Co/Co_(7)Fe_(3)heterostructures with controllable alloying degree on carbon spheres as bifunctional electrocatalyst forrechargeable zinc-air batteries

Exploring efficient and nonprecious metal electrocatalysts of oxygen reduction reaction(ORR)and oxygen evolution reaction(OER)is crucial for developing rechargeable zinc-air batteries(ZABs).Herein,an alloying-degree control strategy was employed to fabricate nitrogen-doped carbon sphere(NCS)decorated with dual-phase Co/Co_(7)Fe_(3)heterojunctions(CoFe@NCS).The phase composition of materials has been adjusted by controlling the alloying degree.The optimal CoFe_(0.08)@NCS electrocatalyst displays a half-wave potential of 0.80 V for ORR and an overpotential of 283 mV at 10 mA·cm^(-2)for OER in an alkaline electrolyte.The intriguing bifunctional electrocatalytic activity and durability is attributed to the hierarchically porous structure and interfacial electron coupling of highly-active Co_(7)Fe_(3)alloy and metallic Co species.When the CoFe_(0.08)@NCS material is used as air-cathode catalyst of rechargeable liquid-state zinc-air battery(ZAB),the device shows a high peak power-density(157 mW·cm^(-2))and maintains a stable voltage gap over 150 h,outperforming those of the benchmark(Pt/C+RuO_(2))-based device.In particular,the as-fabricated solid-state flexible ZAB delivers a reliable compatibility under different bending conditions.Our work provides a promising strategy to develop metal/alloy-based electrocatalysts for the application in renewable energy conversion technologies.

Novel N-doped carbon nanotubes impregnated Mn spheres with polydopamine coating as an efficient polysulfide immobilizer for Li-S batteries

Lithium-sulfur(Li-S)batteries are one of the most promising energy storage and conversion devices due to the high theoretical capacity and cost-effectiveness of sulfur.However,they still suffer from sluggish redox kinetics and the shuttle effect caused by complex polysulfides.In this work,graphitic carbon nitride(g-C_(3)N_(4))is utilized as a template and further hydrothermally treated with an Mn source and glucose.The pyrolysis of g-C_(3)N_(4)gives rise to N-doped carbon nanotubes,producing abundant sites for physical confinement and chemical adsorption of polysulfides,while glucose carbonization brings forth amorphous carbon and Mn source produces metal spheres.Afterward,polydopamine(PDA)induces N-doped carbon coating and promotes interface connection as well as electron immigration.This synergistic design possesses a high surface area of micropores and mesopores to aggregate sulfur and accelerate redox kinetics.As a result,the N-doped carbon nanotube with Mn spheres and PDA coating@sulfur(CN/Mn-PDA@S)exhibits a high reversible capacity of 813.5 mAh g^(-1)at 1 C with a decay rate of 0.064%per cycle and remarkable capacity retention at 2 C with rate performance up to 4 C.Therefore,the novel design of N-doped carbon nanotubes with Mn spheres and PDA coating serves as an efficient polysulfide immobilizer for Li-S batteries.

CalliSpheres微球联合空白微球TACE治疗中晚期肝癌的近期疗效及安全性研究

目的探讨CalliSpheres载药微球联合空白微球(8Spheres)TACE治疗中晚期肝癌近期临床疗效和安全性。方法回顾性分析2016年7月至2017年11月行CalliSpheres载药微球联合8Spheres栓塞微球(DEB-TACE组)TACE 50例,罂粟乙碘化油联合8Spheres栓塞微球(cTACE组)48例患者的临床资料,比较两组间疾病缓解率、控制率及并发症发生率,比较两组患者术前和术后3 d肝功能指标。结果基线数据在两组间差异无统计学意义(P>0.05)。DEB-TACE组3、6个月疾病缓解率均高于cTACE组(P<0.05),且DEB-TACE组6个月疾病进展发生率、血清AFP升高率较低,近期疗效优于cTACE组(P<0.05)。术后3 d cTACE组ALT、AST较DEB-TACE组升高明显(P<0.05)。两组患者术后均无严重不良反应发生。结论 CalliSpheres载药微球联合8Spheres栓塞微球TACE在中晚期肝癌中的近期临床疗效优于罂粟乙碘油联合8Spheres栓塞微球,且安全性较高。

Prediction of Coefficient of Restitution for Impact Elastoplastic Spheres Considering Finite Plate Thickness

Collisions between objects are a relatively common phenomenon in nature.Analyses of collision processes can greatly contribute to solving problems such as impact-rub faults and particle impacts.The coefficient of restitution is a critical parameter in the analysis of collision processes.Many experiments have shown that the coefficient of restitution is closely related to the plate thickness,and the smaller the plate thickness,the more inaccurate the coefficient of restitution predicted by the existing model,which seriously affects the process of collision analysis.To remedy this shortcoming,this paper proposes a plate thickness influence factor with the ratio of sphere diameter to plate thickness as the variable.The plate thickness influence factor can optimize the coefficient of restitution model to effectively predict the coefficient of restitution of impacting elastoplastic spheres with finite plate thickness.Finally,the validity of the new model is verified using a large amount of experimental data.

Recent advances in producing hollow carbon spheres for use in sodium−sulfur and potassium−sulfur batteries

Sodium-sulfur(Na-S)and potassium-sulfur(K-S)batteries for use at room temperature have received widespread attention because of the abundance and low cost of their raw materials and their high energy density.However,their development is restricted by the shuttling of polysulfides,large volume expansion and poor conductivity.To overcome these obstacles,an effective approach is to use carbon-based materials with abundant space for the sulfur that has sulfiphilic sites to immobilize it,and a high electrical conductivity.Hollow carbon spheres(HCSs)with a controllable structure and composition are promising for this purpose.We consider recent progress in optimizing the electrochemical performance of Na-/K-S batteries by using these materials.First,the advantages of HCSs,their synthesis methods,and strategies for preparing HCSs/sulfur composite materials are reviewed.Second,the use of HCSs in Na-/K-S batteries,along with mechanisms underlying the resulting performance improvement,are discussed.Finally,prospects for the further development of HCSs for metal−S batteries are presented.

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.

Poly(ethylenimine)-assisted synthesis of hollow carbon spheres comprising multi-sized Ni species for CO_(2) electroreduction

Electrochemical CO_(2) reduction to produce value-added chemicals and fuels is one of the research hotspots in the field of energy conversion.The development of efficient catalysts with high conductivity and readily accessible active sites for CO_(2) electroreduction remains challenging yet indispensable.In this work,a reliable poly(ethyleneimine)(PEI)-assisted strategy is developed to prepare a hollow carbon nanocomposite comprising a single-site Ni-modified carbon shell and confined Ni nanoparticles(NPs)(denoted as Ni@NHCS),where PEI not only functions as a mediator to induce the highly dispersed growth of Ni NPs within hollow carbon spheres,but also as a nitrogen precursor to construct highly active atomically-dispersed Ni-Nx sites.Benefiting from the unique structural properties of Ni@NHCS,the aggregation and exposure of Ni NPs can be effectively prevented,while the accessibility of abundant catalytically active Ni-Nx sites can be ensured.As a result,Ni@NHCS exhibits a high CO partial current density of 26.9 mA cm^(-2) and a Faradaic efficiency of 93.0% at-1.0 V vs.RHE,outperforming those of its PEI-free analog.Apart from the excellent activity and selectivity,the shell confinement effect of the hollow carbon sphere endows this catalyst with long-term stability.The findings here are anticipated to help understand the structure-activity relationship in Ni-based carbon catalyst systems for electrocatalytic CO_(2) reduction.Furthermore,the PEI-assisted synthetic concept is potentially applicable to the preparation of high-performance metal-based nanoconfined materials tailored for diverse energy conversion applications and beyond.

应用碘油和8Spheres聚乙烯醇栓塞微球联合明胶海绵行经导管动脉化疗栓塞术治疗大肝癌的临床效果观察

目的观察应用碘油和8Spheres聚乙烯醇栓塞微球联合明胶海绵行经导管动脉化疗栓塞术(TACE)治疗大肝癌的近期效果和安全性。方法将124例大肝癌(病灶直径≥5cm)患者随机分为两组,每组62例,观察组采用碘油+化疗药物+8Spheres聚乙烯醇栓塞微球+明胶海绵行TACE治疗,对照组采用化疗药物+8Spheres聚乙烯醇栓塞微球行TACE治疗。比较两组患者近期临床疗效及手术前后血清甲胎蛋白水平、不良反应发生率。结果两组患者均顺利完成手术,中位随访时间10个月。观察组患者术后3个月、6个月治疗总有效率分别为90.32%、77.42%,均高于对照组的70.97%、51.61%,观察组中位疾病进展时间为8.1个月,长于对照组的6.2个月(均P<0.05);两组的不良反应发生率差异无统计学意义(P>0.05)。结论采用碘油+化疗药物+8Spheres聚乙烯醇栓塞微球联合明胶海绵行TACE治疗大肝癌近期效果好,安全性高。

Preparation of BiVO4 Hollow Spheres and its Photocatalytic Degradation of Methylene Blue

Monoclinic BiVO4 hollow nanospheres were successfully prepared via template-free method using citric acid （C6H8O7） as chelating agent and characterized by X-ray diffraction patterns, transmission electron microscope, UV-Vis DRS, and TG-DTA technique. C6H8O7 played an important role in the formation of hollow spheres. Morphology observations revealed that when appropriate amount of C6H8O7 was introduced, the cavity with the diameter of 40 nm was obtained in BiVO4 nanospheres. UV-Vis diffuse reflectance spectra indicated that the samples had absorption in both UV and visible light region. The photocatalytic activities were evaluated by the degradation of methylene blue under Xe lamp irradiation. Hollow spheres endow BiVO4 samples with greatly improved photocatalytic activity. A possible formation mechanism of hollow spheres was proposed.

Assisting Bi_(2)MoO_(6) microspheres with phenolic resin-based ACSs as attractive tailor-made supporter for highly-efficient photocatalytic CO_(2) reduction

It is rather essential to design glorious system with high CO_(2) adsorption capacity and electron migration efficiency for improving selective and effective CO_(2) reduction into solar fuels.Here,as-synthesized phenolic resin spheres via suspension polymerization were carbonized and activated by water vapor to obtain activated carbon spheres(ACSs).Subsequently,Bi_(2)MoO_(6)/ACSs were prepared via hydrothermal-impregnated method.The systematical characterizations of samples,including XRD,XPS,SEM,EDX,DRS,BET,PL,CO_(2) adsorption isotherm,EIS and transient photocurrent,were analyzed.The results clearly demonstrated that Bi_(2)MoO_(6) with suitable oxidation reduction potentials and bandgap and ACSs with admirable CO_(2) adsorption and electrical conductivity not only enhanced separation efficiency of photoindued electron-hole pair,but also displayed as 1.8 times CO_(2) reduction activity to CO as single Bi_(2)MoO_(6) sample under Xe-lamp irradiation.Finally,a concerned photocatalytic CO_(2) reduction mechanism was proposed and investigated.Our findings should provide innovative guidance for designing a series of photocatalytic CO_(2) reduction materials with highly efficient and selective ability.

Hydrothermal synthesis of monodisperse Zn_(x)Cd_(1-x)S spheres and their photocatalytic properties

Monodisperse ZnxCd1-xS spheres were successfully fabricated with a high yield by a facile hydrothermal route.The as-prepared samples were characterized by X-ray diffractometry,scanning electron microscopy and UV-vis diffusion reflectance spectroscopy.The results indicate that all the prepared samples have the same hexagonal wurtzite phase and exhibit good size uniformity and regularity.Degradation of rhodamine-B（RhB） was used to evaluate the photocatalytic activities of ZnxCd1-xS samples.Zn0.4Cd0.6S possessed the best photocatalytic activity and exhibited high stability during the reaction.

Size-controlled preparation of hollow silica spheres and glyphosate release

Different-sized hollow SiO2 spheres of 249–1348 nm in diameter were successfully prepared by using Na2SiO3 as the precursor and using polystyrene and polystyrene-methyl acrylic acid latexes as the templates. The diameter and shell thickness of the hollow SiO2 spheres increase with increasing the latex template diameter at a given mass ratio of SiO2 to latex template. The diameter and shell thickness of the hollow SiO2 spheres also increase with increasing the mass ratios of SiO2 to latex template. The presence of carboxylic acid groups on the surfaces of polystyrene-methyl acrylic acid latex templates favors the formation of dense and uniform SiO2 shells. The hollow SiO2 sphere is constructed by mesoporous shell with large specific surface area. When glyphosate is used as a release model chemical, glyphosate release rate is tuned by varying the shell thickness.

Highly crystalline carbon nitride hollow spheres with enhanced photocatalytic performance

Graphitic carbon nitride(g-C_(3)N_(4))has emerged as a remarkably promising photocatalyst for addressing environmental and energy issues;however,it exhibits only moderate photocatalytic activity because of its low specific surface area and high recombination of carriers.Preparation of crystalline g-C_(3)N_(4) by the molten salt method has proven to be an effective method to improve the photocatalytic activity.However,crystalline g-C_(3)N_(4) prepared by the conventional molten salt method exhibits a less regular morphology.Herein,highly crystalline g-C_(3)N_(4) hollow spheres(CCNHS)were successfully prepared by the molten salt method using cyanuric acid-melamine as a precursor.The higher crystallization of the CCNHS samples not only repaired the structural defects at the surface of the CCNHS samples but also established a built-in electric field between heptazine-based g-C_(3)N_(4) and triazine-based g-C_(3)N_(4).The hollow structure improved the level of light energy utilization and increased the number of active sites for photocatalytic reactions.Because of the above characteristics,the as-prepared CCNHS samples simultaneously realized photocatalytic hydrogen evolution with the degradation of the plasticizer bisphenol A.This research offers a new perspective on the structural optimization of supramolecular self-assembly.

Hydrothermal Synthesis and Formation Mechanism of Micrometer-sized MoO_2 Hollow Spheres

Micrometer-sized MoO2 hollow spheres were synthesized hydrothermally with ammonium heptamolybdate tetrahydrate as molybdenum source, Cetyltrimethylammonium bromide as structure-directing agent and C2H5OH as reducing agent, respectively. The products were investigated by X-ray diffraction, thermo gravimetry and differential thermal analysis, scanning electron microscopy, transmission electron micraseopy and X-ray photoelectron spectroscopy. A morphology transition of ＂blocks-solid spheres-hollow spheres＂ during the growth procfess was observed and the possible mechanism for the formation of MoO2 samples was proposed to be through a microscale Kirkendall effcct.

THE INTERACTION BETWEEN SHOCK WAVES AND SOLID SPHERES ARRAYS IN A SHOCK TUBE

When a shock wave interacts with a group of solid spheres,non-linear aerodynamic behaviors come into effect.The complicated wave reflections such as the Mach reflection occur in the wave propagation process.The wave interactions with vortices behind each sphere's wake cause fluctuation in the pressure profiles of shock waves.This paper reports an experimental study for the aerodynamic processes involved in the interaction between shock waves and solid spheres.A schlieren photography was applied to visualize the various shock waves passing through solid spheres.Pressure measurements were performed along different downstream positions.The experiments were conducted in both rectangular and circular shock tubes.The data with respect to the effect of the sphere array, size,interval distance,incident Mach number,etc.,on the shock wave attenuation were obtained.

Three‑Dimensional Ordered Mesoporous Carbon Spheres Modified with Ultrafine Zinc Oxide Nanoparticles for Enhanced Microwave Absorption Properties

Currently,electromagnetic radiation and interference have a significant effect on the operation of electronic devices and human health systems.Thus,developing excellent microwave absorbers have a huge significance in the material research field.Herein,a kind of ultrafine zinc oxide(ZnO)nanoparticles(NPs)supported on three-dimensional(3D)ordered mesoporous carbon spheres(ZnO/OMCS)is prepared from silica inverse opal by using phenolic resol precursor as carbon source.The prepared lightweight ZnO/OMCS nanocomposites exhibit 3D ordered carbon sphere array and highly dispersed ultrafine ZnO NPs on the mesoporous cell walls of carbon spheres.ZnO/OMCS-30 shows microwave absorbing ability with a strong absorption(−39.3 dB at 10.4 GHz with a small thickness of 2 mm)and a broad effective absorption bandwidth(9.1 GHz).The outstanding microwave absorbing ability benefits to the well-dispersed ultrafine ZnO NPs and the 3D ordered mesoporous carbon spheres structure.This work opened up a unique way for developing lightweight and high-efficient carbon-based microwave absorbing materials.

Evolution and Spatial Patterns of Spheres of Urban Influence in China

This article presents the findings of a study of the spheres of urban influence with regard to all cities in China(not including Hong Kong,Macao and Taiwan Province of China)in the years 1990,2000 and 2009.An optimized gravity model with comprehensive time distance was used to carry out a detailed analysis of the spatial patterns of Chinese spheres of urban influence and the spatial characteristics of urban agglomerations.Such urban agglomerations are characterized by high density population and a developed economy,which are also considered as the national competition unit.This paper initially identifies four spatial patterns of urban agglomerations based on the spatial layout of city groups during their evolution.Some basic characteristics of urban agglomerations are outlined,including the number of cities,the size of cities and the functions of urban centers.These characteristics are examined by using statistical methods and Geographic Information System(GIS).The main findings from this research are that the development stages and structures of urban agglomerations in China vary significantly.It is also clear that the stages and evolution of spatial patterns are strongly affected and dominated by both policy and location factors.

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.

Hierarchically mesoporous carbon spheres coated with a single atomic Fe-N-C layer for balancing activity and mass transfer in fuel cells

Novel cost-effective fuel cells have become more attractive due to the demands for rare and expensive platinum-group metal(PGM)catalysts for mitigating the sluggish kinetics of the oxygen reduction reaction(ORR).The high-cost PGM catalyst in fuel cells can be replaced by earth-abundant transition-metalbased catalysts,that is,an Fe-N-C catalyst,which is considered one of the most promising alternatives.However,the performance of the Fe-N-C catalyst is hindered by the low catalytic activity and poor stability,which is caused by insufficient active sites and the lack of optimization of the triple-phase interface for mass transportation.Herein,a novel Fe–N–C catalyst consisting of mono-dispersed hierarchically mesoporous carbon sphere cores and single Fe atom-dispersed functional shells are presented.The synergistic effect between highly dispersed Fe-active sites and well-organized porous structures yields the combination of high ORR activity and high mass transfer performance.The half-wave potential of the catalyst in 0.1M H_(2)SO_(4) is 0.82 V versus reversible hydrogen electrode,and the peak power density is 812 mW·cm^(−2) in H_(2)–O_(2) fuel cells.Furthermore,it shows superior methanol tolerance,which is almost immune to methanol poisoning and generates up to 162 mW·cm^(−2) power density in direct methanol fuel cells.

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.