Mass-Based Environmental Factor and Energy Assessment of Microwave-Assisted Synthesized Transition Metal Nanostructures

This paper describes mass-based energy phase-space projection of microwave-assisted synthesis of transition metals (zinc oxide, palladium, silver, platinum, and gold) nanostructures. The projection uses process energy budget (measured in kJ) on the horizontal axes and process density (measured in kJg−1) on the vertical axes. These two axes allow both mass usage efficiency (Environmental-Factor) and energy efficiency to be evaluated for a range of microwave applicator and metal synthesis. The metrics are allied to the: second, sixth and eleventh principle of the twelve principle of Green Chemistry. This analytical approach to microwave synthesis (widely considered as a useful Green Chemistry energy source) allows a quantified dynamic environmental quotient to be given to renewable plant-based biomass associated with the reduction of the metal precursors. Thus allowing a degree of quantification of claimed “eco-friendly” and “sustainable” synthesis with regard to waste production and energy usage.

Green Chemistry Allometry Test of Microwave-Assisted Synthesis of Transition Metal Nanostructures

Microwave irradiation is considered an important approach to Green Chemistry, because of its ability to rapidly increase the internal temperature of polar-organic compounds that lead to synthesis times of minutes rather than hours when compared to conventional thermal heating. This works describes a dual allometry test for the discrimination between the solvents and reagents used in the microwave-assisted synthesis of transition metal (zinc oxide, palladium silver, platinum, and gold) nanostructures. The test is performed in log-log process energy phase-space projection, where the synthesis data (kJ against kJ·mol-1) has a power-law signature. The test is shown to discriminate between recommended Green Chemistry, problematic Green Chemistry, and Green Chemistry hazardous solvents. Typically, recommended Green chemistry exhibits a broad y-axes distribution within an upper exponent = 1 and lower exponent = 0.5. Problematic Green Chemistry exhibits a y-axes narrower distribution with an upper exponent = 0.94 and lower exponent = 0.64. Non-Green Chemistry hazardous data exhibits a further narrowing of the y-axes distribution within upper exponent = 0.87 and lower exponent = 0.66. In all three cases, the y-axes is aligned to original database power-law signature. It is also shown that in the x-axes direction (process energy budget) the grouped order of magnitude decreases from four orders for recommended Green Chemistry solvent and reagent data, through two orders for non-Green Chemistry hazardous material and down to one order for problematic Green Chemistry.

Anodized metal oxide nanostructures for photoelectrochemical water splitting

Photoelectrochemical(PEC) water splitting offers the capability of harvesting, storing, and converting solar energy into clean and sustainable hydrogen energy. Metal oxides are appealing photoelectrode materials because of their easy manufacturing and relatively high stability. In particular, metal oxides prepared by electrochemical anodization are typical of ordered nanostructures, which are beneficial for light harvesting, charge transfer and transport, and the adsorption and desorption of reactive species due to their high specific surface area and rich channels. However, bare anodic oxides still suffer from low charge separation and sunlight absorption efficiencies. Accordingly, many strategies of modifying anodic oxides have been explored and investigated. In this review, we attempt to summarize the recent advances in the rational design and modifications of these oxides from processes before, during, and after anodization. Rational design strategies are thoroughly addressed for each part with an aim to boost overall PEC performance. The ongoing efforts and challenges for future development of practical PEC electrodes are also presented.

Metal Oxide Nanostructures from Simple Metal-oxygen Reaction in Air

Metal oxide nanostructures （CuO, Co3O4, ZnO and α-Fe2O3） have been successfully fabricated by a simple and efficient method： heating the appropriate metals in air at low temperatures ranging from 200 to 400℃. The chemical composition, morphology and crystallinity of the nanostructures have been characterized by micro-Raman spectroscopy, X-ray diffraction, scanning electron microscopy and transmission electron microscopy. Two mechanisms： vapor-solid and surface diffusion play dominant roles in the growth of metal oxide nanostructures starting with low melting point metals （Zn and Cu） and high melting point metals （Fe and Co）, respectively. With sharp ends and large aspect ratio, the metal oxide nanostructures exhibit impressive field-induced electron emission properties, indicating their potentials as future electron source and displays. The water wettability and anti-wettability properties of iron oxide nanoflakes were also discussed in this work.

Splitting the surface wave in metal/dielectric nanostructures

We investigate a modified surface wave splitter with a double-layer structure, which consists of symmetrical metallic grating and an asymmetrical dielectric, using the finite-difference time-domain （FDTD） simulation method. The metal/dielectric interface structure at this two-side aperture can support bound waves of different wavelengths, thus guiding waves in opposite directions. The covered dielectric films play an important role in the enhancement and confinement of the diffraction wave by the waveguide modes. The simulation result shows that the optical intensities of the guided surface wave at wavelengths of 760-nm and 1000-nm are about 100 times and 4-5 times those of the weaker side, respectively, which means that the surface wave is split by the proposed device.

Intrinsic luminescence from metal nanostructures and its applications

Intrinsic luminescence from metal nanostructures complements conventional scattering and absorption behaviors and has many interesting and unique features. This phenomenon has attracted considerable research attention in recent years because of its various potential applications. In this review, we discuss recent advances in this field, summarize potential applications for this type of luminescence, and compare theoretical models to describe the phenomena. On the basis of the excitation process, the characteristic features and corresponding applications are summarized briefly in three parts, namely, continuous-wave light, pulsed laser, and electron excitation. A universal physical mechanism likely operates in all these emission processes regardless of differences in the excitation processes; however, there remains some debate surrounding the details of the theoretical model. Further insight into these luminescence phenomena will not only provide a deeper fundamental understanding of plasmonic nanostructures but will also advance and extend their applications.

A Review on Metal Nanostructures: Preparation Methods and Their Potential Applications

Metal nanostructures have been of great research interest in recent years due to their physicochemical, plasmonic properties and potential applications. A lot of work has been done on the controlled synthesis of metal nanostructures for various applications. In this review, we try to focus on recent developments in synthesis and applications of metal nanostructures. Firstly, we summarized different preparation methods and then briefly explained their potential applications.

Synthesis and applications of MOF-derived porous nanostructures

Metal organic frameworks(MOFs) represent a class of porous material which is formed by strong bonds between metal ions and organic linkers. By careful selection of constituents, MOFs can exhibit very high surface area, large pore volume, and excellent chemical stability.Research on synthesis, structures and properties of various MOFs has shown that they are promising materials for many applications, such as energy storage, gas storage, heterogeneous catalysis and sensing. Apart from direct use, MOFs have also been used as support substrates for nanomaterials or as sacrificial templates/precursors for preparation of various functional nanostructures. In this review, we aim to present the most recent development of MOFs as precursors for the preparation of various nanostructures and their potential applications in energy-related devices and processes. Specifically, this present survey intends to push the boundaries and covers the literatures from the year 2013 to early 2017,on supercapacitors, lithium ion batteries, electrocatalysts, photocatalyst, gas sensing, water treatment, solar cells, and carbon dioxide capture.Finally, an outlook in terms of future challenges and potential prospects towards industrial applications are also discussed.

Uncovering the magnetic response of open-shell graphene nanostructures on metallic surfaces at different doping levels

Open-shell graphene nanostructures(GNs)are promising candidates for future spintronics and quantum technologies.Recent progress based on on-surface synthetic approach has successfully created such GNs on metallic surfaces.Meanwhile,the doping effect of metallic surfaces is inevitably present and can significantly tune their electronic and magnetic properties.Here,we investigate the zigzag end states of open-shell 7-armchair graphene nanoribbons(7-AGNRs)on Au(111),Au(100)and Ag(111)surfaces.Combined with the manipulation of a scanning tunneling microscope,we demonstrate that the end states can be tuned from empty states to singly occupied states and to doubly occupied states by substrate doping.Furthermore,the singly occupied states can be finely tuned,with the occupancy number of the states and related magnetic behaviors uncovered by experiments at different temperatures and magnetic fields.Our results provide a comprehensive study of the magnetic response of open-shell GNs on metallic surfaces at different doping levels.

Nanostructured Ternary Metal Tungstate-Based Photocatalysts for Environmental Purification and Solar Water Splitting:A Review

Visible-light-responsive ternary metal tungstate(MWO_4) photocatalysts are being increasingly investigated for energy conversion and environmental purification applications owing to their striking features, including low cost,eco-friendliness, and high stability under acidic and oxidative conditions. However, rapid recombination of photoinduced electron–hole pairs and a narrow light response range to the solar spectrum lead to low photocatalytic activity of MWO_4-based materials, thus significantly hampering their wide usage in practice. To enable their widespread practical usage, significant efforts have been devoted, by developing new concepts and innovative strategies. In this review, we aim to provide an integrated overview of the fundamentals and recent progress of MWO_4-based photocatalysts. Furthermore, different strategies, including morphological control, surface modification, heteroatom doping, and heterojunction fabrication, which are employed to promote the photocatalyticactivities of MWO_4-based materials, are systematically summarized and discussed. Finally, existing challenges and a future perspective are also provided to shed light on the development of highly efficient MWO_4-based photocatalysts.

Friction and Wear Behaviors of Nanostructured Metals

Nanostructured （ns） materials, i.e., polycrystalline materials with grain sizes in the nanometer regime （typically below 100 nm）, have drawn considerable attention in the past decades due to their unique properties such as high strength and hardness. Wear resistance of ns materials, one of the most important properties for engineering materials, has been extensively investigated in the past decades. Obvious differences have been identified in friction and wear behaviors Between the ns materials and their corresponding coarse-grained （cg） counterparts, consistently correlating with their unique structure characteristics and mechanical properties. On the other hand, the superior tribological properties of ns materials illustrate their potential applications under contact loads. The present overview will summarize the important progresses achieved on friction and wear behaviors of ns metallic materials, including ultrafine-grained （ufg） materials in recent years. Tribological properties and effects on friction and wear behaviors of ns materials will be discussed under different wear conditions including abrasive wear, sliding wear, and fretting wear. Their correlations with mechanical properties will be analyzed. Perspectives on development of this field will be highlighted as well.

Processing of nanostructured metallic matrix composites by a modified accumulative roll bonding method with structural and mechanical considerations

Particulate reinforced metallic matrix composites have attracted considerable attention due to their lightweight, high strength, high specific modulus, and good wear resistance. A1/B4C composite strips were produced in this work by a modified accumulative roll bonding process where the strips were rotated 90° around the normal direction between successive passes. Transmission electron microscopy and X-ray diffraction analyses reveal the development of nanostructures in the Al matrix after seven passes. It is found that the B4C reinforcement distribution in the matrix is improved by progression of the process. Additionally, the tensile yield strength and elongation of the processed materials are increased with the increase of passes.

2D and 3D orientation mapping in nanostructured metals: A review

Nanostructured metals possess various excellent properties and offer the potential for a wide range of applications.Improvements in the properties and performance of nanostructured metal components motivate a complete characterization of the microstructures and crystallographic orientations of nanostructured metals with nanoscale spatial resolution.Two well developed orientation mapping techniques for such characterization are electron backscatter diffraction(EBSD)in the scanning electron microscope and precession electron diffraction(PED)using diffraction spots in the transmission electron microscope.However,these methods can only characterize the structure in two dimensions.It is still a great challenge to characterize grains in three dimensions,i.e.from the interior of the nanostructured metals.Recently,three-dimensional orientation mapping in the transmission electron microscope(3 D-OMi TEM)was developed and further improvements of this technique are introduced in this paper.Utilization of these orientation mapping techniques for structural and orientational characterizations are demonstrated by examples of surface-deformed metals with gradient nanostructures,and a sputtered gold film of nano-islands containing nanograins.The merits and challenges of each of these techniques are discussed and suggestions for further developments are proposed.

Three-dimensional noble-metal nanostructure: A new kind of substrate for sensitive, uniform, and reproducible surface-enhanced Raman scattering

Surface-enhanced Raman spectroscopy （SERS） is a powerful vibrational spectroscopy technique for highly sensitive structural detection of low concentration analyte. The SERS activities largely depend on the topography of the substrate. In this review, we summarize the recent progress in SERS substrate, especially focusing on the three-dimensional （3D） noble-metal substrate with hierarchical nanostructure. Firstly, we introduce the background and general mechanism of 3D hierarchical SERS nanostructures. Then, a systematic overview on the fabrication, growth mechanism, and SERS property of various noble-metal substrates with 3D hierarchical nanostructures is presented. Finally, the applications of 3D hierarchical nanostructures as SERS substrates in many fields are discussed.

Partial electrical potential distribution around nanospheres in metallic nanostructured films

In light of the nanostructured surface model, where half-spherical nanoparticles grow out symmetrically from a plane metallic film, the mathematical model for the partial electrical potential around nanospheres is developed when a uniform external electric field is applied. On the basis of these models, the three-dimensional spatial distribution of the partial electrical potential is obtained and given in the form of a curved surface using a numerical computation method. Our results show that the electrical potential distribution around the nanospheres exhibits an obvious geometrical symmetry. These results could serve as a reference for investigating many abnormal phenomena such as abnormal infrared effects, which are found when CO molecules are adsorbed on the surface of nanostructured transition metals.

Absorptive Fabry–Pérot Interference in a Metallic Nanostructure

In conventional optics, the Fabry–Pérot(FP) effect is only considered for transparent materials at a macroscopic dimension. Down to the nanometer scale, for absorptive metallic structures, the FP effect has not been directly observed so far. It is unclear whether such a macroscopic effect still holds for a subwavelength metallic nanostructure. Here, we demonstrate the probing of FP interference in a series of nanometer-thick Au films with subwavelength hole arrays. The evidence from both linear and second harmonic generation signals, together with angle-resolved investigations, exhibit features of a FP effect. We also derive an absorptive FP interference equation, which well explains our experimental results. Our results for the first time experimentally confirm the long-persisting hypothesis that the FP effect holds ubiquitously in a metallic nanostructure.

Achieving high strength and high ductility in nanostructured metals: Experiment and modelling

Department of Mechanical and Biomedical Engineering, City University of Hong Kong, Kowloon, Hong Kong, Chinagrains to a^1-martensite nanograins with bimodal grain size distribution for lower strain rates to nanotwins in the ultrafine/coarse grained austenite phase for higher strain rates. Meanwhile, we will further address the mechanism-based plastic models to describe the yield strength, strain hardening and ductility in nanostructured metals with bimodal grain size distribution and nanotwinned polycrystalline metals. The proposed theoretical models can comprehensively describe the plastic deformation in these two kinds of nanostructured metals and excellent agreement is achieved between the numerical and experimental results. These models can be utilized to optimize the strength and ductility in nanostructured metals by controlling the size and distribution of nanostructures.

金属材料表面纳米化研究与进展

大多数金属材料的失效都是从其表面开始的,进而影响整个材料的整体性能。研究表明,在金属材料表面制备纳米晶,实现表面纳米化,可以提升材料的表面性能,延长其使用寿命。金属材料表面纳米化是指利用反复剧烈塑性变形让表层粗晶粒逐步得到细化,材料中形成晶粒沿厚度方向呈梯度变化的纳米结构层,分别为表面无织构纳米晶层、亚微米细晶层、粗晶变形层和基体层,这种独特的梯度纳米结构对金属材料表面性能的大幅度提升效果显著。根据国内外表面纳米化的研究成果,首先对表面涂层或沉积、表面自纳米化以及混合纳米化3种金属表面纳米化方法进行了简要概述,阐述了各自优缺点,总结了表面自纳米化技术的优势,在此基础上重点分析了位错和孪晶在金属材料表面自纳米化过程中所起的关键作用,提出了金属材料表面自纳米化机制与材料结构、层错能大小有着密不可分的联系,对金属材料表面自纳米化机制的研究现状进行了归纳;阐明了表面纳米化技术在金属材料性能提升上的巨大优势,主要包括对硬度、强度、腐蚀、耐磨、疲劳等性能的改善。最后总结了现有表面强化工艺需要克服的关键技术,对未来的研究工作进行了展望,并提出将表面纳米化技术与电镀、气相沉积、粘涂、喷涂、化学热处理等现有的一些表面处理技术相结合,取代高成本的制造技术,制备出价格低廉、性能更加优异的复相表层。

金属/高熵合金纳米多层膜的制备、微观结构及力学性能研究进展

通过表面防护涂层技术制备综合力学性能与摩擦性能优异的涂层材料,对降低构件因碰撞摩擦磨损所引起的损伤失效问题十分重要。相较于单层膜结构防护涂层,金属纳米多层膜涂层材料由于其微观组织结构的独特性与可控性,表现出优异的服役特性,且其综合性能可通过结合新组元或界面调控得到进一步提高,因此该类材料受到了广泛关注。新颖的成分设计理念使得高熵合金具有独特的四大效应,即高熵效应、晶格畸变效应、迟滞扩散效应和性能鸡尾酒效应,进而呈现出良好的综合性能。因此,在传统的双金属纳米多层膜结构材料中引入高熵合金组元,形成金属/高熵合金纳米多层膜,有望突破传统金属纳米多层膜的性能局限,极大地提高多层膜结构材料的力学性能。从功能基元序构的视角,围绕近几年金属/高熵合金纳米多层膜的相关研究,首先介绍了其制备方法和工艺原理,针对功能基元微观结构特征,从晶粒形貌、界面结构、组元成分等方面进行了阐释,在此基础上论述了其力学行为以及相应的内在机制,并提出了调控金属/高熵合金纳米多层膜力学性能的优化策略,最后对金属/高熵合金纳米多层膜的未来研究方向和面临的挑战进行展望。