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.

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.

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.

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.

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.

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.

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.

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.

VN nanoparticle-assembled hollow microspheres/N-doped carbon nanofibers:An anode material for superior potassium storage

Thanks to inexpensive and bountiful potassium resources,potassium ion batteries(PIBs)have come into the spotlight as viable alternatives for next-generation battery systems.However,poor electrochemical kinetics due to the large size of the K^(+) is a major challenge for PIB anodes.In this paper,an ingenious design of VN nanoparticleassembled hollow microspheres within N-containing intertwined carbon nanofibers(VN-NPs/N-CNFs)via an electrospinning process is reported.Employed as PIB anodes,VN-NPs/N-CNFs exhibit a superb rate property and prolonged cyclability,surpassing that of other reported metal nitride-based anodes.This is ascribed to:(i)the VN NP-assembled hollow microspheres,which shorten the K^(+) diffusion distance,and mitigate volume expansion;and(ii)the interconnected N-CNFs,which supply numerous active sites for K^(+) adsorption and facilitate rapid electron/ion transport.

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.

Preparation of Amorphous LiZn Ferrites Hollow Microspheres by Self-reactive Quenching Technology

NaCl aqueous solution（15 wt%） was used as the quenching medium to prepare amorphous Lithium-Zinc ferrite hollow microspheres（LiZn FHMs） based on self-reactive quenching technology. Investigations by scanning electro microscope, X-ray diffraction, electron diffraction of transmission electron microscope, and differential scanning calorimetry prove that LiZn FHMs are susceptible to amorphization. It is indicated that NaCl aqueous solution（15 wt%） has ultra-fast quenching speed, and the growth rate of crystals on LiZn FHMs is so large that the formation and growth of the crystal nucleus are significantly restrained. This is the main reason for the formation of amorphous LiZn FHMs.

Effects of Heat Treatment Temperature and Time on Structure and Static Magnetic Property of W-type Ferrite Hollow Microspheres

Hollow spheres of hexagonal ferrite BaCozFelrO27 were fabricated through a spray pyrolysis technique using co-precipitation ferrite powder precursor as materials, followed by calcinations in an air atmosphere. The phase composition, micro-morphology, and static magnetic property of the particles were measured by XRD, SEM, and VSM. The results indicate that the method for preparation of ferrite hollow microspheres （FHM） results in a broad particles size distribution. The density of FHM decreased from 5.31 g/ cm^3 to 2.31 g/cm^3. When the heating rate was 5℃/min, and temperature was 1 200℃ for 4 hours, pure W-type ferrites were formed. With the heat treatment temperature and time increasing, the crystal structure becomes perfect, the saturation magnetization is increased and the coercive force is decreased.

Self-templating construction of hollow microspheres assembled by nanosheets with exposed active planes for sodium ion storage

P2-type layered metal oxides have been considered as one of the promising cathode candidates for high-performance Na-ion batteries(SIBs).However,it is still challenging to balance the contradiction of high energy density and long cycle life due to the structural degradation and sluggish ion diffusion dynamics.Here,the hierarchical P2-Na2/3Ni1/3Mn2/3O2 hollow microspheres assembled by nanosheets are constructed via a self-template approach.The obtained nanosheets with more exposed electrochemical active planes serving as desodiation/sodiation reactors can provide substantial Na+channels,shorten the diffusion pathways,and accommodate the volume changes during charge/discharge process.Benefiting from the facile Na+diffusion paths and optimal architecture modulation,the cathode delivers a high initial Coulombic efficiency of 96.0%with a high energy density of 299.7 Wh·kg^(−1).The highly reversible structural evolutions processes are verified by galvanostatic intermittent titration technique(GITT)and operando electrochemical impedance spectroscopy(EIS)measurement,which would significantly improve the cycle stability(83.3%capacity retention at 1.0 C over 500 loops).Furthermore,the full cell assembled by hard carbon presents a high reversible capacity of 71 mAh·g^(−1)at 0.2 C and promising capacity retention(91.5%after 50 cycles).The designing concept of morphological configuration in this work paves an accessible route for building high-performance electrode materials.

Denatured proteins show new vitality:Green synthesis of germanium oxide hollow microspheres with versatile functions by denaturing proteins around bubbles

The hollow structure has long attracted great attention because of its excellent properties.However,this special structure is usually synthesized through some complex approaches.Herein,we discovered that denatured bovine serum albumin(BSA)can trigger unusual biomineralization for the simple,green and shape-controllable synthesis of germanium oxide(GeOx)hollow microsphere(HMS).At high temperature(60℃),BSA was denatured,and a compact BSA layer was formed around the H2 bubbles.The denatured BSA layer was stable and suitable for anchoring and growing GeOx.By simply changing the BSA concentration and temperature,various morphologies of GeOx could be obtained.Due to the denatured protein skeletons and microenvironment-regulated collapse,GeOx HMS showed great potential for intelligently responsive pesticide delivery in the insect gut,showing superiority over traditional delivery systems,which early release pesticides in the mouth and stomach.Inspired by its large specific surface area,excellent biocompatibility,modifiable functional groups,and high electrocatalytic activity,GeOx HMS was also applied to versatile sensors for H_(2)O_(2) assays at physiological pH and rapid coronavirus COVID-19 detection.This work not only provides some evidence for understanding proteins in depth but also paves a new avenue for the biomineralization-inspired synthesis of hollow structures with versatile functions.

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.

Step-scheme CdS/TiO_(2) nanocomposite hollow microsphere with enhanced photocatalytic CO_(2) reduction activity

Converting solar energy into chemical energy by artificial photosynthesis is promising in addressing the issues of the greenhouse effect and fossil fuel crisis.Herein,a novel photocatalyst,i.e.CdS/TiO_(2) hollow microspheres(HS),were dedicatedly designed to boost overall photocatalytic efficiency.TiO_(2) nanoparticles were in-situ decorated on the inside and outside the shell of Cd S HS,ensuring close contact between TiO_(2) and CdS.The CdS/TiO2 HS with abundant mesopores inside of the shell boost the light absorption via multiscattering effect as well as accessible to reactions in all directions.The heterojunction was scrutinized and the charge transfer across it was revealed by in-situ irradiated X-ray photoelectron spectroscopy(ISI-XPS).Ultimately,the charge transfer in this composite was determined to follow stepscheme mechanism,which not only facilitates the separation of charge carriers but also preserves strong redox ability.Benefited from the intimate linkage between Cd S and TiO_(2) and the favorable step-scheme heterojunction,enhanced photocatalytic CO_(2) reduction activity was accomplished.The CH4 yield rate of CdS/TiO_(2) reaches 27.85μmol g^(–1) h^(–1),which is 145.6 and 3.8 times higher than those of pristine CdS and TiO_(2),respectively.This work presents a novel insight into constructing step-scheme photocatalytic system with desirable performance.

Multi-shelled TiO2/Fe2TiO5 heterostructured hollow microspheres for enhanced solar water oxidation

There remains a pressing challenge in the fabrication of superior photocatalysts for light-driven water oxidation.Here,we designed and fabricated heterostructured TiO2/Fe2TiO5 hollow microspheres with single-,double-,closed-double-,triple-,and core-shell structures and different Fe/Ti molar ratios using a facile sequential templating approach.The closed-double-shelled TiO2/Fe2TiO5 hollow microspheres with 35% Fe exhibited the highest oxygen evolution reaction rate up to 375 μmol＆#183;g-1＆#183;h-1 and good stability for 5 h.The high performance can be attributed to the closed-double shell,which had more reactive sites and greater light-harvesting ability,self-supported thin shells with short charge-transfer paths,and a favorable staggered band alignment between the TiO2 and Fe2TiOs.

MnS hollow microspheres combined with carbon nanotubes for enhanced performance sodium-ion battery anode

MnS as anode material for sodium-ion batteries(SIBs)has recently attracted great attention because of the high theoretical capacity,great natural abundance,and low cost.However,it suffers from inferior electrical conductivity and large volume expansion during the charge/discharge process,leading to tremendous damage of electrodes and subsequently fast capacity fading.To mitigate these issues,herein,a three-dimensional(3D)interlaced carbon nanotubes(CNTs)threaded into or between MnS hollow microspheres(hollow MnS/CNTs composite)has been designed and synthesized as an enhanced anode material.It can effectively improve the electrical conductivity,buffer the volume change,and maintain the integrity of the electrode during the charging and discharging process based on the synergistic interaction and the integrative structure.Therefore,when evaluated as anode for SIBs,the hollow MnS/CNTs electrode displays enhanced reve rsible capacity(275 mAh/g at 100 mA/g after 100 cycles),which is much better than that of pure MnS electrode(25 mAh/g at 100 mA/g after 100 cycles)prepared without the addition of CNTs.Even increasing the current density to 500 mA/g,the hollow MnS/CNTs electrode still delivers a five times higher reversible capacity than that of the pure MnS electrode.The rate performance of the hollow MnS/CNTs electrode is also superior to that of pure MnS electrode at various current densities from 50 mA/g to 1000 mA/g.

Rational synthesis of SnS_2@C hollow microspheres with superior stability for lithium-ion batteries

Tin-based nanomaterials have been extensively explored as high-capacity anode materials for lithium ion batteries（LIBs）. However,the large volume changes upon repeated cycling always cause the pulverization of the electrode materials. Herein,we report the fabrication of uniform SnS_2@C hollow microspheres from hydrothermally prepared SnO_2@C hollow microspheres by a solid-state sulfurization process. The as-prepared hollow SnS_2@C microspheres with unique carbon shell,as electrodes in LIBs,exhibit high reversible capacity of 814 mA h g^（-1） at a current density of 100 mA g^（-1）,good cycling performance（783 mA h g^（-1） for 200 cycles maintained with an average degradation rate of 0.02% per cycle） and remarkable rate capability（reversible capabilities of 433 mA h g^（-1）at 2C）. The hollow space could serve as extra space for volume expansion during the charge-discharge cycling,while the carbon shell can ensure the structural integrity of the microspheres. The preeminent electrochemical performances of the SnS_2@C electrodes demonstrate their promising application as anode materials in the next-generation LIBs.