Synthesis of Hollow Three-Dimensional Channels LiNi_(0.5)Mn_(1.5)O_4 Microsphere by PEO Soft Template Assisted with Solvothermal Method

A appropriate size with three-dimension(3 D) channels for lithium diffusion plays an important role in constructing highperforming LiNi_(0.5)Mn_(1.5)O_4(LNMO) cathode materials, as it can not only reduce the transport path of lithium ions and electrons, but also reduce the side effects and withstand the structural strain in the process of repetitive Li~+ intercalation/deintercalation. In this work, an e fficient method for designing the hollow LNMO microsphere with 3 D channels structure by using polyethylene oxide(PEO) as soft template agent assisted solvothermal method is proposed. Experimental results indicate that PEO can make the reagents mingle evenly and nucleate slowly in the solvothermal process, thus obtaining a homogeneous distribution of carbonate precursors. In the final LNMO products, the hollow 3 D channels structure obtained by the decomposition of PEO and carbonate precursor in the calcination can provide abundant electroactive zones and electron/ion transport paths during the charge/discharge process, which benefits to improve the cycling performance and rate capability. The LNMO prepared by adding 1 g PEO possesses the most outstanding electrochemical performance, which presented an excellent discharge capacity of 143.1 mAh g~(-1) at 0.1 C and with a capacity retention of 92.2% after 100 cycles at 1 C. The superior performance attributed to the 3 D channels structure of hollow microspheres, which provide uninterrupted conductive systems and therefore achieve the stable transfer for electron/ion.     

Influence of CO2 inleakage on the slight-alkalization of generator internal cooling water

The slight-alkalization of generator internal cooling water (GICW) is widely used to inhibit the corrosion of hollow copper conductor and thereby ensure the safe operation of the generator. CO₂ inleakage is increasingly identified as a potential security risk for GICW system. In this paper, the influence of CO₂ inleakage on the slight-alkalization of GICW was theoretically discussed. Based on the equilibriums of the CO₂-NaOH-H₂O system, CO₂ inleakage saturation was derived to quantify the amount of the dissolved CO₂ in GICW. This parameter can be directly calculated with the measured conductivity and the [Na⁺] of GICW. The influence of CO₂ inleakage on the slight-alkalization conditioning of GICW and the measurement of its water quality parameters were then analyzed. The more severe the inleakage, the narrower the water quality operation ranges of GICW, resulting in the more difficult the slight-alkalization conditioning of GICW. The temperature calibrations of the conductivity and the pH value of GICW show non-linear correlations with the amount of CO₂ inleakage and the NaOH dosage. This study provides insights into the influence of CO₂ inleakage on the slight-alkalization of GICW, which can serve as the theoretical basis for the actual slight-alkalization when CO₂ inleakage occurs.     

Al2O3/Yttria‐Stabilized Zirconia Hollow‐Fiber Membrane Incorporated with Iron Oxide for Pb(II) Removal

Removal by absorptive ceramic membranes can simultaneously absorb and separate metal ions from water. Alumina/yttria‐stabilized zirconia (Al₂O₃/YSZ) hollow‐fiber membranes, fabricated using phase inversion and sintering process, were deposited with iron oxide by an in‐situ hydrothermal process. The results showed that α‐Fe₂O₃ was produced and incorporated across the membranes. A reduction in flux was recorded with the deposition of α‐Fe₂O_3. However, it improved the adsorption capacity for heavy metal adsorption. The adsorption‐separation test demonstrated that the optimized membrane is able to completely remove Pb(II) ions after two hours.     

ZnIn2S4/In(OH)3 hollow microspheres fabricated by one-step l-cysteine-mediated hydrothermal growth for enhanced hydrogen production and MB degradation

An intervening barrier for photocatalytic water decomposition and pollutant degradation is the frustratingly quick recombination of e⁻ - h⁺ pairs. Delicate design of heterojunction photocatalysts by coupling the semiconductors at nanoscale with well-matched geometrical and electronic alignments is an effective strategy to ameliorate the charge separation. Here a facile and environment-friendly l-cysteine-assisted hydrothermal process under weakly alkaline conditions is demonstrated for the first time to fabricate ZnIn₂S₄/In(OH)₃ hollow microspheres with intimate contact, which are verified by XRD, SEM, (HR)TEM, XPS, N₂ adsorption-desorption, UV–Vis DRS and photoluminescence spectra. ZnIn₂S₄/In(OH)₃ heterostructure (L-cys/Zn²⁺ = 4, molar ratio) with a band-gap of 2.50 eV, demonstrates the best photocatalytic performance for water reduction and MB degradation under visible light, outperforming its counterparts (In(OH)₃ and ZnIn₂S₄). The excellent activity of ZnIn₂S₄/In(OH)₃ heterostructure arises from the intercrossed band-edge positions as well as the unique hollow structure with large surface area and wide pore-size distribution, which are beneficial for the efficient charge migration from bulk to surface as well as at the interface between ZnIn₂S₄ and In(OH)₃. This work provides an efficient and eco-friendly strategy for one-pot synthesis of heterostructured composites with intimate contact for photocatalytic application.     

Colloidal Synthesis of Hollow Cobalt Sulfide Nanocrystals

Formation of cobalt sulfide hollow nanocrystals through a mechanism similar to the Kirkendall Effect has been investigated in detail. It is found that performing the reaction at > 120 °C leads to fast formation of a single void inside each shell, whereas at room temperature multiple voids are formed within each shell, which can be attributed to strongly temperature‐dependent diffusivities for vacancies. The void formation process is dominated by outward diffusion of cobalt cations; still, the occurrence of significant inward transport of sulfur anions can be inferred as the final voids are smaller in diameter than the original cobalt nanocrystals. Comparison of volume distributions for initial and final nanostructures indicates excess apparent volume in shells, implying significant porosity and/or a defective structure. Indirect evidence for fracture of shells during growth at lower temperatures was observed in shell‐size statistics and transmission electron microscopy images of as‐grown shells. An idealized model of the diffusional process imposes two minimal requirements on material parameters for shell growth to be obtainable within a specific synthetic system.     

Encapsulation and Ostwald Ripening of Au and Au–Cl Complex Nanostructures in Silica Shells

We report a general template strategy for rational fabrication of a new class of nanostructured materials consisting of multicore shell particles. Our approach is demonstrated by encapsulating Au or Pt nanoparticles in silica shells. Other superstructures of these hollow shells, like dimers, trimers, and tetramers can also be formed by nanoparticle‐mediated self‐assembly. We have also used the as‐prepared multicore Au–silica hollow particles to perform the first studies of Ostwald ripening in confined microspace, in which chloride was found to be an efficient mediating ligand. After treatment with aqua regia, Au–Cl complex is formed inside the shell, and is found to be very active under in situ transmission electron microscopy observations while confined in a microcell. This aspect of the work is expected to motivate further in situ studies of confined crystal growth.     

Fabrication of multi-walled carbon nanotube reinforced polyelectrolyte hollow nanofibers by electrospinning

Hybrid hollow multi-walled carbon nanotubes (MWCNTs)/polyelectrolytes (PE) nanofibers were prepared by a combination of the electrospinning method and layer-by-layer (LbL) technique. The mixed polystyrene (PS)/MWCNTs nanofibers were obtained by electrospinning method, which were employed as templates to self-assembly multilayered polyelectrolytes by LbL technique. Hollow MWCNTs/PE nanofibers were obtained by selectively removed part of the template: PS, which is confirmed by Raman spectra, transmission electron microscopy (TEM) and scanning electron microscopy (SEM).     

Preparation of submicrometer-sized titania hollow spheres by templating sulfonated polystyrene latex particles

Submicrometer-sized titania hollow spheres with tunable shell thickness and smooth surfaces have been successfully synthesized by employing sulfonated polystyrene (PS) latex particles as a template in sol-gel method. The structure of the particles was characterized by scanning electron microscopy and transmission electron microscopy. The shell thickness was readily tuned by altering the concentration of titanium tetrabutoxide (TBOT) in ethanol solutions. The surface roughness as well as the shell thickness has the tendency to increase with the increase in the concentration of TBOT. The diameter of the hollow spheres was on the average of 20-26% smaller than the diameter of template PS latex particles. Some titania fragments were also observed for the sample with the highest TBOT concentration.     

Novel one-step route for synthesizing sub-micrometer PSt hollow spheres via redox interfacial-initiated method in inversed emulsion

Interfacial-initiated polymerization of styrene (St) was carried out in inversed emulsion with cumene hydroperoxide (CHPO) and ferrous sulfate (FeSO₄)/disodium ethylenediaminetetraacetate (NaEDTA)/sodium formaldehyde sulfoxylate (SFS) as the redox initiation system. The water-soluble Fe²⁺-NaEDTA-SFS acted as the reducing component and the oil-soluble CHPO as the oxidant component of the redox initiation system. Therefore, the primary radicals were produced mainly at the oil/water interface to initiate the polymerization of St. Thus, sub-micrometer hollow polystyrene (PSt) spheres were obtained by one-stage polymerization, which was supported by the techniques of transmission electron microscopy (TEM) and field emission scanning electron microscopy (FESEM).     

Characterization of hollow fiber membranes in a permeator using binary gas mixtures

We have studied the CO₂/CH₄ mixed gas permeation through hollow fiber membranes in a permeator. An approach to characterize the true separation performance of hollow fiber membranes for binary gas mixtures was provided based on experiments and simulations. Experiments were carried out to measure the retentate and permeate flow rates and compositions at each outlet. The influences of pressure drop within the hollow fibers, non-ideal gas behavior in the mixture and concentration polarization were taken into consideration in the mathematics model. The calculation results indicate that the net influence of the non-ideal gas behavior, competitive sorption and plasticization yields the calculated CO₂ permeance in a mixed gas permeator close to that obtained in pure gas tests. Whereas the CH₄ permeance is higher in the mixed gas tests than that in the pure gas tests, as the plasticization caused by CO₂ dominates the permeation process. As a result, the CO₂/CH₄ mixed gas selectivity is smaller than those obtained in pure gas tests at equivalent pressures.The calculated membrane performance shows little changes with stage cut if the effect of concentration polarization is accounted for in the calculation. The integration method developed in this study could provide more accurate characterizations of mixed gas permeance of hollow membranes than other estimation methods, as our model considers the roles of non-ideal gas behavior and concentration polarization properly.