Heterostructured Mn_(3)O_(4)-MnS Multi-Shelled Hollow Spheres for Enhanced Polysulfide Regulation in Lithium-Sulfur Batteries

Constructing heterojunctions and hollow multi-shelled structures can render materials with fascinating physicochemical properties,and have been regarded as two promising strategies to overcome the severe shuttling and sluggish kinetics of polysulfide in lithium-sulfur(Li-S)batteries.However,a single strategy can only take limited effect.Modulating catalytic hosts with synergistic effects are urgently desired.Herein,Mn_(3)O_(4)-MnS heterogeneous multi-shelled hollow spheres are meticulously designed by controlled sulfuration of Mn2O3 hollow spheres,and then applied as advanced encapsulation hosts for Li-S batteries.Benefiting from the separated spatial confinement by hollow multi-shelled structure,ample exposed active sites and built-in electric field by heterogeneous interface,and synergistic effects between Mn_(3)O_(4)(strong adsorption)and MnS(fast conversion)components,the assembled battery achieves prominent rate capability and decent cyclability(0.016%decay per cycle at 2 C,1000 cycles).More crucially,satisfactory areal capacity reaches up to 7.1 mAh cm^(-2)even with high sulfur loading(8.0 mg cm^(-2))and lean electrolyte(E/S=4.0 pL mg^(-1))conditions.This work will provide inspiration for the rational design of hollow multi-shelled heterostructure for various electrocatalysis applications.

Novel Bilayer-Shelled N,O-Doped Hollow Porous Carbon Microspheres as High Performance Anode for Potassium-Ion Hybrid Capacitors

With the advantages of high energy/power density,long cycling life and low cost,dual-carbon potassium ion hybrid capacitors(PIHCs)have great potential in the field of energy storage.Here,a novel bilayer-shelled N,O-doped hollow porous carbon microspheres(NOHPC)anode has been prepared by a self-template method,which is consisted of a dense thin shell and a hollow porous spherical core.Excitingly,the NOHPC anode possesses a high K-storage capacity of 325.9 mA h g^(−1)at 0.1 A g^(−1)and a capacity of 201.1 mAh g^(−1)at 5 A g^(−1)after 6000 cycles.In combination with ex situ characterizations and density functional theory calculations,the high reversible capacity has been demonstrated to be attributed to the co-doping of N/O heteroatoms and porous structure improved K+adsorption and intercalation capabilities,and the stable long-cycling performance originating from the bilayer-shelled hollow porous carbon sphere structure.Meanwhile,the hollow porous activated carbon microspheres(HPAC)cathode with a high specific surface area(1472.65 m^(2)g^(−1))deriving from etching NOHPC with KOH,contributing to a high electrochemical adsorption capacity of 71.2 mAh g^(−1)at 1 A g^(−1).Notably,the NOHPC//HPAC PIHC delivers a high energy density of 90.1 Wh kg^(−1)at a power density of 939.6 W kg^(−1)after 6000 consecutive charge-discharge cycles.

α-MnO_2 nanoneedle-based hollow microspheres coated with Pd nanoparticles as a novel catalyst for rechargeable lithium-air batteries

The hollow α-MnO2 nanoneedle-based microspheres coated with Pd nanoparticles were reported as a novel catalyst for rechargeable lithium-air batteries. The hollow microspheres are composed ofα-MnO2 nanoneedles. Pd nanoparticles are deposited on the hollow microspheres through an aqueous-solution reduction of PdCl2 with NaBH4 at room temperature. The results of TEM, XRD, and EDS show that the Pd nanoparticles are coated on the surface ofα-MnO2 nanoneedles uniformly and the mass fraction of Pd in the Pd-coated α-MnO2 catalyst is about 8.88%. Compared with the counterpart of the hollow α-MnO2 catalyst, the hollow Pd-coated α-MnO2 catalyst improves the energy conversion efficiency and the charge-discharge cycling performance of the air electrode. The initial specific discharge capacity of an air electrode composed of Super P carbon and the as-prepared Pd-coatedα-MnO2 catalyst is 1220 mA＆#183;h/g （based on the total electrode mass） at a current density of 0.1 mA/cm2, and the capacity retention rate is about 47.3% after 13 charge-discharge cycles. The results of charge-discharge cycling tests demonstrate that this novel Pd-coatedα-MnO2 catalyst with a hierarchical core-shell structure is a promising catalyst for the lithium-air battery.

Salt-assisted Synthesis of Hollow Bi_2WO_6 Microspheres with Superior Photocatalytic Activity for NO Removal

Hollow Bi2WO6 microspheres are successfully synthesized by a facile ultrasonic spray pyrolysis（USP） method using NaCl as a salt template.The as-prepared hollow microspheres assembled as nanoplates with dimensions of approximately 41-148 nm and are dispersed with non-uniform pores on the template surface.By swapping the salt template with KC1 or Na2SO4,different morphologies of Bi2WO6 are obtained.The experimental results demonstrate that NaCl plays a key role on the formation of Bi2WO6 with hollow structures.The specific growth mechanism of hollow microspheres was studied in detail.The Bi2WO6 hollow microspheres exhibit an excellent photocatalytic efficiency for NO removal under solar light irradiation,which is 1.73 times higher than for the Bi2WO6 obtained in the absence of any salt template.This enhancement can be ascribed to the simultaneous improvement on the surface area and visible light-harvesting ability from the hollow structures.Electron spin resonance（ESR） results suggest that both radicals of ·OH and ·O2^- are involved in the photocatalytic process over the BWO-NaCl sample.The production of ·O2^- radicals offers better durability for NO removal.

Preparation of Hollow Silica Microspheres via Poly（N-isopropylacrylamide）

Core-shell structured SiO2/poly（N-isopropylacrylamide） （SiO2/PNIPAM） microspheres were successfully fabricated through hydrolysis and condensation reaction of tertraethyl orthosilicate （TEOS） on the surface of PNIPAM template at 50 ~C. The PNIPAM template can be easily removed by water at room temperature so that SiO2 hollow microspheres were finally obtained. The transmission electron microscope and scanning electron microscope observations indicated that SiO2 hollow microspheres with an average diameter of 150 nm can be formed only if there are enough concentration of PNIPAM and TEOS, and the hy- drolysis time of TEOS. FTIR analysis showed that part of PNIPAM remained on the wall of SiO2 because of the strong interaction between PNIPAM and silica. This work provides a clean and efficient way to prepare hollow microspheres.

Battery Separators Functionalized with Edge-Rich MoS2/C Hollow Microspheres for the Uniform Deposition of Li2S in High-Performance Lithium-Sulfur Batteries

As promising energy storage systems,lithium-sulfur(Li-S)batteries have attracted significant attention because of their ultra-high energy densities.However,Li-S battery suffers problems related to the complex phase conversion that occurs during the charge-discharge process,particularly the deposition of solid Li2S from the liquid-phase polysulfides,which greatly limits its practical application.In this paper,edge-rich MoS2/C hollow microspheres(Edg-MoS2/C HMs)were designed and used to functionalize separator for Li-S battery,resulting in the uniform deposition of Li2S.The microspheres were fabricated through the facile hydrothermal treatment of MoO3-aniline nanowires and a subsequent carbonization process.The obtained Edg-MoS2/C HMs have a strong chemical absorption capability and high density of Li2S binding sites,and exhibit excellent electrocatalytic performance and can effectively hinder the polysulfide shuttle effect and guide the uniform nucleation and growth of Li2S.Furthermore,we demonstrate that the Edg-MoS2/C HMs can effectively regulate the deposition of Li2S and significantly improve the reversibility of the phase conversion of the active sulfur species,especially at high sulfur loadings and high C-rates.As a result,a cell containing a separator functionalized with Edg-MoS2/C HMs exhibited an initial discharge capacity of 935 mAh g-1 at 1.0 C and maintained a capacity of 494 mAh g-1 after 1000 cycles with a sulfur loading of 1.7 mg cm-2.Impressively,at a high sulfur loading of 6.1 mg cm-2 and high rate of 0.5 C,the cell still delivered a high reversible discharge capacity of 478 mAh g-1 after 300 cycles.This work provides fresh insights into energy storage systems related to complex phase conversions.

Template-Free Synthesis of Sb_2S_3 Hollow Microspheres as Anode Materials for Lithium-Ion and Sodium-Ion Batteries

Hierarchical Sb_2S_3 hollow microspheres assembled by nanowires have been successfully synthesized by a simple and practical hydrothermal reaction. The possible formation process of this architecture was investigated by X-ray diffraction, focused-ion beam-scanning electron microscopy dual-beam system, and transmission electron microscopy. When used as the anode material for lithium-ion batteries, Sb_2S_3 hollow microspheres manifest excellent rate property and enhanced lithium-storage capability and can deliver a discharge capacity of 674 m Ah g^(-1) at a current density of 200 m A g^(-1) after 50 cycles. Even at a high currentdensity of 5000 m A g^(-1), a discharge capacity of541 m Ah g^(-1) is achieved. Sb_2S_3 hollow microspheres also display a prominent sodium-storage capacity and maintain a reversible discharge capacity of 384 m Ah g^(-1) at a current density of 200 m A g^(-1) after 50 cycles. The remarkable lithium/sodium-storage property may be attributed to the synergetic effect of its nanometer size and three-dimensional hierarchical architecture, and the outstanding stability property is attributed to the sufficient interior void space,which can buffer the volume expansion.

Fabrication of TiO_2 hollow microspheres using K_3PW_(12)O_(40) as template

Fabrication of TiO 2 hollow microspheres（TiO 2-HMSs） has attracted considerable attention owing to their low density,high photoreactivity,and easy to separate and reuse. A fluoride-free method for the fabrication of TiO 2-HMSs is reported by refluxing a mixed solution of H3PW12O40（0.4 mmol）,KCl（2.5 mmol） and Ti（SO4）2（2–25 mmol） at 125 °C for 8 h,followed by decomposition of the K3PW12O40（KPW） template in basic solution. The prepared TiO 2-HMSs are characterized by X-ray diffraction,transmission electron microscopy,scanning electron microscopy,Fourier transform infrared spectroscopy,ultraviolet-visible diffuse reflectance spectroscopy and X-ray photoelectron spectroscopy. The activities of the photocatalysts are evaluated by photocatalytic degradation of Brilliant Red X-3B,an anionic dye,under UV irradiation. It is observed that the TiO 2-HMSs exhibit diameters of approximately 0.5–1 μm,and the photocatalytic activity of TiO 2-HMSs initially increases and then decreases with an increasing amount of Ti（SO4）2. The TiO 2-HMSs prepared in the presence of 4 mmol Ti（SO4）2 exhibit the highest photocatalytic activity,which is 2.1 times higher than TiO 2 nanoparticles（prepared in the absence of the KPW template）. The enhanced photocatalytic activity of the prepared TiO 2-HMSs is ascribed to the improved crystallization,coupling effect between TiO 2and the residual KPW template,and the unique hollow structures of TiO 2-HMSs.

A review of recent progress in preparation of hollow polymer microspheres

The preparation methods of hollow polymer microspheres both at home and abroad are summarized, and their preparation mechanisms and developmental states are presented. These methods include the liquid droplet method, dried-gel droplet method, self-assembly method, microencapsulation method, emulsion polymerization method and the template method. Hollow polystyrene microspheres are the most extensively studied in the research of hollow polymer microspheres. Through comparison of the advantages and disadvantages of different preparation methods, it is concluded that microencapsulation method is most suitable for preparing polystyrene hollow microspheres.

SYNTHESIS OF MONODISPERSE HOLLOW POLYMER MICROSPHERES WITH FUNCTIONAL GROUPS BY DISTILLATION PRECIPITATION POLYMERIZATION

Monodisperse hollow polymer microspheres having various functional groups on the shell-layer, such as carboxylic acid, pyridyl and amide, were prepared by two-stage distillation precipitation polymerization in neat acetonitrile in the absence of any stabilizer or additive, during which monodisperse poly（methacrylic acid） （PMAA） afforded from the first-stage polymerization was utilized as the seeds for the second-stage polymerization. The shell layer with different functional groups was formed during the second-stage copolymerization of either divinylbenzene （DVB） or ethyleneglycol dimethacrylate （EGDMA） as crosslinker and the functional comonomers, in which the hydrogen-bonding interaction between the carboxylic acid group of PMAA core and the functional groups of the corresponding comonomers, including carboxylic acid, amide and pyridyl, played an essential role for the formation of monodisperse core-shell functional microspheres. The hollow polymer microspheres were then developed after the subsequent removal of PMAA cores by dissolution in ethanol under basic condition. Transmission electron microscopy （TEM） and scanning electron microscopy （SEM） were used to determine the morphology of the resultant PMAA core, functional core-shell microspheres and the corresponding hollow polymer microspheres with different functional groups. FT-IR spectra confirmed the successful incorporation of the various functional groups on the shell layer of the hollow polymer microspheres.

Hollow Carbon Microspheres/MnO_2 Nanosheets Composites:Hydrothermal Synthesis and Electrochemical Behaviors

This article reported the electrochemical behaviors of a novel hollow carbon microspheres/manganese dioxide nanosheets(micro-HC/nano-MnO2) composite prepared by an in situ self-limiting deposition method under hydrothermal condition. The results of scanning electron microscopy reveal that MnO2 nanosheets homogeneously grow onto the surface of micro-HC to form a loose-packed microstructure. The quantity of MnO2 required in the electrode layer has thereby been reduced significantly, and higher specific capacitances have been achieved. The micro-HC/nano-MnO2 electrode presents a high capacitance of 239.0 F g-1 at a current density of 5 m A cm-2, which is a strong promise for high-rate electrochemical capacitive energy storage applications.

Preparation of Hollow Porous HAP Microspheres as Drug Delivery Vehicles

Hollow HAP microspheres in sub-millimeter size were prepared and investigated as a drug delivery vehicle. The LCB （lithium-calcium borate） glass microspheres, which were made through flame spray process, were chosen as precursor for hollow HAP microspheres. The LCB glass microspheres reacted with phosphate buffer （K2HPO4） solution for 5 days at 37 ℃. During the reaction the Ca-P-OH compound precipitated on the surface of LCB glass microspheres and formed porous shells. Then the microspheres turned to be hollow ones with the same diameter as the glass microspheres after LCB glass run out in the chemical reaction. After heat-treated at 600 ℃ for 4 h, the Ca-P-OH compound became HAP, thus the hollow HAP microspheres were produced. The mechanism of forming hollow HAP microspheres through the chemical reaction between phosphate buffer and LCB glass was confirmed by the XRD analysis. The microstructure characteristics of the hollow, porous microspheres were observed by SEM.

Lithium Storage Performance of Hollow and Core/Shell TiO_2 Microspheres Containing Carbon

TiO2 microspheres containing carbon have been synthesized viaa one-pot hydrothermal process using CTAB as the mesoporous template and nanoparticle stabilizer and Ti(SO4)2and sucrose as titanium and carbon precursors,respectively. Through well designed calcinations, Ti O2 microspheres with various amounts of carbon-residue,such as core/shell C@TiO2, hollow neat H–TiO2, and hollow C/TiO2 composites, are obtained. When these microspheres are used as anode materials for lithium ion batteries, the lithium storage performance is significantly influenced by the structure and carbon-residue. With a thin shell of TiO2 nanoparticles and carbon-residue, the capacity of hollow C/TiO2 composites maintains at 143.3 m A·h·g-1at 0.5 C(83.5 m A·g-1) after 100 cycles.Moreover, after high rate charge/discharge cycles from 0.2 C to 20 C and back to 0.2 C again, the reversible capacity recovers atas high as 195.1 m A·h·g-1with respect to its initial value of 205.0 m A·h·g-1. The results of cycle voltammograms and electrochemical impedance spectroscopy further reveal that Li+insertion/extraction processes are reversible, and the diffusion coefficient of Li+in the hollow C/TiO2 composites is much higher than those of others, because the hollow structure can act as the ion-buffering reservoir and facilitate Li+transfer from both sides of the shell, and the carbon-residue in the shell improves the conductivity as well.

Step-scheme ZnO@ZnS hollow microspheres for improved photocatalytic H_(2) production performance

Constructing a step-scheme heterojunction at the interface between two semiconductors is an efficient way to optimize the redox ability and accelerate the charge carrier separation of a photocatalytic system for achieving high photocatalytic performance.In this study,we prepared a hierarchical ZnO@ZnS step-scheme photocatalyst by incorporating ZnS into the outer shell of hollow ZnO microspheres via a simple in situ sulfidation strategy.The ZnO@ZnS step-scheme photocatalysts had a large surface area,high light utilization capacity,and superior separation efficiency for photogenerated charge carriers.In addition,the material simulation revealed that the formation of the step-scheme heterojunction between ZnO and ZnS was due to the presence of the built-in electric field.Our study paves the way for design of high-performance photocatalysts for H_(2) production.

Effect of particle size on the preparation and microwave absorption properties of FeSiAl magnetically soft alloy hollow microspheres

FeSiAl magnetically soft alloy hollow microspheres(MSAHMs) were prepared by self-reactive quenching technology based on Fe + Si + AI + KNO_3 reactive systems, in order to obtain absorbents with light weight, low frequency and high efficiency. Firstly, twice-balling adhesive precursor method was used to obtain FeSiAl magnetically soft alloy agglomerate powders. Then agglomerate powders with the mesh number of 150-240, 240-325 and 325-400 were sprayed through the flame field into the quenching water. At last, FeSiAl MSAHMs with coarse(average at 86.97 μm), medium(average at 52.16 μm) and fine particles(average at 31.80 μm) were got. Effect of particle size on the phases and microwave absorption properties in low frequency band was studied by XRD and vector network analyzer. The results show that,Fe_3 Si_(0.7)Al_(0.3) and Fe_3 Si_(0.5)Al_(0.5) appear in the phase components of FeSiAl MSAHMs,which is important to improve the microwave absorption properties in low frequency. In addition, the real part(ε′) and imaginary part(ε″) of complex permittivity, the real part(μ′) and imaginary part(μ″) of complex permeability of FeSiAl MSAHMs all present the trend of fine particles > medium particles > coarse particles. The microwave absorption properties in low frequency are improved with the increasing of particle size, and the absorption peak moves to lower frequency range. The properties of fine particles are the best. Their matching thickness of samples is at 5 mm, and the minimum reflectivity is-43 dB at this thickness. The absorption frequency band lower than-10 dB is 4.6-7.6 GHz with a bandwidth of 3 GHz.

Rambutan-like Co P@Mo-Co-O hollow microspheres for efficient hydrogen evolution reaction in alkaline solution

Water electrolysis has attracted a lot of attention in recent years for hydrogen production.CoP has been widely investigated as a traditional electrocatalyst for hydrogen evolution reaction(HER).However,the strong bond strength of P-H bond and weak chemical stability are still the key problems in affecting catalytic performance of CoP.In this work,we synthesized rambutan-like CoP@Mo-Co-O hollow microspheres as HER electrocatalyst,solving the two problems of CoP as electrocatalyst.Benefiting from the unique three-dimensional space structure and interface effect between CoP and Mo-Co-O,the synthesized CoP@Mo-Co-O shows a small overpotential of 62 mV at the current density of 10 mA cm^-2 for HER,which is much lower than the corresponding overpotential of pure CoP microspheres(117 mV).Rambutan-like CoP@Mo-Co-O hollow microspheres also show robust long-term stability and excellent cycling stability.This work provides a new method for the design and improvement of non-precious HER electrocatalysts.

Facile Preparation of Al2O3 Hollow Microspheres Via a Urea-mediated Precipitation Process

Al2 O3 hollow microspheres without noticeable aggregation have been prepared via a facile templating route with urea-mediated precipitation. The precipitation process is different from the surfaceadsorption method which is confined to the adsorption capacity of the template surface. TEM and SEM images indicate that most of these Al2 O3 hollow microspheres with shell thickness of tens of nanometers and diameters in a narrow range of 100-200 nm consist of a shell of closely packed nanoparticles. The optimal amount of H2 O and EtOH are 40 and 120 m L, respectively. The specific surface area, average pore size and pore volume of the Al2 O3 hollow microspheres（calcinated at 600 ℃） are 328.52 m2/g, 17.496 nm and 1.985 cm3/g, respectively. As the calcination temperature increases from 600 to 1 100 ℃, the phase composition changes from γ-Al2 O3 to θ-Al2 O3 and a-Al2 O3, and the surface morphology appears to change from a relatively rough surface formed by nanoparticles to a smooth surface formed by lamellar, which lead to the closure of pore channels and the reduction of specific surface.

Controllable preparation of hierarchical NiO hollow microspheres with high pseudo-capacitance

Nickel oxide(NiO)hollow microspheres with hierarchical structure were fabricated through a process consisting of a self-assembling,hydrothermal reaction and calcination.The prepared NiO hollow microspheres composed of many nanoflakes,are about 2-3μm in diameter.The length of the NiO flakes,having clear edges,is about 500-700 nm,while the thickness is only about 40-50 nm.This indicates that the NiO microspheres possess a hierarchical structure that can provide porous channels to facilitate the transmission of both electrons and electrolyte ions.NiO microspheres exhibit a high specific capacitance of about 1340 F/g at a current density of 1 A/g and high capacitance retention about 96.5%after 1000 cycles.What’s more,the conductive mechanism of nickel oxide for electrochemical capacitor electrodes was also studied.

Highly photoreactive TiO_2 hollow microspheres with super thermal stability for acetone oxidation

TiO2hollow microspheres(TiO2‐HMSs)have attracted much attention because of their high photoreactivity,low density,and good permeability.However,anatase TiO2‐HMSs have poor thermal stability.In this study,surface‐fluorinated TiO2‐HMSs were assembled from hollow nanoparticles by the hydrothermal reaction of the mixed Ti(SO4)2–NH4HF–H2O2solution at180°C.The effect of the calcination temperature on the structure and photoreactivity of the TiO2‐HMSs was systematically investigated,which was evaluated by photocatalytic oxidation of acetone in air under ultraviolet irradiation.We found that after calcination at300°C,the photoreactivity of the TiO2‐HMSs decreases from1.39×10?3min?1(TiO2‐HMS precursor)to0.82×10?3min?1because of removal of surface‐adsorbed fluoride ions.With increasing calcination temperature from300to900°C,the building blocks of the TiO2‐HMSs evolve from truncated bipyramidal shaped hollow nanoparticles to round solid nanoparticles,and the photoreactivity of the TiO2‐HMSs steady increases from0.82×10?3to2.09×10?3min?1because of enhanced crystallization.Further increasing the calcination temperature to1000and1100°C results in a decrease of the photoreactivity,which is ascribed to a sharp decrease of the Brunauer–Emmett–Teller surface area and the beginning of the anatase–rutile phase transformation at1100°C.The effect of surface‐adsorbed fluoride ions on the thermal stability of the TiO2‐HMSs is also discussed.

Silver Hollow Microspheres: Large-scale Synthesis, Characterization and Electromagnetic Shielding Property

A facile and large-scale synthesis method to fabricate silver hollow microspheres with controllable morphologies and shell thickness is described using low-cost glass microspheres as templates. The method mainly involves two steps of the preparation of silver-coated glass microsphere core–shell particles by a controllable liquid reduced reaction of Ag[（NH3）2]＋ solution, which only produces silver nanoparticles anchored on the surface of the thiolated glass microsphere templates, and the removal of glass microspheres by wet chemical etching with HF solution. The products are well characterized by field emitted scanning electron microscopy （SEM）, transmitted electron microscopy （TEM）, X-ray photoelectron spectra （XPS）, X-ray diffraction （XRD） and energy dispersive X-ray （EDX） etc. The as-prepared core-shell particles and hollow particles have even and compact silver shells. The electromagnetic shielding coatings based on the silver hollow microspheres are demonstrated to have high conductivity, excellent shielding effectiveness and long durability, suggesting that the silver hollow microspheres obtained here are a novel light-weight electromagnetic shielding filler and will have extensive applications in the electromagnetic compatibility fields.