Ionothermal Synthesis of High-Voltage Alluaudite Na2+2xFe2-x(SO4)(3) Sodium Insertion Compound: Structural, Electronic, and Magnetic Insights

Exploring future cathode materials for sodium-ion batteries, alluaudite class of Na2Fe2II(SO4)(3) has been recently unveiled as a 3.8 V positive insertion candidate (Barpanda et al. Nat. Commun. 2014, 5, 4358). It forms an Fe-based polyanionic compound delivering the highest Fe-redox potential along with excellent rate kinetics and reversibility. However, like all known SO4-based insertion materials, its synthesis is cumbersome that warrants careful processing avoiding any aqueous exposure. Here, an alternate low temperature ionothermal synthesis has been described to produce the alluaudite Na2+2xFe2-xII(SO4)(3). It marks the first demonstration of solvothermal synthesis of alluaudite Na2+2xM2-xII(SO4)(3) (M = 3d metals) family of cathodes. Unlike classical solid-state route, this solvothermal route favors sustainable synthesis of homogeneous nanostructured alluaudite products at only 300 degrees C, the lowest temperature value until date. The current work reports the synthetic aspects of pristine and modified ionothermal synthesis of Na2+2xFe2-xII(SO4)(3) having tunable size (300 nm similar to 5 mu m) and morphology. It shows antiferromagnetic ordering below 12 K. A reversible capacity in excess of 80 mAh/g was obtained with good rate kinetics and cycling stability over 50 cycles. Using a synergistic approach combining experimental and ab initio DFT analysis, the structural, magnetic, electronic, and electrochemical properties and the structural limitation to extract full capacity have been described.

Synthesis of Cu-In-S ternary nanocrystals with tunable structure and composition

Nearly monodisperse Cu-In-S ternary nanocrystals with tunable composition, crystalline structure, and size were synthesized by a hot-injection method using mixed generic precursors. Such ternary nanocrystals with zincblende and wurtzite structure were reported for the first time.

Synthesis and characterization of 1D Co/CoFe2O4 composites with tunable morphologies

1D Co/CoFe2O4 composites with tunable morphologies were fabricated by a facile solvothermal route in the presence of a surfactant poly(vinylpyrrolidone) (PVP); they may be very attractive for potential applications because of their outstanding soft magnetism.

A simple single-source precursor route to the nanostructures of AIN, GaN and InN

In an effort to find a simple and common single-source precursor route for the group 13 metal nitride semiconductor nanostructures, the complexes formed by the trichlorides of Al, Ga and In with urea have been investigated. The complexes, characterized by X-ray crystallography and other techniques, yield the nitrides on thermal decomposition. Single crystalline nanowires of AlN, GaN and InN have been deposited on Si substrates covered with Au islands by using the complexes as precursors. The urea complexes yield single crystalline nanocrystals under solvothermal conditions. The successful synthesis of the nanowires and nanocrystals of these three important nitrides by a simple single-precursor route is noteworthy and the method may indeed be useful in practice.

Metal-Ion Metathesis in Metal-Organic Frameworks: A Synthetic Route to New Metal-Organic Frameworks

A porous metalorganic framework, Mn(H3O)(Mn4Cl)(3)(hmtt)(8)] (POST-65), was prepared by the reaction of 5,5',10,10',15,15'-hexamethyltruxene-2,7,12-tricarboxylic acid (H(3)hmtt) with MnCl2 under solvothermal conditions. POST-65(Mn) was subjected to post-synthetic modification with Fe, Co, Ni, and Cu according to an ion-exchange method that resulted in the formation of three isomorphous frameworks, POST-65(Co/Ni/Cu), as well as a new framework, POST-65(Fe). The ion-exchanged samples could not be prepared by regular solvothermal reactions. The complete exchange of the metal ions and retention of the framework structure were verified by inductively coupled plasmaatomic emission spectrometry (ICP-AES), powder X-ray diffraction (PXRD), and BrunauerEmmettTeller (BET) surface-area analysis. Single-crystal X-ray diffractions studies revealed a single-crystal-to-single-crystal (SCSC)-transformation nature of the ion-exchange process. Hydrogen-sorption and magnetization measurements showed metal-specific properties of POST-65.

Solvothermal synthesis and characterization of Ln (Eu3+, Tb3+) doped hydroxyapatite

Luminescent Ln (Eu3+, Tb3+) doped hydroxyapatite (Eu:HAp, Tb:HAp) phosphors were successfully fabricated via the cetyltrimethylammonium bromide (CTAB)/n-octane/n-butanol/water microemulsion-mediated solvothermal process. The structure, morphology, and optical properties were systematically characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray photoelectron spectra (XPS), Fourier transform infrared spectroscopy (FT-IR), and photoluminescence (PL) spectra as well as the kinetic decays, respectively.

Microemulsion-mediated solvothermal synthesis and photoluminescent property of 3D flowerlike MnWO4 micro/nanocomposite structure

Novel three-dimensional (3D) flowerlike MnWO4 micro/nanocomposite structure has been successfully synthesized for the first time. The synthesized products were systematically studied by X-ray powder diffraction (XRD), field-emission scanning electron microscopy (FESEM) and transmission electron microscopy (TEM) and photoluminescence (PL) spectra. It is found that both reaction time and temperature have significant effects on the morphology of the products.

A new low temperature synthesis route of fraipontite (Zn,Al)3(Si,Al)2O5(OH)4

A low temperature synthesis method based on the decomposition of urea at 90°C in water has been developed to synthesise fraipontite. This material is characterised by a basal reflection 001 at 7.44 Å. The trioctahedral nature of the fraipontite is shown by the presence of a 06l band around 1.54 Å, while a minor band around 1.51 Å indicates some cation ordering between Zn and Al resulting in Al-rich areas with a more dioctahedral nature. TEM and IR indicate that no separate kaolinite phase is present. An increase in the Al content however, did result in the formation of some SiO2 in the form of quartz. Minor impurities of carbonate salts were observed during the synthesis caused by to the formation of CO32- during the decomposition of urea.

An Improved Synthetic Route to the Potent Angiogenesis Inhibitor Benzyl Manα(1→3)-Manα(1→3)-Manα(1→3)-Manα(1→2)-Man Hexadecasulfate

An improved synthetic route to α(1→3)/α(1→2)-linked mannooligosaccharides has been developed and applied to a more efficient preparation of the potent anti-angiogenic sulfated pentasaccharide, benzyl Manα(1→3)-Manα(1→3)-Manα(1→3)-Manα(1→2)-Man hexadecasulfate, using only two monosaccharide building blocks. Of particular note are improvements in the preparation of both building blocks and a simpler, final deprotection strategy. The route also provides common intermediates for the introduction of aglycones other than benzyl, either at the building block stage or after oligosaccharide assembly. The anti-angiogenic activity of the synthesized target compound was confirmed via the rat aortic assay.

Modelling urban public transit users' route choice behaviour: review and outlook

This paper reviews the main development of approaches to modelling urban public transit users’ route choice behaviour from 1960s to the present. The approaches reviewed include the early heuristic studies on finding the least cost transit route and all-or-nothing transit assignment, the bus common line problem and corresponding network representation methods, the disaggregate discrete choice models which are based on random utility maximization assumptions, the deterministic use equilibrium and stochastic user equilibrium transit assignment models, and the recent dynamic transit assignment models using either frequency or schedule based network formulation. In addition to reviewing past outcomes, this paper also gives an outlook into the possible future directions of modelling transit users’ route choice behaviour. Based on the comparison with the development of models for motorists’ route choice and traffic assignment problems in an urban road area, this paper points out that it is rewarding for transit route choice research to draw inspiration from the intellectual outcomes out of the road area. Particularly, in light of the recent advancement of modelling motorists’ complex road route choice behaviour, this paper advocates that the modelling practice of transit users’ route choice should further explore the complexities of the problem.

Silylation of layered double hydroxides via a calcination−rehydration route

Silylated layered double hydroxides (LDHs) were synthesized through a surfactant-free method involving an in situ condensation of silane with the surface hydroxyl group of LDHs during its reconstruction in carbonate solution. X-ray diffraction (XRD) patterns showed the silylation reaction occurred on the external surfaces of LDHs layers. The successful silylation was evidenced by 29Si cross-polarization magic-angle spinning nuclear magnetic resonance (29Si CP/MAS NMR) spectroscopy, attenuated total reflection Fourier transform infrared (ATR FTIR) spectroscopy, and infrared emission spectroscopy (IES). The ribbon shaped crystallites with a “rodlike” aggregation were observed through transmission electron microscopy (TEM) images. The aggregation was explained by the T2 and T3 types of linkage between adjacent silane molecules as indicated in the 29Si NMR spectrum. In addition, the silylated products show high thermal stability by maintained Si related bands even when the temperature was increased to 1000 °C as observed in IES spectra.

Modelling urban public transit users’ route choice behaviour : a review and outlook

Public transport is one of the key promoters of sustainable urban transport. To encourage and increase public transport patronage it is important to investigate the route choice behaviours of urban public transit users. This chapter reviews the main developments of modelling urban public transit users’ route choice behaviours in a historical perspective, from the 1960s to the present time. The approaches re- viewed for this study include the early heuristic studies on finding the least-cost transit route and all-or- nothing transit assignment, the bus common lines problem, the disaggregate discrete choice models, the deterministic and stochastic user equilibrium transit assignment models, and the recent dynamic transit assignment models. This chapter also provides an outlook for the future directions of modelling transit users’ route choice behaviours. Through the comparison with the development of models for motorists’ route choice and traffic assignment problems, this chapter advocates that transit route choice research should draw inspiration from the research outcomes from the road area, and that the modelling practice of transit users’ route choice should further explore the behavioural complexities.

Transit users' route-choice modelling in transit assignment : a review

This paper reviews the main studies on transit users’ route choice in thecontext of transit assignment. The studies are categorized into three groups: static transit assignment, within-day dynamic transit assignment, and emerging approaches. The motivations and behavioural assumptions of these approaches are re-examined. The first group includes shortest-path heuristics in all-or-nothing assignment, random utility maximization route-choice models in stochastic assignment, and user equilibrium based assignment. The second group covers within-day dynamics in transit users’ route choice, transit network formulations, and dynamic transit assignment. The third group introduces the emerging studies on behavioural complexities, day-to-day dynamics, and real-time dynamics in transit users’ route choice. Future research directions are also discussed.