Microwave-Assisted Synthesis of NiCo_2O_4 Double-Shelled Hollow Spheres for High-Performance Sodium Ion Batteries

The ternary transitional metal oxide NiCo_2O_4 is a promising anode material for sodium ion batteries due to its high theoretical capacity and superior electrical conductivity. However, its sodium storage capability is severely limited by the sluggish sodiation/desodiation reaction kinetics. Herein, NiCo_2O_4 double-shelled hollow spheres were synthesized via a microwave-assisted, fast solvothermal synthetic procedure in a mixture of isopropanol and glycerol, followed by annealing. Isopropanol played a vital role in the precipitation of nickel and cobalt,and the shrinkage of the glycerol quasi-emulsion under heat treatment was responsible for the formation of the double-shelled nanostructure. The as-synthesized productwas tested as an anode material in a sodium ion battery,was found to exhibit a high reversible specific capacity of 511 m Ahg^(-1) at 100 m Ag^(-1), and deliver high capacity retention after 100 cycles.

Core-shell mesoporous carbon hollow spheres as Se hosts for advanced Al-Se batteries

Incorporating a selenium(Se)positive electrode into aluminum(Al)-ion batteries is an effective strategy for improving the overall battery performance.However,the cycling stability of Se positive electrodes has challenges due to the dissolution of intermediate reaction products.In this work,we aim to harness the advantages of Se while reducing its limitations by preparing a core-shell mesoporous carbon hollow sphere with a titanium nitride(C@TiN)host to load 63.9wt%Se as the positive electrode material for Al-Se batteries.Using the physical and chemical confinement offered by the hollow mesoporous carbon and TiN,the obtained core-shell mesoporous carbon hollow spheres coated with Se(Se@C@TiN)display superior utilization of the active material and remarkable cycling stability.As a result,Al-Se batteries equipped with the as-prepared Se@C@TiN composite positive electrodes show an initial discharge specific capacity of 377 mAh·g^(-1)at a current density of 1000 mA·g^(-1)while maintaining a discharge specific capacity of 86.0 mAh·g^(-1)over 200 cycles.This improved cycling performance is ascribed to the high electrical conductivity of the core-shell mesoporous carbon hollow spheres and the unique three-dimensional hierarchical architecture of Se@C@TiN.

Ultrafine Pt nanoparticles supported on double-shelled C/TiO2 hollow spheres material as highly efficient methanol oxidation catalysts

Catalyst support is extremely important for future fuel cell devices.In this work,we developed doubleshelled C/TiO2(DSCT)hollow spheres as an excellent catalyst support via a template-directed method.The combination of hollow structure,TiO2 shell and carbon layer results in excellent electron conductivity,electrocatalytic activity,and chemical stability.These uniformed DSCT hollow spheres are used as catalyst support to synthesize Pt/DSCT hollow spheres electrocatalyst.The resulting Pt/DSCT hollow spheres exhibited high catalytic performance with a current density of 462 mA mg^-1 for methanol oxidation reaction,which is 2.52 times higher than that of the commercial Pt/C.Furthermore,the increased tolerance to carbonaceous poisoning with a higher If/Ibratio and a better long-term stability in acid media suggests that the DSCT hollow sphere is a promising C/TiO2-based catalyst support for direct methanol fuel cells applications.

Preparation and Photocatalytic Performance of Double-Shelled Hollow W_(18)O_(49)@C_(3)N_(4)@Ti_(3)C_(2)Microspheres

C_(3)N_(4),C_(3)N_(4)@Ti_(3)C_(2)and W_(18)O_(49)@C_(3)N_(4)@Ti_(3)C_(2)hollow spheres were successfully prepared by using SiO_(2)template followed by gradual deposition method.The degradation of phenol solution and photolysis ability were tested to characterize its photocatalytic activity.Compared with the single-shelled C_(3)N_(4)and C_(3)N_(4)@Ti_(3)C_(2)hollow spheres,double-shelled W_(18)O_(49)@C_(3)N_(4)@Ti_(3)C_(2)hollow spheres possessed larger surface area and fast charge separation efficiency,exhibiting about 8.9 times and 4.0 times higher H_(2)evolution than those of C_(3)N_(4),C_(3)N_(4)@Ti_(3)C_(2)hollow spheres,respectively.The photocatalytic mechanism of the W_(18)O_(49)@C_(3)N_(4)@Ti_(3)C_(2)hollow spheres were carefully investigated according to the results of morphology design and photoelectric performance.A Z scheme mechanism based on the construction of heterojunctions was proposed to explain the improvement of photocatalytic performance.This new charge transfer mechanism appears to greatly inhibit the recombination of electrons/holes during the charge transfer process,while maintaining its strong hydrogen reduction ability,resulting in a higher photocatalytic performance.

Electrochemical hydrogen evolution efficiently boosted by interfacial charge redistribution in Ru/MoSe_(2) embedded mesoporous hollow carbon spheres

The strong metal-support interaction inducing combined effect plays a crucial role in the catalysis reaction. Herein, we revealed that the combined advantages of MoSe_(2), Ru, and hollow carbon spheres in the form of Ru nanoparticles(NPs) anchored on a two-dimensionally ordered MoSe_(2) nanosheet-embedded mesoporous hollow carbon spheres surface(Ru/MoSe_(2)@MHCS) for the largely boosted hydrogen evolution reaction(HER) performance. The combined advantages from the conductive support, oxyphilic MoSe_(2), and Ru active sites imparted a strong synergistic effect and charge redistribution in the Ru periphery which induced high catalytic activity, stability, and kinetics for HER. Specifically, the obtained Ru/MoSe_(2)@MHCS required a small overpotential of 25.5 and 38.4 mV to drive the kinetic current density of 10 mA cm^(-2)both in acid and alkaline media, respectively, which was comparable to that of the Pt/C catalyst. Experimental and theoretical results demonstrated that the charge transfer from MoSe_(2) to Ru NPs enriched the electronic density of Ru sites and thus facilitated hydrogen adsorption and water dissociation. The current work showed the significant interfacial engineering in Ru-based catalysts development and catalysis promotion effect understanding via the metal-support interaction.

MoS_2 Nanosheet Arrays Rooted on Hollow rGO Spheres as Bifunctional Hydrogen Evolution Catalyst and Supercapacitor Electrode

MoS_2 has attracted attention as a promising hydrogen evolution reaction(HER) catalyst and a supercapacitor electrode material. However, its catalytic activity and capacitive performance are still hindered by its aggregation and poor intrinsic conductivity. Here, hollow rGO sphere-supported ultrathin MoS_2 nanosheet arrays(hrGO@MoS_2) are constructed via a dual-template approach and employed as bifunctional HER catalyst and supercapacitor electrode material. Because of the expanded interlayer spacing in MoS_2 nanosheets and more exposed electroactive S–Mo–S edges, the constructed h-rGO@MoS_2 architectures exhibit enhanced HER performance. Furthermore, benefiting from the synergistic effect of the improved conductivity and boosted specific surface areas(144.9 m^2 g^(-1), ca. 4.6-times that of pristine MoS_2), the h-rGO@MoS_2 architecture shows a high specific capacitance(238 F g^(-1) at a current density of 0.5 A g^(-1)), excellent rate capacitance, and remarkable cycle stability. Our synthesis method may be extended to construct other vertically aligned hollow architectures,which may serve both as efficient HER catalysts and supercapacitor electrodes.

Fabrication of triple-shelled hollow spheres with optical properties via RAFT polymerization

The triple-shelled hollow spheres with optical properties were prepared via reversible addition-fragmentation chain transfer (RAFT) polymerization.After removal the core templates of the poly(styrene),the hollow silica spheres were obtained.The coating process of poly(methyl methacrylate)(PMMA) on the hollow silica spheres surface via surface RAFT polymerization was performed subsequently.The polymers coated on the hollow spheres surfaces were end-functionalized by trithiocarbonate,and they were used as RAFT agent to proceed the chain extension polymerization using Tb complex as monomer.The samples were characterized by FT-IR,SEM and luminescence spectroscopy respectively.The results indicated that the triple-shelled hollow spheres had been prepared successfully and the average diameter of the hollow core was about 1μm.

Fluidized bed coating efficiency and morphology of coatings for producing Al-based nanocomposite hollow spheres

Abstract： We performed fluidized bed coating ofAl-based nanoeomposite powder-binder suspensions onto polymer substrates. The effects of the type and amount of the binder and nanoparticle additive on the coating process efficiency and coating characteristics were investigated. The efficiency decreased from 52% to 49% as the processing time increased from 15 to 20 min. However, the amount and thickness of the coating also increased as the processing time and amount of the binder were increased. The addition of nanoparticles to the system decreased the thickness of the coating from 222 to 207 μm when polyvinyl alcohol （PVA） was used as a binder. The suspension containing 3wt% R-4410 binder exhibited the greatest efficiency of 60%.

TiO_2-coated SnO_2 hollow spheres as anode materials for lithium ion batteries

TiO2-coated SnO2 （TCS） hollow spheres, which are new anode materials for lithium ion （Li-ion） batteries, were prepared and characterized with X-ray diffraction （XRD）, scanning electron microscopy （SEM）, transmission electron microscopy （TEM）, cyclic voltammetry （CV）, and galvanostatic charge/discharge tests. The results obtained from XRD, SEM, and TEM show that TiO2 can be uniforrrdy coated on the surface of SnO2 hollow spheres with the assistance of anionic surfactant. The cyclic voltammograms indicate that both TiO2 and SnO2 exhibit the activity for Li-ion storage. The charge/discharge tests show that the prepared TCS hollow spheres have a higher reversible coulomb efficiency and a better cycling stability than the uncoated SnO2 hollow spheres.

Facile Synthesis of Uniform Hollow Hematite Sub-micro Spheres with Controllable Shell Thickness

A simple method was developed to prepare the uniform hematite hollow submicro-spheres with controllable structure and different diameter based on monodisperse poly（styrene-co-acrylic acid） [P（St-co-AA）] particles. The structure and formation mechanism of the hollow spheres were investigated in detail. The control mechanism of shell thickness was also discussed. The results indicated that the shell thickness and coarseness of the synthesized core-shell hematite hollow spheres could be tuned simply by the surface carboxyl content of the P（St-co-AA） particles. This method provided a new approach for the structure control in the preparation of hollow spheres. A Brunauer-Emmett-Teller （BET） test shows that the prepared hollow spheres have large surface areas which were decreased along with the increase of the diameter. The magnetic properties of the as-obtained hematite hollow spheres were investigated. The result showed that the coercivity and saturated magnetization were increased along with the increase of the shell thickness, and the remanent magnetization was increased along with the decrease of the diameter.

Fabrication of functional hollow carbon spheres with large hollow interior as active colloidal catalysts

In this study, we have established a facile method to synthesize functional hollow carbon spheres with large hollow interior, which can act as active colloidal catalysts. The method includes the following steps： first, hollow polymer spheres with large hollow interior were prepared using sodium oleate as the hollow core generator, and 2,4-dihydroxybenzoic acid and hexamethylene tetramine （HMT） as the polymer precursors under hydrothermal conditions; Fe3＋ or Ag＋ cations were then introduced into the as-prepared hollow polymer spheres through the carboxyl groups; finally, the hollow polymer spheres can be pseudomorphically converted to hollow carbon spheres during pyrolysis process, meanwhile iron or silver nanoparticles can also be formed in the carbon shell simultaneously. The structures of the obtained functional hollow carbon spheres were characterized by TEM, XRD, and TG. As an example, Ag-doped hollow carbon spheres were used as colloid catalysts which showed high catalytic activity in 4-nitrophenol reduction reaction.

Preparation of CaCO_3 Hollow Spheres in an Aqueous Binary-additive System

CaCO3 hollow spheres were prepared easily in anion surfactants （sodium dodecylbenzenesulfonate （SDBS）） and aspartic （Asp） acid binary-additive system by using an easy rapid agitation method. The as-prepared products were characterized with scanning electron microscopy （SEM）, FT-IR and X-ray diffraction. The results suggested that the CaCO3 hollow spheres have diameters ranging from 1 to 2 μm, and their wall is constituted of many nano-particles. Moreover, the possible formation mechanism of the hollow spherical structure was proposed.

A Bi-layer Composite Film Based on TiO_2 Hollow Spheres, P25,and Multi-walled Carbon Nanotubes for Efficient Photoanode of Dye-sensitized Solar Cell

A bi-layer photoanode for dye-sensitized solar cell(DSSC) was fabricated, in which TiO_2 hollow spheres(THSs) were designed as a scattering layer and P25/multi-walled carbon nanotubes(MWNTs) as an under-layer. The THSs were synthesized by a sacrifice template method and showed good light scattering ability as an over-layer of the photoanode. MWNTs were mixed with P25 to form an under-layer of the photoanode to improve the electron transmission ability of the photoanode. The power conversion efficiency of this kind of DSSC with bi-layer was enhanced to 5.13 %,which is 14.25 % higher than that of pure P25 DSSC.Graphical Abstract A bi-layer composite photoanode based on P25/MWNTs-THSs with improved light scattering and electron transmission, which will provide a new insight into fabrication and structure design of highly efficient dyesensitized solar cells.

Sulfonic Acid Modified Hollow Silica Spheres and Its Application in Proton Exchange Membranes

In order to improve the proton conductivity of hollow silica spheres （HSS）/perfluorosulfonic acid ion-exchange （PFSA） composite membranes as proton exchange membrane,sulfonic acid groups were grafted onto the surfaces of HSS via post grafting methods.TEM images and FT-IR spectra of the obtained sulfonic acid groups modified hollow silica spheres （SAMHSS） illustrated that the sulfonic acid groups were successfully grafted onto the surfaces of HSS.Water uptake and swelling degree of SAMHSS/PFSA composite membranes were found much higher than those of HSS/PFSA membranes due to the introduction of hydrophilic sulfonic acid groups.In a range from 50 ℃ to 130 ℃,the highest conductivity of composite membranes was obtained when 5 wt% SAMHSS was loaded.The maximum conductivity reached 7.5×10-2 S·cm-1 at 100 ℃ and 100% relative humidity,even the temperature increased to 130 ℃,the conductivity of composite membranes with 5 wt% SAMHSS could reach 3.7×10-2 S·cm-1 at 100 % relative humidity,while the conductivity of the recast PFSA was only 2.2×10-3 S·cm-1.

Hierarchical porous nitrogen,oxygen,and phosphorus ternary doped hollow biomass carbon spheres for high-speed and long-life potassium storage

Limited lithium resources have promoted the exploration of new battery technologies.Among them,potassium-ion batteries are considered as promising alternatives.At present,commercial graphite and other carbon-based materials have shown good prospects as anodes for potassium-ion batteries.However,the volume expansion and structural collapse caused by periodic K+insertion/extraction have severely restricted further development and application of potassium-ion batteries.A hollow biomass carbon ball(NOP-PB)ternarily doped with N,O,and P was synthesized and used as the negative electrode of a potassium-ion battery.X-ray photoelectron spectroscopy,Fourier‐transform infrared spectroscopy,and transmission electron microscopy confirmed that the hollow biomass carbon spheres were successfully doped with N,O,and P.Further analysis proved that N,O,and P ternary doping expands the interlayer distance of the graphite surface and introduces more defect sites.DFT calculations simultaneously proved that the K adsorption energy of the doped structure is greatly improved.The solid hollow hierarchical porous structure buffers the volume expansion of the potassium insertion process,maintains the original structure after a long cycle and promotes the transfer of potassium ions and electrons.Therefore,the NOP‐PB negative electrode shows extremely enhanced electrochemical performance,including high specific capacity,excellent long‐term stability,and good rate stability.

Rambutan-like hollow carbon spheres decorated with vacancy-rich nickel oxide for energy conversion and storage

Transition metal oxides hold great promise for lithium-ion batteries(LIBs)and electrocatalytic water splitting because of their high abundance and high energy density.However,designing and fabrication of efficient,stable,high power density electrode materials are challenging.Herein,we report rambutan-like hollow carbon spheres formed by carbon nanosheet decorated with nickel oxide(NiO)rich inmetal vacancies(denoted as h-NiO/C)as a bifunctional electrode material for LIBs and electrocatalytic oxygen evolution reaction(OER).When being used as the anode of LIBs,the h-NiO/C electrode shows a large initial capacity of 885mAh g−1,a robust stability with a high capacity of 817mAh g−1 after 400 cycles,and great rate capability with a high reversible capacity of 523mAh g−1 at 10Ag−1 after 600 cycles.Moreover,working as an OER electrocatalyst,the h-NiO/C electrode shows a small overpotential of 260mV at 10mAcm−2,a Tafel slope of 37.6mVdec−1 along with good stability.Our work offers a cost-effective method for the fabrication of efficient electrode for LIBs and OER.

Facile Synthesis of SnO_2 Hollow Microspheres and Their Optical Property

SnO2 hollow microspheres were fabricated via a hydrothermal synthesis method assisting by the complex surfactant system of polyacrylamide and polyethylene glycol.Observation by field emission scanning electron microscopy （FESEM） showed the SnO2 hollow spheres were composed of nanoparticles.The growth mechanism for the formation of hollow spheres was proposed.UV spectroscopy and photoluminescence （PL） were used to investigate the optical properties of the products.The PL result showed that four peaks,containing the emission from recombination of free excitons,were observed in the photoluminescence spectrum.

Template-free Polyoxometalate-assisted Synthesis of Au/ZnO Hollow Sphere Hererostructures for Photocatalytic Water Purification

The controlled synthesis of ZnO hollow spheres is successfully achieved through a facile solvothermal method using a Keggin-type silicotungstic acid（H_4 Si（W_3 O_（10））_4：HSW） as structure directing agent. The formation process of these hollow spheres is proposed based on a variety of controlled experiments. In addition, Au nanoparticles are loaded onto the surface of ZnO hollow spheres. It is found that the Au-loaded ZnO（Au/ZnO） composites exhibit greatly enhanced activity on oxidizing Rhodamine B（Rh B） under simulated UV or visible light irradiation, compared to the pristine ZnO hollow spheres. The improved performance of Au/ZnO heterostructures is mainly attributed to the enhanced optical absorption and the accelerated separation and migration of photogenerated charge carriers. Moreover, the photocatalytic reaction mechanisms are proposed based on the results of electron spin resonance（ESR） analysis, photoelectrochemical measurements, and photocatalytic evaluation. The results and findings are expected to provide significance to the synthesis of noble metal-semiconductor hybrids towards water purification.

Template Polymerization Based on Stober Method:an Improved Method for Fabrication of Hollow Polysiloxane Spheres

A modified Stober method has been developed which permits the controlled growth of spherical hollow spheres with diameters between 197 and 208 nanometers by consecutively cocondensed methyltrimethoxysilane and dimethyldimethoxysilane monomers onto microemulsion of polydimethylsiloxane and subsequently removing the templated polydimethylsiloxane by exposure to solvents. Ammonia was used as a morphological catalyst. The morphology of the polymer spheres was demonstrated by transmission electron micrographs （TEM） and atomic force microscopy （AFM）.

ON THE FREE VIBRATION OF A SUBMERGED FGM HOLLOW SPHERE

The free vibration of a functionally graded material hollow spheresubmerged in a compress- ible fluid medium is exactly analyzed. Thesphere is assumed to be spherically isotropic with material consta-nts being inhomogeneous along the radial direction. By employing aseparation technique as well as the spherical harmonics expansionmethod, the governing equations are simplified to an uncoupledsecond-order ordinary differential equation, and a coupled system oftwo such equations. Solutions to these equations are given when theelastic constants and the mass density are power functions of theradial coordinate. Numerical examples are finally given to show theeffect of the material gradient on the natural frequencies.