Facile in situ synthesis and characterization of Fe@Si/zeolite Na composites with magnetic core–shell structures from natural materials for enhanced curcumin loading capacity

Curcumin is a natural polyphenol that is used in various traditional medicines.However,its inherent properties,such as its rapid degradation and metabolism,low bioavailability,and short half-life,are serious problems that must be resolved.To this end,a drug carrier incorporating natural magnetic cores in a zeolite framework was developed and applied to the loading of curcumin in ethanol solutions.In this system,curcumin is encapsulated in a zeolite Na(ZNA)magnetic core–shell structure(Fe@Si/ZNA),which can be easily synthesized using an in situ method.Synthesis of Fe_(3)O_(4) nanoparticles was carried out from natural materials using a co-precipitation method.Analysis of the prepared magnetic core–shell structures and composites was carried out using vibrating-sample magnetometery,Fourier transform infrared spectroscopy,transmission electron microscopy,and x-ray diffraction.The cumulative loading of curcumin in the ZNA composite with 9%nanoparticles was found to reach 90.70%with a relatively long half-life of 32.49 min.Stability tests of curcumin loading in the composite showed that adding magnetic particles to the zeolite framework also increased the stability of the composite structure.Adsorption kinetics and isotherm studies also found that the system follows the pseudo-second-order and Langmuir isotherm models.

Engineering core–shell Co_(9)S_(8)/Co nanoparticles on reduced graphene oxide: Efficient bifunctional Mott–Schottky electrocatalysts in neutral rechargeable Zn–Air batteries

It is significant for the rational construction of the high–efficient bifunctional electrocatalysts for in–depth understandings of how to improve the electron transfer and ion/oxygen transport in catalyzing oxygen reduction reaction and oxygen evolution reaction(ORR and OER),but still full of vital challenges.Herein,we synthesize the novel“three–in–one”catalyst that engineers core–shell Mott–Schottky Co_(9)S_(8)/Co heterostructure on the defective reduced graphene oxide(Co_(9)S_(8)/Co–rGO).The Co_(9)S_(8)/Co–rGO catalyst exhibits abundant Mott–Schottky heterogeneous–interfaces,the well–defined core–shell nanostructure as well as the defective carbon architecture,which provide the multiple guarantees for enhancing the electron transfer and ion/oxygen transport,thus boosting the catalytic ORR and OER activities in neutral electrolyte.As expected,the integrated core–shell Mott–Schottky Co_(9)S_(8)/Co–rGO catalyst delivers the most robust and efficient rechargeable ZABs performance in neutral solution electrolytes accompanied with a power density of 59.5 mW cm^(-2) and superior cycling stability at 5 mA cm^(-2) over 200 h.This work not only emphasizes the rational designing of the high–efficient bifunctional oxygen catalysts from the fundamental understanding of accelerating the electron transfer and ion/oxygen transport,but also sheds light on the practical application prospects in more friendly environmentally neutral rechargeable ZABs.

Stability of Ag@SiO2 core–shell particles in conditions of photocatalytic overall water-splitting

Core–shell nanoparticles containing plasmonic metals（Ag or Au） have been frequently reported to enhance performance of photo-electrochemical（PEC） devices. However, the stability of these particles in water-splitting conditions is usually not addressed. In this study we demonstrate that Ag@SiOcore–shell particles are instable in the acidic conditions in which WO-based PEC cells typically operate, Ag in the core being prone to oxidation, even if the SiOshell has a thickness in the order of 10 nm. This is evident from in situ voltammetry studies of several anode composites. Similar to the results of the PEC experiments, the Ag@SiOcore–shell particles are instable in slurry-based, Pt/ZnO induced photocatalytic water-splitting. This was evidenced by in situ photodeposition of Ag nanoparticles on the Pt-loaded ZnO catalyst, observed in TEM micrographs obtained after reaction. We explain the instability of Ag@SiOby OH-radical induced oxidation of Ag, yielding dissolved Ag+. Our results imply that a decrease in shell permeability for OH-radicals is necessary to obtain stable, Ag-based plasmonic entities in photo-electrochemical and photocatalytic water splitting.

Controlled generation of cell–laden hydrogel microspheres with core–shell scaffold mimicking microenvironment of tumor

Development of an in vitro three-dimensional(3D) model that closely mimics actual environment of tissue has become extraordinarily important for anti-cancer study. In recent years, various 3D cell culture systems have been developed,with multicellular tumor spheroids being the most popular and effective model. In this work, we present a microfluidic device used as a robust platform for generating core–shell hydrogel microspheres with precisely controlled sizes and varied components of hydrogel matrix. To gain a better understanding of the governing mechanism of microsphere formation,computational models based on multiphase flow were developed to numerically model the droplet generation and velocity field evolution process with COMSOL Multiphysics software. Our modeling results show good agreement with experiments in size dependence on flow rate as well as effect of vortex flow on microsphere formation. With real-time tuning of the flow rates of aqueous phase and oil phase, tumor cells were encapsulated into the microspheres with controllable core–shell structure and different volume ratios of core(comprised of alginate, Matrigel, and/or Collagen) and shell(comprised of alginate). Viability of cells in four different hydrogel matrices were evaluated by standard acridine orange(AO) and propidium iodide(PI) staining. The proposed microfluidic system can play an important role in engineering the in vitro micro-environment of tumor spheroids to better mimic the actual in vivo 3D spatial structure of a tumor and perfect the 3D tumor models for more effective clinical therapies.

Ionic liquid-derived core–shell gold@palladium nanoparticles with tiny sizes for highly efficient electrooxidation of ethanol

To maximize the size and structural advantages of nanomaterials in electrooxidation of ethanol, we herein report the synthesis of core–shell gold(Au)@Palladium(Pd) nanoparticles smaller than 3 nm in an ionic liquid, which combines the advantages of ionic liquids in preparing fine metal nanoparticles with the benefits of core–shell nanostructures. This synthetic strategy relies on the use of an ionic liquid(1-(2'-aminoethyl)-3-methyl-imidazolum tetrafluoroborate) as a stabilizer to produce Au particles with an average size of ca. 2.41 nm, which are then served as seeds for the formation of tiny core–shell Au@Pd nanoparticles with different Au/Pd molar ratios. The strong electronic coupling between Au core and Pd shell endows the Pd shell with an electronic structure favorable for the ethanol oxidation reaction. In specific, the ionic liquidderived core–shell Au@Pd nanoparticles at an Au/Pd molar ratio of 1/1 exhibit the highest mass-and area-based activities, approximately 11 times than those of commercial Pd/C catalyst for ethanol electrooxidation.

Understanding the growth mechanisms of metal-based core–shell nanostructures revealed by in situ liquid cell transmission electron microscopy

Metal-based core-shell nanostructures have garnered enduring interest due to their unique properties and functionalities.However,their growth and transformation mechanisms in liquid media remain largely unknown because they lack direct observation of the dynamic growth process with high spatial and temporal resolution.Developing the in situ liquid cell transmission electron microscopy(TEM)technique offers unprecedented real-time imaging and spectroscopy capabilities to directly track the evolution of structural and chemical transformation of metal-based core–shell nanostructures in liquid media under their working condition.Here,this review highlights recent progress in utilizing in situ liquid cell TEM characterization technique in investigating the dynamic evolution of material structure and morphology of metal-based core–shell nanostructures at the nano/atomic scale in real-time.A brief introduction of the development of liquid cells for in situ TEM is first given.Subsequently,recent advances in in situ liquid cell TEM for the fundamental study of growth mechanisms of metal based core–shell nanostructures are discussed.Finally,the challenge and future developments of metalbased core–shell nanostructures for in situ liquid cell TEM are proposed.Our review is anticipated to inspire ongoing interest in revealing unseen growth dynamics of core–shell nanostructures by in situ liquid cell TEM technique.

Size-dependent thermal stresses in the core–shell nanoparticles

The thermal stress in a magnetic core–shell nanoparticle during a thermal process is an important parameter to be known and controlled in the magnetization process of the core–shell system. In this paper we analyze the stress that appears in a core–shell nanoparticle subjected to a cooling process. The external surface temperature of the system, considered in equilibrium at room temperature, is instantly reduced to a target temperature. The thermal evolution of the system in time and the induced stress are studied using an analytical model based on a time-dependent heat conduction equation and a differential displacement equation in the formalism of elastic displacements. The source of internal stress is the difference in contraction between core and shell materials due to the temperature change. The thermal stress decreases in time and is minimized when the system reaches the thermal equilibrium. The radial and azimuthal stress components depend on system geometry, material properties, and initial and final temperatures. The magnitude of the stress changes the magnetic state of the core–shell system. For some materials, the values of the thermal stresses are larger than their specific elastic limits and the materials begin to deform plastically in the cooling process. The presence of the induced anisotropy due to the plastic deformation modifies the magnetic domain structure and the magnetic behavior of the system.

Optimization of conditions for preparation of ZSM-5@silicalite-1 core–shell catalysts via hydrothermal synthesis

Although the preparation of ZSM-5@silicalite-1(ZS) core–shell catalysts has been reported in the literature,their selectivity to para-xylene(PX)in the toluene alkylation with methanol is difficult to control.Here we present the effects of water and ZSM-5 adding amounts in the synthesis solution,the hydrothermal synthesis time,and the Si/Al ratio of core ZSM-5 on the catalytic performance of ZS core–shell catalysts.The ZS core–shell catalysts were characterized by X-ray diffraction (XRD),N_2 adsorption,and NH_3 temperature-programmed desorption (NH_3-TPD) techniques.The highest PX selectivity of 95.5%was obtained for the ZS(Si/Al=140) catalyst prepared in the synthesis solution with a molar ratio of 0.2 TPAOH:1TEOS:250H_2O at 175°C and 10 r·min^(-1) for only 2 h and the corresponding toluene conversion is as high as 22.8% for the alkylation of toluene with methanol.

Porous core–shell CoMn_2O_4 microspheres as anode of lithium ion battery with excellent performances and their conversion reaction mechanism investigated by XAFS

Porous core-shell CoMn204 microspheres of ca. 3-5μm in diameter were synthesized and served as an-ode of lithium ion battery. Results demonstrate that the as-synthesized CoMn204 materials exhibit excel-lent electrochemical properties. The CoMn204 anode can deliver a large capacity of 1070 mAh g-1 in thefirst discharge, a reversible capacity of 500 mAh g^-1 after 100 cycles with a coulombic efficiency of 98.5% at a charge-discharge current density of 200 mA g^-l, and a specific capacity of 385 mAh g^-1 at a muchhigher charge-discharge current density of 1600mA g^-1. Synchrotron X-ray absorption fine structure（XAFS） techniques were applied to investigate the conversion reaction mechanism of the CoMn204 anode.The X-ray absorption near edge structure （XANES） spectra revealed that, in the first discharge-charge cy-cle, Co and Mn in CoMn204 were reduced to metallic Co and Mn when the electrode was discharged to0.01 V, while they were oxidized respectively to CoO and MnO when the electrode was charged to 3.0V.Experiments of both XANE5 and extended X-ray absorption fine structure （EXAFS） revealed that neithervalence evolution nor phase transition of the porous core-shell CoMn204 microspheres could happen inthe discharge plateau from 0.8 to 0.6V, which demonstrates the formation of solid electrolyte interface（SEI） on the anode.

Structural response of aluminum core–shell particles in detonation environment

Natural aluminum particles have the core-shell structure.The structure response refers to the mechanical behavior of the aluminum particle structure caused by external influences.The dynamic behavior of the structural response of aluminum core-shell particles before combustion is of great importance for the aluminum powder burning mechanism and its applications.In this paper,an aluminum particle combustion experiment in a detonation environment is conducted and analyzed;the breakage factors of aluminum particles shell in detonation environment are analyzed.The experiment results show that the aluminum particle burns in a gaseous state and condenses into a sub-micron particle cluster.The calculation and simulation demonstrate that the rupture of aluminum particle shell in the detonation environment is mainly caused by the impact of the detonation wave.The detonation wave impacts the aluminum particles,resulting in shell cracking,and due to the shrinkage-expansion of the aluminum core and stripping of the detonation product,the cracked shell is fractured and peeled with the aluminum reacting with the detonation product.

Engineering three-layer core–shell S-1/TS-1@dendritic-SiO_(2) supported Au catalysts towards improved performance for propene epoxidation with H_(2) and O_(2)

The advocacy of green chemical industry has led to the development of highly efficient catalysts for direct gas-phase propene epoxidation with green,sustainable and simple essence.The S-1/TS-1@dendritic-SiO_(2) material with three-layer core–shell structure was developed and used as the support for Au catalysts,which showed simultaneously fantastic PO formation rate,PO selectivity and stability(over 100 h)for propene epoxidation with H_(2) and O_(2).It is found that silicalite-1(S-1)core and the middle thin layer of TS-1 offer great mass transfer ability,which could be responsible for the excellent stability.The designed dendritic SiO_(2) shell covers part of the acid sites on the external surface of TS-1,inhibiting the side reactions and improving the PO selectivity.Furthermore,three kinds of SiO_(2) shell morphologies(i.e.,dendritic,net,mesoporous shell)were designed,and relationship between shell morphology and catalytic performance was elucidated.The results in this paper harbour tremendous guiding significance for the design of highly efficient epoxidation catalysts.

Enhanced transient photovoltaic characteristics of core–shell ZnSe/ZnS/L-Cys quantum-dot-sensitized TiO_2 thin-film

Photoanodic properties greatly determine the overall performance of quantum-dot-sensitized solar cells（QDSCs）. In the present report, the microdynamic behaviors of carriers in the nanocomposite thin-film, a Zn Se QD-sensitized mesoporous La-doped nano-TiO2 thin-film, as a potential candidate for photoanode, are probed via nanosecond transient photovoltaic（TPV） spectroscopy. The results confirm that the L-Cys ligand has a dual function serving as a stabilizer and molecular linker. Large quantities of interface states are located at the energy level with a photoelectric threshold of1.58 eV and a quantum well（QW） depth of 0.67 eV. This QW depth is approximately 0.14 eV deeper than the depth of QW buried in the Zn Se QDs, and a deeper QW results in a higher quantum confinement energy. A strong quantum confinement effect of the interface state may be responsible for the excellent TPV characteristics of the photoanode. For example, the peak intensity of the TPV response of the QD-sensitized thin-film lasts a long time, from 9.40 × 10^（-7） s to 2.96 × 10^（-4） s,and the end time of the PTV response of the QD-sensitized thin-film is extended by approximately an order of magnitude compared with those of the TiO2 substrate and the QDs. The TPV characteristics of the QD-sensitized thin-film change from p-type to n-type for the QDs before and after sensitizing. These properties strongly depend on the extended diffusion length of the photogenerated carries and the reduced recombination rate of photogenerated electron-hole pairs, resulting in prolonged carrier lifetime and an increased level of electron injection into the TiO2 thin-film substrate.

Bio-Derived Hierarchical Multicore–Shell Fe2N-Nanoparticle-Impregnated N-Doped Carbon Nanofiber Bundles:A Host Material for Lithium-/Potassium-Ion Storage

Despite the significant progress in the fabrication of advanced electrode materials,complex control strategies and tedious processing are often involved for most targeted materials to tailor their compositions,morphologies,and chemistries.Inspired by the unique geometric structures of natural biomacromolecules together with their high affinities for metal species,we propose the use of skin collagen fibers for the template crafting of a novel multicore-shell Fe2N-carbon framework anode configuration,composed of hierarchical N-doped carbon nanofiber bundles firmly embedded with Fe2N nanoparticles(Fe2N@N-CFBs).In the resultant heterostructure,the Fe2N nanoparticles firmly confined inside the carbon shells are spatially isolated but electronically well connected by the long-range carbon nanofiber framework.This not only provides direct and continuous conductive pathways to facilitate electron/ion transport,but also helps cushion the volume expansion of the encapsulated Fe2N to preserve the electrode microstructure.Considering its unique structural characteristics,Fe2N@N-CFBs as an advanced anode material exhibits remarkable electrochemical performances for lithium-and potassium-ion batteries.Moreover,this bio-derived structural strategy can pave the way for novel low-cost and high-efficiency syntheses of metal-nitride/carbon nanofiber heterostructures for potential applications in energy-related fields and beyond.

Bifunctional core–shell co-catalyst for boosting photocatalytic CO_(2) reduction to CH_(4)

Solar-light-driven CO_(2) reduction CO to CH_(4) and C2H6 is a complex process involving multiple elementary reactions and energy barriers.Therefore,achieving high CH_(4) activity and selectivity remains a significant challenge.Here,we integrate bifunctional Cu2O and Cu-MOF(MOF=metal-organic framework)core–shell co-catalysts(Cu2O@Cu-MOF)with semiconductor TiO_(2).Experiments and theoretical calculations demonstrate that Cu2O(Cu+facilitates charge separation)and Cu-MOF(Cu2+improves the CO_(2) adsorption and activation)in the core–shell structure have a synergistic effect on photocatalytic CO_(2) reduction,reducing the formation barrier of the key intermediate*COOH and*CHO.The photocatalyst exhibits high CH_(4) yield(366.0μmol·g^(-1)·h^(-1)),efficient electron transfer(3283μmol·g^(-1)·h^(-1))and hydrocarbon selectivity(95.5%),which represents the highest activity of Cu-MOF-based catalysts in photocatalytic CO_(2) reduction reaction.This work provides a strategy for designing efficient photocatalysts from the perspective of precise regulation of components.

Heteroepitaxial growth of Au@Pd core–shell nanocrystals with intrinsic chiral surfaces for enantiomeric recognition

Noble metal surfaces with intrinsic chirality serve as an ideal candidate for investigating enantioselective chemistry due to their superior chemical durability and high catalytic activity.Recently,significant advance has been made in synthesizing metal nanocrystals with intrinsic chirality.Nonetheless,the majority reports are limited to gold.Herein,through a heteroepitaxial growth strategy,the synthesis of metal nanocrystals with intrinsic chirality to palladium was extended for the first time and their application in enantioselective recognition was demonstrated.The heteroepitaxial growth strategy allows for transferring the chirality of homochiral Au nanocrystals to Au@Pd core–shell nanocrystals.By employing the chiral Au@Pd nanocrystals as enantiomeric recognizing elements,a series of electrochemical sensors for chiral discrimination were developed.Under optimal conditions,the peak potential between D-dihydroxyphenylalanine(D-DOPA)and L-dihydroxyphenylalanine(L-DOPA)is about 80 m V,and the peak current of D-DOPA is 2 times as much as that of L-DOPA,which enables the determination of the enantiomeric excess(EE,%)of L-DOPA.Overall,this report not only introduces a heteroepitaxial growth strategy to synthesize metal nanocrystals with intrinsic chirality,but also demonstrates the superior capability of integrating intrinsic chirality and catalytic properties into metal nanocrystals for chiral recognition.

Assembly of a core–shell MOF with stability into polyacrylamide hydrogel for boosting extraction of uranium from seawater

Efficient and selective extraction of uranium(U(VI))from seawater is essential for sustainable nuclear power production.This study reports a novel adsorbent zeolitic imidazolate framework(ZIF)-67@SiO_(2)-A/polyacrylamide(PAM)which was synthesized by grafting the core–shell metal–organic frameworks(MOFs)-based nanostructures coated with the 3-aminopropyl triethoxysilane(APTES)functionalized SiO_(2)(SiO_(2)-A)onto PAM hydrogel.The SiO_(2) shell was grown on the surface of MOF,which improved the acid-base resistance of MOF.The introduction of ZIF-67@SiO_(2)-A enhances the specific surface area and adsorption efficiency of the PAM.The ZIF-67@SiO_(2)-A/PAM shows remarkable adsorption capacity,fast adsorption kinetics,and good reusability for uranium.It has excellent adsorption property(6.33 mg·g^(-1),30 d)in natural seawater.The X-ray photoelectron spectroscopy(XPS),Fourier transform infrared(FTIR),energy dispersive spectroscopy(EDS)mappings,and density functional theory reveal that the coordination by N and O in ZIF-67@SiO_(2)-A/PAM with uranium is the main mechanism of uranium adsorption.Thus,ZIF-67@SiO_(2)-A/PAM has great potential to capture uranium from natural seawater.

Dynamics of a rotating ring-stiffened sandwich conical shell with an auxetic honeycomb core

The free vibration analysis of a rotating sandwich conical shell with a reentrant auxetic honeycomb core and homogenous isotropic face layers reinforced with a ring support is studied.The shell is modeled utilizing the first-order shear deformation theory(FSDT)incorporating the relative,centripetal,and Coriolis accelerations alongside the initial hoop tension created by the rotation.The governing equations,compatibility conditions,and boundary conditions are attained using Hamilton’s principle.Utilizing trigonometric functions,an analytical solution is derived in the circumferential direction,and a numerical one is presented in the meridional direction via the differential quadrature method(DQM).The effects of various factors on the critical rotational speeds and forward and backward frequencies of the shell are studied.The present work is the first theoretical work regarding the dynamic analysis of a rotating sandwich conical shell with an auxetic honeycomb core strengthened with a ring support.

Mechanical property of cylindrical sandwich shell with gradient core of entangled wire mesh

To explore the wide-frequency damping and vibration-attenuation performances in the application of aerospace components,the cylindrical sandwich shell structure with a gradient core of entangled wire mesh was proposed in this paper.Firstly,the gradient cores of entangled wire mesh in the axial and radial directions were prepared by using an in-house Numerical Control weaving machine,and the metallurgical connection between skin sheets and the gradient core was performed using vacuum brazing.Secondly,to investigate the mechanical properties of cylindrical sandwich shells with axial or radial gradient cores,quasi-static and dynamic mechanical experiments were carried out.The primary evaluations of mechanical properties include secant stiffness,natural frequency,Specific Energy Absorption(SEA),vibration acceleration level,and so on.The results suggest that the vibration-attenuation performance of the sandwich shell is remarkable when the high-density core layer is at the end of the shell or abuts the inner skin.The axial gradient material has almost no influence on the vibration frequencies of the shell,whereas the vibration frequencies increase dramatically when the high-density core layer approaches the skin.Moreover,compared to the conventional sandwich shells,the proposed functional grading cylindrical sandwich shell exhibits more potential in mass reduction,stiffness designing,and energy dissipation.

Transient responses of double-curved sandwich two-layer shells resting on Kerr's foundations with laminated three-phase polymer/GNP/fiber surface and auxetic honeycomb core subjected to the blast load

This work uses refined first-order shear theory to analyze the free vibration and transient responses of double-curved sandwich two-layer shells made of auxetic honeycomb core and laminated three-phase polymer/GNP/fiber surface subjected to the blast load.Each of the two layers that make up the double-curved shell structure is made up of an auxetic honeycomb core and two laminated sheets of three-phase polymer/GNP/fiber.The exterior is supported by a Kerr elastic foundation with three characteristics.The key innovation of the proposed theory is that the transverse shear stresses are zero at two free surfaces of each layer.In contrast to previous first-order shear deformation theories,no shear correction factor is required.Navier's exact solution was used to treat the double-curved shell problem with a single title boundary,while the finite element technique and an eight-node quadrilateral were used to address the other boundary requirements.To ensure the accuracy of these results,a thorough comparison technique is employed in conjunction with credible statements.The problem model's edge cases allow for this kind of analysis.The study's findings may be used in the post-construction evaluation of military and civil works structures for their ability to sustain explosive loads.In addition,this is also an important basis for the calculation and design of shell structures made of smart materials when subjected to shock waves or explosive loads.

A 3D hierarchical electrocatalyst:Core–shell Cu@Cu(OH)_(2)nanorods/MOF octahedra supported on N-doped carbon for oxygen evolution reaction

Cu-based materials are seldom reported as oxygen evolution reaction(OER)electrocatalysts due to their inherent electron orbital configuration,which makes them difficult to adsorb oxygen-intermediates during OER.Reasonably engineering the hierarchical architectures and the electronic structures can improve the performance of Cu-based OER catalysts,such as constructing multilevel morphology,inducing the porous materials,improving the Cu valence,building heterostructures,doping heteroatoms,etc.In this work,copper-1,3,5-benzenetricarboxylate(HKUST-1)octahedra in-situ grow on the Cu nanorod(NR)-supported N-doped carbon microplates,meanwhile an active layer of Cu(OH)_(2)forms on the surface of the original conductive Cu NRs.The octahedral HKUST-1,serving as a spacer between the microplates,greatly improves the porosity and increases the available active sites,facilitating the mass transport and electron transfer,thus resulting in greatly enhanced OER performance.