Unprecedented and highly stable lithium storage capacity of (001) faceted nanosheet-constructed hierarchically porous TiO2/rGO hybrid architecture for high-performance Li-ion batteries

Active crystal facets can generate special properties for various applications. Herein, we report a (001) faceted nanosheet-constructed hierarchically porous TiO₂/rGO hybrid architecture with unprecedented and highly stable lithium storage performance. Density functional theory calculations show that the (001) faceted TiO₂ nanosheets enable enhanced reaction kinetics by reinforcing their contact with the electrolyte and shortening the path length of Li⁺ diffusion and insertion-extraction. The reduced graphene oxide (rGO) nanosheets in this TiO₂/rGO hybrid largely improve charge transport, while the porous hierarchy at different length scales favors continuous electrolyte permeation and accommodates volume change. This hierarchically porous TiO₂/rGO hybrid anode material demonstrates an excellent reversible capacity of 250 mAh g^–1 at 1 C (1 C = 335 mA g^–1) at a voltage window of 1.0–3.0 V. Even after 1000 cycles at 5 C and 500 cycles at 10 C, the anode retains exceptional and stable capacities of 176 and 160 mAh g^–1, respectively. Moreover, the formed Li₂Ti₂O₄ nanodots facilitate reversed Li⁺ insertion-extraction during the cycling process. The above results indicate the best performance of TiO₂-based materials as anodes for lithium-ion batteries reported in the literature.     

新型电力系统背景下氢能综合利用站发展的商业模式研究

适应可再生能源大规模发展的新型电力系统构建是促进“双碳”目标实现的重要保障。新型电力系统构建离不开储能、尤其是具有中长期储能特征的氢储能的发展。氢能综合利用站包括电解水制氢、氢储能、以及氢燃料电池发电,是新型电力系统下重要的灵活性电力负荷和储能资源。但目前适用于氢能综合利用站（以下简称为:氢能电站）发展的商业模式还不够清晰,其经济效益问题阻碍了氢能电站的推广。本文首先从氢能综合利用的发展现状入手,基于氢能电站各设备模块实际的运行特点,以及氢能电站中各设备的投资及运维成本构建了技术经济分析模型;在此基础上根据能源价格、各设备运行效率等参数模拟氢能电站运行情况,分析了“氢储能套利”、“可再生能源制氢+氢储能套利”、“可再生能源制氢+氢储能套利+售氢”、“氢储能套利+调频”、“氢储能套利+调频+售氢”五种模式下氢能电站的经济效益,探究了适合氢能电站发展更加可行的商业模式;最后,提出了促进氢能电站发展的相应政策建议。。     

Water molecules bonded to the carboxylate groups at the inorganic–organic interface of an inorganic nanocrystal coated with alkanoate ligands

High-quality colloidal nanocrystals are commonly synthesized in hydrocarbon solvents with alkanoates as the most common organic ligand. Water molecules with an approximately equal number of surface alkanoate ligands are identified at the inorganic–organic interface for all types of colloidal nanocrystals studied, and investigated quantitatively using CdSe nanocrystals as the model system. Carboxylate ligands are coordinated to the surface metal ions and the first monolayer of water molecules is found to bond to the carboxylate groups of alkanoate ligands through hydrogen bonds. Additional monolayer(s) of water molecules can further be adsorbed through hydrogen bonds to the first monolayer of water molecules. The nearly ideal environment for hydrogen bonding at the inorganic–organic interface of alkanoate-coated nanocrystals helps to rapidly and stably enrich the interface-bonded water molecules, most of which are difficult to remove through vacuum treatment, thermal annealing and chemical drying. The water-enriched structure of the inorganic–organic interface of high-quality colloidal nanocrystals must be taken into account in order to understand the synthesis, processing and properties of these novel materials.     

Nanomechanics of graphene

The super-high strength of single-layer graphene has attracted great interest. In practice, defects resulting from thermodynamics or introduced by fabrication, naturally or artificially, play a pivotal role in the mechanical behaviors of graphene. More importantly, high strength is just one aspect of the magnificent mechanical properties of graphene: its atomic-thin geometry not only leads to ultra-low bending rigidity, but also brings in many other unique properties of graphene in terms of mechanics in contrast to other carbon allotropes, including fullerenes and carbon nanotubes. The out-of-plane deformation is of a ‘soft’ nature, which gives rise to rich morphology and is crucial for morphology control. In this review article, we aim to summarize current theoretical advances in describing the mechanics of defects in graphene and the theory to capture the out-of-plane deformation. The structure–mechanical property relationship in graphene, in terms of its elasticity, strength, bending and wrinkling, with or without the influence of imperfections, is presented.     

A new twist on graphene: an interview with Pablo Jarillo-Herrero and Allan MacDonald

Graphene is the building block of graphite, made of carbon atoms bonded into sheets of hexagonal rings just a single atom thick. Although such isolated sheets had been predicted for many decades to exist, and had been grown on other surfaces, interest in this material exploded after the discovery in 2004 that single sheets could be made easily and cheaply by separating them mechanically from graphite flakes (a process called exfoliation). Although graphene is often advertised as a ‘wonder material’—electronically conducting, transparent and extremely strong and flexible—much of the interest in it is more fundamental. As a 2D conductor, graphene shows unusual electronic and magnetic properties that enable the study of quantum-mechanical effects of confinement and of correlations between electron motions—some of which might find applications in electronic devices. The excitement of this discovery was reflected in the award of the 2010 Nobel Prize in Physics to two pioneers in the field: Andre Geim and Konstantin Novoselov of the University of Manchester in the UK.This rich behavior is broadened still further when two graphene sheets are brought close enough to interact with one another. In particular, the electronic properties may then depend on the relative orientation of the sheets: how aligned the two ‘honeycomb’ lattices are. Two grids superimposed on one another may create ‘superlattices’: regularities at larger scales than the grid spacing, due to registry (commensurability) between the two at certain angles. This so-called moiré effect is sometimes evident for two closely spaced grid-like fences seen from afar. Experimentally exploring the electronic properties of such ‘twisted bilayer graphene’ requires an ability to precisely control the position and orientation of the two sheets. These phenomena are now recognized as generic to other 2D materials, such as hexagonal sheets of boron nitride. They have revealed a fertile playground for condensed-matter physics. In particular, striking electronic properties appear at certain ‘magic-angle’ twists of the layers.NSR spoke to two of the leading experts in the study of magic-angle twisted bilayer graphene (MATBG): experimentalist Pablo Jarillo-Herrero of the Massachusetts Institute of Technology and theorist Allan MacDonald of the University of Texas at Austin.     

Ultrafast growth of large single crystals of monolayer WS2 and WSe2

Monolayer transition metal dichalcogenides (TMDs) have attracted considerable attention as atomically thin semiconductors for the ultimate transistor scaling. For practical applications in integrated electronics, large monolayer single crystals are essential for ensuring consistent electronic properties and high device yield. The TMDs available today are generally obtained by mechanical exfoliation or chemical vapor deposition (CVD) growth, but are often of mixed layer thickness, limited single crystal domain size or have very slow growth rate. Scalable and rapid growth of large single crystals of monolayer TMDs requires maximization of lateral growth rate while completely suppressing the vertical growth, which represents a fundamental synthetic challenge and has motivated considerable efforts. Herein we report a modified CVD approach with controllable reverse flow for rapid growth of large domain single crystals of monolayer TMDs. With the use of reverse flow to precisely control the chemical vapor supply in the thermal CVD process, we can effectively prevent undesired nucleation before reaching optimum growth temperature and enable rapid nucleation and growth of monolayer TMD single crystals at a high temperature that is difficult to attain with use of a typical thermal CVD process. We show that monolayer single crystals of 450 μm lateral size can be prepared in 10 s, with the highest lateral growth rate up to 45 μm/s. Electronic characterization shows that the resulting monolayer WSe₂ material exhibits excellent electronic properties with carrier mobility up to 90 cm² V⁻¹ s⁻¹, comparable to that of the best exfoliated monolayers. Our study provides a robust pathway for rapid growth of high-quality TMD single crystals.     

Rock-salt and helix structures of silver iodides under ambient conditions

Many different phase structures have been discovered for silver iodides. The β and γ phases were found to be the most common ones at ambient conditions, while the rock-salt phase was found to be stable under pressures between 400 MPa and 11.3 GPa. Recently, the α phase was demonstrated to be stable under ambient conditions when the particle sizes were reduced to below 10 nm. However, no other phase has been reported to be stable for silver iodides under ambient conditions. Rock-salt and helix structures have been found to be stable under ambient conditions in this study. The structures have been characterized by elemental mapping, Raman scattering, and high-resolution transmission electron microscopy. The stabilities of these structures were also confirmed by molecular dynamics and density functional theory.     

Calcium carbonate polymorph control using droplet-based microfluidics

Calcium carbonate (CaCO(3)) is one of the most abundant minerals and of high importance in many areas of science including global CO(2) exchange, industrial water treatment energy storage, and the formation of shells and skeletons. Industrially, calcium carbonate is also used in the production of cement, glasses, paints, plastics, rubbers, ceramics, and steel, as well as being a key material in oil refining and iron ore purification. CaCO(3) displays a complex polymorphic behaviour which, despite numerous experiments, remains poorly characterised. In this paper, we report the use of a segmented-flow microfluidic reactor for the controlled precipitation of calcium carbonate and compare the resulting crystal properties with those obtained using both continuous flow microfluidic reactors and conventional bulk methods. Through combination of equal volumes of equimolar aqueous solutions of calcium chloride and sodium carbonate on the picoliter scale, it was possible to achieve excellent definition of both crystal size and size distribution. Furthermore, highly reproducible control over crystal polymorph could be realised, such that pure calcite, pure vaterite, or a mixture of calcite and vaterite could be precipitated depending on the reaction conditions and droplet-volumes employed. In contrast, the crystals precipitated in the continuous flow and bulk systems comprised of a mixture of calcite and vaterite and exhibited a broad distribution of sizes for all reaction conditions investigated.     

Effect of sample type,centrifugation and storage conditions on vitamin D concentration

Introduction:

Studies about vitamin D [25(OH)D] stability in plasma are limited and preanalytical variables such as tube type may affect results. We aimed to evaluate effect of storage conditions, sample type and some preanalytical variables on vitamin D concentration.

Materials and methods:

Blood samples from 15 healthy subjects were centrifuged at different temperatures and stored under different conditions. Serum and plasma 25(OH)D difference, effect of centrifugation temperature and common storage conditions were investigated.

Results:

There was no difference between serum and plasma vitamin D concentration. Centrifugation temperature had no impact on vitamin D concentration. 25(OH)D is stable under common storage conditions: 4 hours at room temperature, 24 hours at 2–8 °C, 7 days at −20 °C, 3 months at −80 °C.

Conclusion:

Vitamin D does not require any special storage conditions and refrigeration. Both serum and plasma can be used for measurement.     

In situ growth of large-area and self-aligned graphene nanoribbon arrays on liquid metal

Intrinsic graphene features semi-metallic characteristics that limit its applications in electronic devices, whereas graphene nanoribbons (GNRs) are promising semiconductors because of their bandgap-opening feature. However, the controllable mass-fabrication of high-quality GNR arrays remains a major challenge. In particular, the in situ growth of GNR arrays through template-free chemical vapor deposition (CVD) has not been realized. Herein, we report a template-free CVD strategy to grow large-area, high-quality and self-aligned GNR arrays on liquid copper surface. The width of as-grown GNR could be optimized to sub-10 nm with aspect ratio up to 387, which is higher than those of reported CVD-GNRs. The study of the growth mechanism indicates that a unique comb-like etching-regulated growth process caused by a trace hydrogen flow guides the formation of the mass-produced self-aligned GNR arrays. Our approach is operationally simple and efficient, offering an assurance for the use of GNR arrays in integrated circuits.     

Self-energy dynamics and the mode-specific phonon threshold effect in Kekulé-ordered graphene

Electron-phonon interaction and related self-energy are fundamental to both the equilibrium properties and non-equilibrium relaxation dynamics of solids. Although electron-phonon interaction has been suggested by various time-resolved measurements to be important for the relaxation dynamics of graphene, the lack of energy- and momentum-resolved self-energy dynamics prohibits direct identification of the role of specific phonon modes in the relaxation dynamics. Here, by performing time- and angle-resolved photoemission spectroscopy measurements on Kekulé-ordered graphene with folded Dirac cones at the Γ point, we have succeeded in resolving the self-energy effect induced by the coupling of electrons to two phonons at Ω₁ = 177 meV and Ω₂ = 54 meV, and revealing its dynamical change in the time domain. Moreover, these strongly coupled phonons define energy thresholds, which separate the hierarchical relaxation dynamics from ultrafast, fast to slow, thereby providing direct experimental evidence for the dominant role of mode-specific phonons in the relaxation dynamics.     

镁基储氢合金材料的性能及研究进展

由于资源丰富,储氢容量较高,价格低廉,应用前景广阔等特点,镁基储氢合金材料成为近年来研究的热点,然而其稳定的热力学性和缓慢的动力学性限制了它的应用,因而对镁基储氢合金材料的改性日益成为了镁基储氢合金发展的重要方向,文章对镁基储氢合金材料的性能及改性方法进行了综述,并对其发展趋势进行了展望。     

The processes involved in the solid-to-liquid phase transition

The detailed study of crystals and the dynamics of the melting process in two and three dimensions is a fundamental and interesting research topic, which is important for increasing our knowledge of solid state physics. In natural crystals, structure information can be obtained principally by Bragg-scattering of neutrons, electrons or photons on the crystal, followed by an analysis in Fourier space. Dynamical aspects cannot be investigated in these systems. Recently, a new crystalline system was discovered whose properties are such that the melting transition can be investigated in great detail — the ‘plasma crystal’. This article presents the results of such an investigation and shows evidence for the existence of intermediate phases between the solid, liquid and gaseous phases. The observed ‘structured’ phase transition may be specific for plasma crystals but, alternatively, it may indicate the existence of intermediate stages in the melting transition more generally.     

A stimuli-responsive pillar[5]arene-based hybrid material with enhanced tunable multicolor luminescence and ion-sensing ability

Tunable luminescent materials are becoming more and more important owing to their broad application potential in various fields. Here we construct a pillar[5]arene-based hybrid material with stimuli-responsive luminescent properties and ion-sensing abilities from a pyridine-modified conjugated pillar[5]arene and a planar chromophore oligo(phenylenevinylene) upon coordination of Cd (II) metal cores. This new material not only shows an optimized luminescence due to the minimized π–π stacking and efficient charge transfer properties benefitting from the existence of pillar[5]arene rings, but also exhibits tunable multicolor emission induced by different external stimuli including solvent, ions and acid, indicating great application potential as a fluorescent sensory material, especially for Fe³⁺. With this pillar[5]arene-based dual-ligand hybrid material, valid optimization and regulation on the fluorescence of the original chromophore have been achieved, which demonstrates a plausible strategy for the design of tunable solid-state luminescent materials and also a prototypical model for the effective regulation of fluorescent properties of planar π systems using synthetic macrocycle-based building blocks.     

A scalable fish-school inspired self-assembled particle system for solar-powered water-solute separation

Complete separation of water and solute is the ultimate goal of water treatment, for maximized resource recycling. However, commercialized approaches such as evaporative crystallizers consume a large amount of electricity with a significant carbon footprint, leading to calls for alternative energy-efficient and eco-friendly strategies. Here, inspired by schooling fish, we demonstrate a collective system self-assembled by expanded polystyrene (EPS)-core/graphene oxide (GO)-shell particles, which enables autonomous, efficient and complete water-solute separation powered by sunlight. By taking advantage of surface tension, these tailored particles school together naturally and are bonded as a system to function collectively and coordinatively, to nucleate, grow and output salt crystals continuously and automatically out of even saturated brine, to complete water-solute separation. Solar-vapor conversion efficiency over 90% and salt production rate as high as 0.39 kg m^–2 h^–1 are achieved under 1-sun illumination for this system. It reduces the carbon footprint of ∼50 kg for treating 1-ton saturated brine compared with the commercialized approaches.     

钻孔石墨烯用于氢气和氮气分离的分子动力学模拟(英文)

利用分子动力学模拟方法,发现不同孔径的钻孔石墨烯对氢气和氮气有很好的分离性.当挖去了10个碳原子,孔径为0.3725 nm时,分离效率可以达到100%.由结果可以预见,钻孔石墨烯将会在气体分离和纯化方面有应用潜力.     

A portable lab-on-a-chip system for gold-nanoparticle-based colorimetric detection of metal ions in water

Heavy metal ions released into various water systems have a severe impact on the environment and human beings, and excess exposure to toxic metal ions through drinking water poses high risks to human health and causes life-threatening diseases. Thus, there is high demand for the development of a rapid, low-cost, and sensitive method for detection of metal ions in water. We present a portable analytical system for colorimetric detection of lead (Pb²⁺) and aluminum (Al³⁺) ions in water based on gold nanoparticle probes and lab-on-a-chip instrumentation. The colorimetric detection of metal ions is conducted via single-step assays with low limits of detection (LODs) and high selectivity. We design a custom-made microwell plate and a handheld colorimetric reader for implementing the assays and quantifying the signal readout. The calibration experiments demonstrate that this portable system provides LODs of 30 ppb for Pb²⁺ and 89 ppb for Al³⁺, both comparable to bench-top analytical spectrometers. It promises an effective platform for metal ion analysis in a more economical and convenient way, which is particularly useful for water quality monitoring in field and resource-poor settings.     

Droplet formation and shrinking in aqueous two-phase systems using a membrane emulsification method

Using a membrane emulsification method based on porous hollow-fiber membranes in combination with an aqueous two-phase system (ATPS), we are able to produce “water-in-water” droplets with narrow-dispersed size distributions. The equilibrium phases of the aqueous two-phase system polyethylene glycol-dipotassium hydrogen phosphate are used for this purpose. The droplet diameter of a given fluid system is determined by the flow rates of the continuous and disperse phase as well as the hollow fiber dimensions. When diluting the disperse phase and thus moving the ATPS system out of equilibrium, the droplet size can be further reduced in comparison to the equilibrium case. Generally, droplets formed with this method have diameters 20%–60% larger than the inner hollow fiber diameter. The new strategy of diluting the disperse phase allows the production of droplet diameter below the inner diameter of the membrane.     

Evidence for oxygenation of Fe-Mg oxides at mid-mantle conditions and the rise of deep oxygen

As the reaction product of subducted water and the iron core, FeO₂ with more oxygen than hematite (Fe₂O₃) has been recently recognized as an important component in the D” layer just above the Earth''s core-mantle boundary. Here, we report a new oxygen-excess phase (Mg, Fe)₂O_3+δ (0 < δ < 1, denoted as ‘OE-phase’). It forms at pressures greater than 40 gigapascal when (Mg, Fe)-bearing hydrous materials are heated over 1500 kelvin. The OE-phase is fully recoverable to ambient conditions for ex situ investigation using transmission electron microscopy, which indicates that the OE-phase contains ferric iron (Fe³⁺) as in Fe₂O₃ but holds excess oxygen through interactions between oxygen atoms. The new OE-phase provides strong evidence that H₂O has extraordinary oxidation power at high pressure. Unlike the formation of pyrite-type FeO₂Hx which usually requires saturated water, the OE-phase can be formed with under-saturated water at mid-mantle conditions, and is expected to be more ubiquitous at depths greater than 1000 km in the Earth''s mantle. The emergence of oxygen-excess reservoirs out of primordial or subducted (Mg, Fe)-bearing hydrous materials may revise our view on the deep-mantle redox chemistry.     

Microfluidic formulation of pectin microbeads for encapsulation and controlled release of nanoparticles

We report a method for formulation of pectin microbeads using microfluidics. The technique uses biocompatible ingredients and allows for controlled external gelation with hydrogen and calcium ions delivered from an organic phase of rapeseed oil. This method allows for encapsulation of nanoparticles into the microparticles of gel and for control of the rate of their release.