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.

Atomically Dispersed Ruthenium Catalysts with Open Hollow Structure for Lithium-Oxygen Batteries

Lithium–oxygen battery with ultrahigh theoretical energy density is considered a highly competitive next-generation energy storage device,but its practical application is severely hindered by issues such as difficult decomposition of discharge products at present.Here,we have developed N-doped carbon anchored atomically dispersed Ru sites cathode catalyst with open hollow structure(h-RuNC)for Lithium–oxygen battery.On one hand,the abundance of atomically dispersed Ru sites can effectively catalyze the formation and decomposition of discharge products,thereby greatly enhancing the redox kinetics.On the other hand,the open hollow structure not only enhances the mass activity of atomically dispersed Ru sites but also improves the diffusion efficiency of catalytic molecules.Therefore,the excellent activity from atomically dispersed Ru sites and the enhanced diffusion from open hollow structure respectively improve the redox kinetics and cycling stability,ultimately achieving a high-performance lithium–oxygen battery.

Vacancy engineering mediated hollow structured ZnO/ZnS S-scheme heterojunction for highly efficient photocatalytic H_(2) production

Designing a step-scheme(S-scheme)heterojunction photocatalyst with vacancy engineering is a reliable approach to achieve highly efficient photocatalytic H_(2)production activity.Herein,a hollow ZnO/ZnS S-scheme heterojunction with O and Zn vacancies(VO,Zn-ZnO/ZnS)is rationally constructed via ion-exchange and calcination treatments.In such a photocatalytic system,the hollow structure combined with the introduction of dual vacancies endows the adequate light absorption.Moreover,the O and Zn vacancies serve as the trapping sites for photo-induced electrons and holes,respectively,which are beneficial for promoting the photo-induced carrier separation.Meanwhile,the S-scheme charge transfer mechanism can not only improve the separation and transfer efficiencies of photo-induced carrier but also retain the strong redox capacity.As expected,the optimized VO,Zn-ZnO/ZnS heterojunction exhibits a superior photocatalytic H_(2) production rate of 160.91 mmol g^(-1)h^(-1),approximately 643.6 times and 214.5 times with respect to that obtained on pure ZnO and ZnS,respectively.Simultaneously,the experimental results and density functional theory calculations disclose that the photo-induced carrier transfer pathway follows the S-scheme heterojunction mechanism and the introduction of O and Zn vacancies reduces the surface reaction barrier.This work provides an innovative strategy of vacancy engineering in S-scheme heterojunction for solar-to-fuel energy conversion.

A 3-Node Co-Rotational Triangular Finite Element for Non-Smooth,Folded and Multi-Shell Laminated Composite Structures

Based on the first-order shear deformation theory,a 3-node co-rotational triangular finite element formulation is developed for large deformation modeling of non-smooth,folded and multi-shell laminated composite structures.The two smaller components of the mid-surface normal vector of shell at a node are defined as nodal rotational variables in the co-rotational local coordinate system.In the global coordinate system,two smaller components of one vector,together with the smallest or second smallest component of another vector,of an orthogonal triad at a node on a non-smooth intersection of plates and/or shells are defined as rotational variables,whereas the two smaller components of the mid-surface normal vector at a node on the smooth part of the plate or shell(away from non-smooth intersections)are defined as rotational variables.All these vectorial rotational variables can be updated in an additive manner during an incremental solution procedure,and thus improve the computational efficiency in the nonlinear solution of these composite shell structures.Due to the commutativity of all nodal variables in calculating of the second derivatives of the local nodal variables with respect to global nodal variables,and the second derivatives of the strain energy functional with respect to local nodal variables,symmetric tangent stiffness matrices in local and global coordinate systems are obtained.To overcome shear locking,the assumed transverse shear strains obtained from the line-integration approach are employed.The reliability and computational accuracy of the present 3-node triangular shell finite element are verified through modeling two patch tests,several smooth and non-smooth laminated composite shells undergoing large displacements and large rotations.

Tuning Metallic Co0.85Se Quantum Dots/Carbon Hollow Polyhedrons with Tertiary Hierarchical Structure for High-Performance Potassium Ion Batteries

Potassium-ion batteries(KIBs)are a potential candidate to lithium-ion batteries(LIBs)but possess unsatisfactory capacity and rate properties.Herein,the metallic cobalt selenide quantum dots(Co0.85Se-QDs)encapsulated in mesoporous carbon matrix were designed via a direct hydrothermal method.Specifically,the cobalt selenide/carbon composite(Co0.85Se-QDs/C)possesses tertiary hierarchical structure,which is the primary quantum dots,the secondary petals flake,and the tertiary hollow micropolyhedron framework.Co0.85Se-QDs are homogenously embedded into the carbon petals flake,which constitute the hollow polyhedral framework.This unique structure can take the advantages of both nanoscale and microscale features:Co0.85Se-QDs can expand in a multidimensional and ductile carbon matrix and reduce the K-intercalation stress in particle dimensions;the micropetals can restrain the agglomeration of active materials and promote the transportation of potassium ion and electron.In addition,the hollow carbon framework buffers volume expansion,maintains the structural integrity,and increases the electronic conductivity.Benefiting from this tertiary hierarchical structure,outstanding K-storage performance(402 mAh g?1 after 100 cycles at 50 mA g?1)is obtained when Co0.85Se-QDs/C is used as KIBs anode.More importantly,the selenization process in this work is newly reported and can be generally extended to prepare other quantum dots encapsulated in edge-limited frameworks for excellent energy storage.

Fe_(3)O_(4)/Fe/FeS Tri-Heterojunction Node Spawning N-Carbon Nanotube Scaffold Structure for High-Performance Sodium-Ion Battery

The Fe-based anode of sodium-ion batteries attracts much attention due to the abundant source,low-cost,and high specific capacity.However,the low electron and ion transfer rate,poor structural stability,and shuttle effect of NaS_(2)intermediate restrain its further development.Herein,the Fe_(3)O_(4)/Fe/FeS tri-heterojunction node spawned N-carbon nanotube scaffold structure(FHNCS)was designed using the modified MIL-88B(Fe)as a template followed by catalytic growth and sulfidation process.During catalytic growth process,the reduced Fe monomers catalyze the growth of N-doped carbon nanotubes to connect the Fe_(3)O_(4)/Fe/FeS tri-heterojunction node,forming a 3D scaffold structure.Wherein the N-doped carbon promotes the transfer of electrons between Fe_(3)O_(4)/Fe/FeS particles,and the tri-heterojunction facilitates the diffusion of electrons at the interface,to organize a 3D conductive network.The unique scaffold structure provides more active sites and shortens the Na^(+)diffusion path.Meanwhile,the structure exhibits excellent mechanical stability to alleviate the volume expansion during circulation.Furthermore,the Fe in Fe_(3)O_(4)/Fe heterojunction can adjust the dband center of Fe in Fe_(3)O_(4)to enhance the adsorption between Fe_(3)O_(4)and Na2S intermediate,which restrains the shuttle effect.Therefore,the FHNCS demonstrates a high specific capacity of 436 mAh g^(-1)at 0.5 A g^(-1),84.7%and 73.4%of the initial capacities are maintained after 100 cycles at 0.5 A g^(-1)and 1000 cycles at 1.0 A g^(-1).We believe that this strategy gives an inspiration for constructing Fe-based anode with excellent rate capability and cycling stability.

Hollow structured Cu@ZrO_(2) derived from Zr-MOF for selective hydrogenation of CO_(2) to methanol

The development of a highly efficient catalyst for CO_(2) activation and selective conversion to methanol is critical to address the issues associated with the high thermal stability of CO_(2) and controllable synthesis of methanol.Cu-based catalysts have been widely studied because of the low cost and excellent performance in mild conditions.However,the improvement of catalytic activity and selectivity remains challenging.Herein,we prepared hollow Cu@ZrO_(2) catalysts through pyrolysis of Cu-loaded Zr-MOF for CO_(2) hydrogenation to methanol.Low-temperature pyrolysis generated highly dispersed Cu nanoparticles with balanced Cu^(0)/Cu^(+)sites,larger amounts of surface basic sites and abundant Cu-ZrO_(2) interface in the hollow structure,contributing to enhanced catalytic capacity for adsorption/activation of CO_(2) and selective hydrogenation to methanol.In situ Fourier Transform Infrared Spectroscopy revealed the methanol formation followed the formate-intermediated pathway.This work would provide a guideline for the design of high-performance catalysts and the understanding of the mechanism and active sites for CO_(2) hydrogenation to methanol.

A novel Ag/ZnO core-shell structure for efficient sterilization synergizing antibiotics and subsequently removing residuals

The massive use of antibiotics has led to the aggravation of bacterial resistance and also brought environmental pollution problems.This poses a great threat to human health.If the dosage of antibiotics is reduced by increasing its bactericidal performance,the emergence of drug resistance is certainly delayed,so that there's not enough time for developing drug resistance during treatment.Therefore,we selected typical representative materials of metal Ag and semiconductor ZnO nano-bactericides to design and synthesize Ag/ZnO hollow core-shell structures(AZ for short).Antibiotics are grafted on the surface of AZ through rational modification to form a composite sterilization system.The research results show that the antibacterial efficiency of the composite system is significantly increased,from the sum(34.7%+22.8%-57.5%)of the antibacterial efficiency of AZ and gentamicin to 80.2%,net synergizes 22.7%,which fully reflects the effect of 1+1>2.Therefore,the dosage of antibiotics can be drastically reduced in this way,which makes both the possibility of bacterial resistance and medical expenses remarkably decrease.Subsequently,residual antibiotics can be degraded under simple illumination using AZ-self as a photocatalyst,which cuts off the path of environmental pollution.In short,such an innovative route has guiding significance for drug resistance.

Revealing interfacial charge redistribution of homologous Ru-RuS_(2) heterostructure toward robust hydrogen oxidation reaction

Precisely tailoring the surface electronic structures of electrocatalysts for optimal hydrogen binding energy and hydroxide binding energy is vital to improve the sluggish kinetics of hydrogen oxidation reac-tion(HOR).Herein,we employ a partial desulfurization strategy to construct a homologous Ru-RuS_(2) heterostructure anchored on hollow mesoporous carbon nanospheres(Ru-RuS_(2)@C).The disparate work functions of the heterostructure contribute to the spontaneous formation of a unique built-in electric field,accelerating charge transfer and boosting conductivity of electrocatalyst.Consequently,Ru-RuS_(2)@C exhibits robust HOR electrocatalytic activity,achieving an exchange current density and mass activity as high as 3.56 mA cm^(-2) and 2.13 mAμg_(Ru)^(-1),respectively.exceeding those of state-of-the-art Pt/C and most contemporary Ru-based HOR electrocatalysts.Surprisingly,Ru-RuS_(2)@C can tolerate 1000 ppm of cO that lacks in Pt/C.Comprehensive analysis reveals that the directional electron transfer across Ru-RuS_(2) heterointerface induces local charge redistribution in interfacial region,which optimizes and balances the adsorption energies of H and OH species,as well as lowers the energy barrier for water formation,thereby promoting theHoR performance.

Design of ZnSe-CoSe heterostructure decorated in hollow N-doped carbon nanocage with generous adsorption and catalysis sites for the reversibly fast kinetics of polysulfide conversion

Although lithium-sulfur batteries(Li SBs)are regarded as one of the most promising candidates for the next-generation energy storage system,the actual industrial application is hindered by the sluggish solid–liquid phase conversion kinetics,severe shuttle effect,and low sulfur loadings.Herein,a zeolitic imidazolate framework(ZIF)derived heterogeneous ZnSe-CoSe nanoparticles encapsulated in hollow N-doped carbon nanocage(ZnSe-CoSe-HNC)was designed by etching with tannic acid as a multifunctional electrocatalyst to boost the polysulfide conversion kinetics in LiSBs.The hollow structure in ZIF ensures large inner voids for sulfur and buffering volume expansions.Abundant exposed ZnSe-CoSe heterogeneous interfaces serve as bifunctional adsorption-catalytic centers to accelerate the conversion kinetics and alleviate the shuttle effect.Together with the highly conductive framework,the ZnSe-CoSeHNC/S cathode exhibits a high initial reversible capacity of 1305.3 m A h g-1at 0.2 C,high-rate capability,and reliable cycling stability under high sulfur loading and lean electrolyte(maintaining at 745 m A h g-1after 200 cycles with a high sulfur loading of 6.4 mg cm-2and a low electrolyte/sulfur ratio of 6μL mg^(-1)).Theoretical calculations have demonstrated the heterostructures of ZnSe-CoSe offer higher binding energy to lithium polysulfides than that of ZnSe or CoSe,facilitating the electron transfer to lithium polysulfides.This work provides a novel heterostructure with superior catalytic ability and hollow conductive architecture,paving the way for the practical application of functional sulfur electrodes.

Design and applications of hollow‐structured nanomaterials for photocatalytic H2 evolution and CO2 reduction

Photocatalysis is considered a prospective way to alleviate the energy crisis and environmental pollution.It is therefore extremely important to design highly efficient photocatalysts for catalytic systems.In recent years,hollow‐structured materials have attracted considerable interest for application in energy conversion fields owing to their large specific surface areas,improved light absorption,and shortened charge carrier transfer path.Because they contain inner and outer surfaces,hollow‐structured materials can provide a superior platform for the deposition of other components.A number of hollow‐structured hierarchical systems have been designed and fabricated in recent decades.It is important to rationally design and construct complex hierarchical structures.In this review,general preparation approaches for hollow‐structured materials are presented,followed by a summary of the recent synthesis methods and mechanisms of typical hollow‐structured materials for applications in the photocatalytic field.Complex hollow‐structured hierarchical photocatalysts are classified into two types,hollow cocatalyst‐based and hollow host photocatalyst‐based,and the design principle and analysis of the photocatalytic reaction mechanism for photocatalytic H2 evolution and CO_(2) reduction are also introduced.The effects of hollow‐structured materials have also been investigated.This review provides a reference for the rational construction of advanced,highly efficient photocatalytic materials.

Fabrication and Applications of Multi-Fluidic Electrospinning Multi-Structure Hollow and Core–Shell Nanofibers

Recently,electrospinning(ESP)has been widely used as a synthetic technology to prepare nanofibers with unique properties from various raw materials.The applications of functionalized nanofibers have gradually developed into one of the most exciting topics in the field of materials science.In this review,we focus on the preparation of multi-structure fibrous nanomaterials by means of multi-fluidic ESP and review the applications of multi-structure nanofibers in energy,catalysis,and biology.First,the working principle and process of ESP are introduced;then,we demonstrate how the microfluidic concept is com-bined with the ESP technique to the multi-fluidic ESP technique.Subsequently,the applications of multi-structure nanofibers in energy(Li^(+)/Na^(+)batteries and Li–S batteries),hetero-catalysis,and biology(drug delivery and tissue engineering)are introduced.Finally,challenges and future directions in this emerging field are summarized.

Bismuth nanorods confined in hollow carbon structures for high performance sodium-and potassium-ion batteries

Bismuth has drawn widespread attention as a prospective alloying-type anode for sodium-ion batteries(SIBs)and potassium-ion batteries(PIBs)due to its large volumetric capacity.However,such material encounters drastic particle pulverization and overgrowth of solid-electrolyte interphase(SEI)upon repeated(de)alloying,thus causing poor rate and cycling degradation.Herein,we report a unique structure design with bismuth nanorods confined in hollow N,S-codoped carbon nanotubes(Bi@NS-C)fabricated by a solvothermal method and in-situ thermal reduction.Ex-situ SEM observations confirm that such a design can significantly suppress the size fining of Bi nanorods,thus inhibiting the particle pulverization and repeated SEI growth upon charging/discharging.The as achieved Bi@NS-C demonstrates outstanding rate capability for SIBs(96.5%capacity retention at 30 A g^(-1) vs.1 A g^(-1)),and a record high rate performance for PIBs(399.5 m Ah g^(-1)@20 A g^(-1)).Notably,the as constructed full cell(Na_(3)V_(2)(PO_(4))_(3)@C|Bi@NS-C)demonstrates impressive performance with a high energy density of 219.8 W h kg^(-1) and a high-power density of 6443.3 W kg^(-1)(based on the total mass of active materials on both electrodes),outperforming the state-of-the-art literature.

Smart heat isolator with hollow multishelled structures

Safe, green and efficient industrial production has always been the pursuit of the chemical industry. Since thermal energy is the driving force for most of chemical reactions, an ideal reaction tank would have the capacity to automatically regulate heat conduction rate. In detail, this reaction tank should endow an ability that resists the heat loss when the reaction temperature is lower than the target, while accelerating the heat dissipation when the system is overheated. In this case, this smart reactor can not only minimize energy consumption but also reduce safety risks.Hollow structures are known to reduce heat conductivity. Particularly, the hollow structure with multishells can provide more interfaces and thus further inhibit heat transmission, which would be more favorable for heat isolation. Step forward, by coupling HoMSs with temperature-sensitive polymer, a smart heat isolation material has been fabricated in this work. It performs as a good heat isolator at a relatively lower temperature. A heat insulation effect of 6.5℃ can be achieved for the TSPU/3S–TiO_(2)HoMSs with a thickness of 1 mm under the temperature field of 50℃.The thermal conductivity of composite material would be raised under overheating conditions. Furthermore, this composite displays an unusual two-stage phase transformation during heating. Benefiting from the unique multishelled structure, energy is found to be gradually guided into the hollow structure and stored inside. This localized heat accumulation enables the composite to be a potential coating material for intelligent thermal-regulator and site-defined micro-reactor.

Constructing BaTiO_(3)/TiO_(2)@polypyrrole composites with hollow multishelled structure for enhanced electromagnetic wave absorbing properties

BaTiO_(3)/TiO_(2)@polypyrrole(PPy)composites with hollow multishelled structure(HoMS)were constructed to enhance the electromagnetic wave absorbing properties of BaTiO_(3)-based absorbing material.BaTiO_(3)/TiO_(2)HoMSs were prepared by hydrothermal crystallization using TiO_(2)Ho MSs as template.Then,FeCl3 was introduced to initiate the oxidative polymerization of pyrrole monomer,forming BaTiO_(3)/TiO_(2)@PPy HoMSs successfully.The electromagnetic wave absorbing properties of BaTiO_(3)/TiO_(2)HoMSs and BaTiO_(3)/TiO_(2)@PPy Ho MSs with different shell number were investigated using a vector network analyzer.The results indicate that BaTiO_(3)/TiO_(2)@PPy HoMSs exhibit improved microwave absorption compared with BaTiO_(3)/TiO_(2)HoMSs.In particular,tripled-shelled BaTiO_(3)/TiO_(2)@PPy HoMS has the most excellent absorbing performance.The best reflection loss can reach up to-21.80 dB at 13.34 GHz with a corresponding absorber thickness of only 1.3 mm,and the qualified absorption bandwidth of tripled-shelled BaTiO_(3)/TiO_(2)@PPy HoMS is up to 4.2 GHz.This work paves a new way for the development of high-performance composite microwave absorbing materials.

Formation and Characterization of CdS Hollow Structures

CdS hollow structures were built up by using the one pot method and using carbon disulfide （CS2） and ethylenediamine as starting materials. CS2 is insoluble in water and could form metastable oil droplets in the water at a moderate temperature. The oil droplets formed chains in the circumvolving water. CdS crystals grew and mineralized on the surfaces of the CS2 droplet chains, forming CdS shells around the unreacted CS2 cores. After the surrounding temperature was raised above the boiling point of CS2, the unreacted CS2 cores vaporized, leaving the CdS shelled hollow structures. The CdS hollow structures were characterized by using a transmission electron microscope, an X-ray diffractometer, a UV-Visible spectrophotometer and a fluorescence spectrophotometer. The CdS hollow structures were mainly tubes with closed ends. The exterior diameter and the interior diameter of tubes were about 50 nm and about 15 nm, respectively. Compared with the absorption onset wavelength of the bulk CdS, the CdS hollow structures exhibited a blue shift of about 57 nm. While excited at 213 nm, the CdS hollow structures emitted greenish blue light centered at 470 nm.

Effects of edge beams on mechanic behavior under lateral load in reinforced concrete hollow slab-column structure

In order to get the formulae for calculating the equivalent frame width coefficient of reinforced concrete hollow slab-column structures with edge beam,the finite element structural program was used in the elastic analysis of reinforced concrete hollow slab-column structure with different dimensions to study internal relationship between effective beam width and the frame dimensions.In addition,the formulas for calculating the increasing coefficient of edge beam were also obtained.

THE STRUCTURE AND PROPERTIES OF FINE DENIER HOLLOW POLY(ETHYLENE TEREPHTALATE) FIBRES

Using brighten white and modified PET chips, fine denier hollow fibres (dpf=0.5～1.5) were prepared on a Fuji Filter MSTC-400 and VC-443A drawn machine, whose structure and properties were tested by X-ray diffraction mater, SOM-II sonic velocity meter and Instron-1122 Tensile tester, electron and light microscopy etc,. The results show: fine denier hollow taken-up yarns prepared at low spinning velocity have radial orientation, higher strength and elongation at rupture because radial stress is higher than normal stress. Fine denier hollow drawn yarns with hollow degree up to 18～35％ and high tenacity, together with high crystalline degree and small crystal and amorphous domains, can be empolyed as products.

Discussion on "Thermomagnetic viscoelastic responses in a functionally graded hollow structure"

Allam and Tantawy [1] presented an analytical solu- tion for stress distribution and perturbations of the magnetic field vector in FGM hollow structures made from viscoelas- tic composite materials .While studying this article, the dis- cusser noticed a confusion in regarding Maxwell＇s electro- magnetic stress expression

Three-Layer Structured SnO_(2)@C@TiO_(2)Hollow Spheres for High-Performance Sodium Storage

The unsatisfactory conductivity and large volume variation severely handicap the application of SnO_(2)in sodium-ion batteries(SIBs).Herein,we design unique three-layer structured SnO_(2)@C@TiO_(2)hollow spheres to tackle the above-mentioned issues.The hollow cavity affords empty space to accommodate the volume variation of SnO_(2),while the C and TiO_(2)protecting shells strengthen the structural integrity and enhances the electrical conductivity.As a result,the three-layer structured SnO_(2)@C@TiO_(2)hollow spheres demonstrate enhanced Na storage performances.The SnO_(2)@C@TiO_(2)manifests a reversible capacity two times to that of pristine SnO_(2)hollow spheres.In addition,Ex situ XRD reveals highly reversible alloying and conversion reactions in SnO_(2)@C@TiO_(2)hollow spheres.This study suggests the introduction of a hollow cavity and robust protecting shells is a promising strategy for constructing SIB anode materials.