the precise adjustment of the morphologies and physical properties of 2D materials, which is essential to the use of fractal‐shaped nanomaterials for the fabrication of new‐generation neural‐network nanodevices.     

1D Ceria Nanomaterials:Versatile Synthesis and Bio-application

Ceria has emerged as a fascinating and lucrative material in bio-application,for instance,disease treatment,bioimaging and drug delivery due to its abilities of transforming oxidation states between Ce~(4+) and Ce~(3+) and scavenging free radicals,which can produce biological effect,such as being potentially antioxidant towards reactive oxygen species.Recently,many studies about one dimension(ID) CeO_2nanomaterials have received much attention because of the unique properties of their length and aspect ratio.We highlight here current research activities focused on the bio-application of 1D ceria nanomaterials.The synthesis methods of 1D cerium oxide nanomaterials were introduced.Several synthesis routes,including template,hydrothermal,sonochemical and other methods,were then discussed with examples developed by recent research.The differences among these methods were also analyzed.This review provides a comprehensive introduction to the synthesis of 1D ceria,its potential applications in biological fields and perspectives on this exciting realm.     

氧化物/氧化物自生复合陶瓷的生长机理与微观结构的研究进展

基于国外定向凝固氧化物／氧化物自生复合陶瓷的晶体生长动力学行为研究,阐述了其动力学机制,分析动力学因素对微观结构的影响,探讨了晶体生长动力学行为与微观结构之间的关系;同时结合以重力、超重力下燃烧合成、快速凝固技术所制备的新型高强韧Al2O3／YSZ自生复合陶瓷,探讨了自生复合陶瓷在快速凝固条件下的晶体生长动力学行为。结合定向凝固与快速凝固两种晶体生长机制,得出过冷度、凝固界面前沿的温度梯度是影响晶体生长方式的重要因素,且受二者控制的晶体生长速率则决定材料的微观结构与形态。     

Interface-modulated approach toward multilevel metal oxide nanotubes for lithium-ion batteries and oxygen reduction reaction

Metal oxide hollow structures with multilevel interiors are of great interest for potential applications such as catalysis,chemical sensing,drug delivery,and energy storage.However,the controlled synthesis of multilevel nanotubes remains a great challenge.Here we develop a facile interface-modulated approach toward the synthesis of complex metal oxide multilevel nanotubes with tunable interior structures through electrospinning followed by controlled heat treatment.This versatile strategy can be effectively applied to fabricate wire-in-tube and tubein-tube nanotubes of various metal oxides.These multilevel nanotubes possess a large specific surface area,fast mass transport,good strain accommodation,and high packing density,which are advantageous for lithium-ion batteries (LIBs)and the oxygen reduction reaction (ORR).Specifically,shrinkable CoMn2O4 tube-in-tube nanotubes as a lithium-ion battery anode deliver a high discharge capacity of ～565 mAh.g-1 at a high rate of 2 A.g-1,maintaining 89％ of the latter after 500 cycles.Further,as an oxygen reduction reaction catalyst,these nanotubes also exhibit excellent stability with about 92％ current retention after 30,000 s,which is higher than that of commercial Pt/C (81％).Therefore,this feasible method may push the rapid development of one-dimensional (1D) nanomaterials.These multifunctional nanotubes have great potential in many frontier fields.     

Shape‐Enhanced Photocatalytic Activities of Thoroughly Mesoporous ZnO Nanofibers

1D mesoporous materials have attracted extensive interest recently, owning to their fascinating properties and versatile applications. However, it remains as a grand challenge to develop a simple and efficient technique to produce oxide nanofibers with mesoporous architectures, controlled morphologies, large surface areas, and optimal performances. In this work, a facile foaming‐assisted electrospinning strategy with foaming agent of tea saponin is used to produce thoroughly mesoporous ZnO nanofibers with high purity and controlled morphology. Interestingly, mesoporous fibers with elliptical cross‐section exhibit the significantly enhanced photocatalytic activity for hydrogen production, as compared to the counterparts with circular and rectangular cross‐sections, and they also perform better than the commercial ZnO nanopowders. The unexpected shape dependence of photocatalytic activities is attributed to the different stacking modes of the mesoporous fibers, and a geometrical model is developed to account for the shape dependence. This work represents an important step toward producing thoroughly mesoporous ZnO nanofibers with tailored morphologies, and the discovery that fibers with elliptical cross‐section render the best performance provides a valuable guideline for improving the photocatalytic performance of such mesoporous nanomaterials.     

Evolution of Zinc Oxide Nanostructures through Kinetics Control

In-depth understanding of the kinetics of the vapor deposition process is substantial for advancing this capable bottom-up nanostructure synthesis approach into a versatile large-scale nanomanufacturing technology. In this paper, we report a systematic study of the vapor deposition kinetics of ZnO nanomaterials under controlled atmosphere and properly refined deposition conditions. The experiments clearly evidenced the self-catalyzed growth of ZnO NWs via the formation of ZnO nanoflowers. This result illustrated how ZnO morphologies were associated with the discrepancy between oxidation rate and condensation rate of Zn. The capability of switching the NW morphologies and possibly mechanisms was demonstrated by kinetically controlling the deposition system. The high Zn composition during the deposition resulted in strongly luminescent NWs, which can be used for optical imaging applications. This research discovered a fundamental kinetics that governs the mechanisms and morphology selection of nanostructures in a non-catalyst growth system.     

不同形貌α-Fe2O3的水热法制备及性能研究

以Fe(NO_3)_3·9H_2O为原料,聚乙烯吡咯烷酮作为表面活性剂,NaOH、Na_2CO_3、CH_3COONa为形貌改变剂,采用水热法制备出不同形貌的α-Fe_2O_3,并研究了不同因素对产物形貌的影响。利用SEM、EDS、XRD、FTIR等手段对其物相及微观形貌进行表征,并探讨其生长机理。通过光催化降解酸性大红模拟废水考察不同形貌α-Fe_2O_3的光催化性能,实验结果表明,类桑葚状α-Fe_2O_3对酸性大红模拟废水的降解效果最好,降解率高达99.01%,具有潜在的光催化应用前景。     

2D Zinc Oxide – Synthesis,Methodologies, Reaction Mechanism,and Applications

Zinc oxide (ZnO) is a thermally stable n-type semiconducting material. ZnO 2D nanosheets have mainly gained substantial attention due to their unique properties, such as direct bandgap and strong excitonic binding energy at room temperature. These are widely utilized in piezotronics, energy storage, photodetectors, light-emitting diodes, solar cells, gas sensors, and photocatalysis. Notably, the chemical properties and performances of ZnO nanosheets largely depend on the nano-structuring that can be regulated and controlled through modulating synthetic strategies. Two synthetic approaches, top–down and bottom–up, are mainly employed for preparing ZnO 2D nanomaterials. However, owing to better results in producing defect-free nanostructures, homogenous chemical composition, etc., the bottom–up approach is extensively used compared to the top–down method for preparing ZnO 2D nanosheets. This review presents a comprehensive study on designing and developing 2D ZnO nanomaterials, followed by accenting its potential applications. To begin with, various synthetic strategies and attributes of ZnO 2D nanosheets are discussed, followed by focusing on methodologies and reaction mechanisms. Then, their deliberation toward batteries, supercapacitors, electronics/optoelectronics, photocatalysis, sensing, and piezoelectronic platforms are further discussed. Finally, the challenges and future opportunities are featured based on its current development.     

Screw dislocation-driven growth of two-dimensional nanoplates

We report the dislocation-driven growth of two-dimensional (2D) nanoplates. They are another type of dislocation-driven nanostructure and could find application in energy storage, catalysis, and nanoelectronics. We first focus on nanoplates of zinc hydroxy sulfate (3Zn(OH)(2)·ZnSO(4)·0.5H(2)O) synthesized from aqueous solutions. Both powder X-ray and electron diffraction confirm the zinc hydroxy sulfate (ZHS) crystal structure as well as their conversion to zinc oxide (ZnO). Scanning electron, atomic force, and transmission electron microscopy reveal the presence of screw dislocations in the ZHS nanoplates. We further demonstrate the generality of this mechanism through the growth of 2D nanoplates of α-Co(OH)(2), Ni(OH)(2), and gold that can also follow the dislocation-driven growth mechanism. Finally, we propose a unified scheme general to any crystalline material that explains the growth of nanoplates as well as different dislocation-driven nanomaterial morphologies previously observed through consideration of the relative crystal growth step velocities at the dislocation core versus the outer edges of the growth spiral under various supersaturations.     

Parallel Aluminum-Cobalt Oxide Nanosheet Arrays with High-Temperature Ferromagnetism

Parallel nanomaterials possess unique properties and show potential applications in industry. Whereas, vertically aligned 2D nanomaterials have plane orientations that are generally chaotic. Simultaneous control of their growth direction and spatial orientation for parallel nanosheets remains a big challenge. Here, a facile preparation of vertically aligned parallel nanosheet arrays of aluminum-cobalt oxide is reported via a collaborative dealloying and hydrothermal method. The parallel growth of nanosheets is attributed to the lattice-matching among the nanosheets, the buffer layer, and the substrate, which is verified by a careful transmission electron microscopy study. Furthermore, the aluminum-cobalt oxide nanosheets exhibit high-temperature ferromagnetism with a 919 K Curie temperature and a 5.22 emu g⁻¹ saturation magnetization at 300 K, implying the potential applications in high-temperature ferromagnetic fields.     

Phase growth patterns for Al_2O_3/GdAlO_3 eutectics over wide ranges of compositions and solidification rates

Phase selection and growth characteristics of directionally solidified Al₂O₃/GdAlO_3(GAP)faceted eutectic ce ramics are investigated over wide ranges of compositions and solidification rates to explore the eutectic coupled zone.Through the obse rvation of the quenched solid-liquid interface,the competitive growth of primary faceted Al₂O₃phase,prima ry non-faceted GAP phase and Al₂O₃/GAP eutectic with diffe rent morphologies is detected.Microstructure transitions from wholly eutectic to primary Al₂O₃(GAP)dendrite plus eutectic and then to wholly eutectic are found in Al₂O₃-2 O mol%Gd₂O₃hypoeutectic(Al₂O₃-26 mol%Gd₂O₃hypereutectic)ceramics with the increase of solidification rate.The dendrite growth of faceted Al₂O₃and non-faceted GAP phases are well predicted by KGT model,which have introduced appro p riate dimensionless supersaturationΩto characterize the anisotropic growth of dendrites.Based on the maximum interface temperature criterion,the competitive growth of primary phase and eutectic is analyzed theoretically and the predicted coupled zone of Al₂O₃/GAP eutectic ceramics is in good agreement with the experimental results.Besides,the influence of microstructure with these different morphologies on the flexural strength of Al₂O₃/GAP eutectic ceramics is studied.     

Multivalent Interactions between 2D Nanomaterials and Biointerfaces

2D nanomaterials, particularly graphene, offer many fascinating physicochemical properties that have generated exciting visions of future biological applications. In order to capitalize on the potential of 2D nanomaterials in this field, a full understanding of their interactions with biointerfaces is crucial. The uptake pathways, toxicity, long‐term fate of 2D nanomaterials in biological systems, and their interactions with the living systems are fundamental questions that must be understood. Here, the latest progress is summarized, with a focus on pathogen, mammalian cell, and tissue interactions. The cellular uptake pathways of graphene derivatives will be discussed, along with health risks, and interactions with membranes—including bacteria and viruses—and the role of chemical structure and modifications. Other novel 2D nanomaterials with potential biomedical applications, such as transition‐metal dichalcogenides, transition‐metal oxide, and black phosphorus will be discussed at the end of this review.