Ni/Pd core/shell nanoparticles supported on graphene as a highly active and reusable catalyst for Suzuki- Miyaura cross-coupling reaction

Monodisperse Ni/Pd core/shell nanoparticles （NPs） have been synthesized by sequential reduction of nickel（II） acetate and palladium（II） bromide in oleylamine （OAm） and trioctylphosphine （TOP）. The Ni/Pd NPs have a narrow size distribution with a mean particle size of 10 nm and a standard deviation of 5% with respect to the particle diameter. Mechanistic studies showed that the presence of TOP was essential to control the reductive decomposition of Ni-TOP and Pd-TOP, and the formation of Ni/Pd core/shell NPs. Using the current synthetic protocol, the composition of the Ni/Pd within the core/shell structure can be readily tuned by simply controlling the initial molar ratio of the Ni and Pd salts. The as-synthesized Ni/Pd core/shell NPs were supported on graphene （G） and used as catalyst in Suzuki-Miyaura cross-coupling reactions. Among three different kinds of Ni/Pd NPs tested, the Ni/Pd （Ni/Pd = 3/2） NPs were found to be the most active catalyst for the Suzuki-Miyaura cross-coupling of arylboronic acids with aryl iodides, bromides and even chlorides in a dimethylformamide/water mixture by using K2CO3 as a base at 110 ℃. The G-Ni/Pd was also stable and reusable, providing 98% conversion after the 5th catalytic run without showing any noticeable Ni/Pd composition change. The G-Ni/Pd structure reported in this paper combines both the efficiency of a homogeneous catalyst and the durability of a heterogeneous catalyst, and is promising catalyst candidate for various Pd-based catalytic applications.

Porous ternary complex metal oxide nanoparticles converted from core/shell nanoparticles

We demonstrate an easy and scalable low-temperature process to convert porous ternary complex metal oxide nanoparticles from solution-synthesized core^shell metal oxide nanopartides by thermal annealing. The final products demonstrate superior electrochemical properties with a large capacity and high stability during fast charging/discharging cycles for potential applications as advanced lithium-ion battery （LIB） electrode materials. In addition, a new breakdown mechanism was observed on these novel electrode materials.

Enhancing electromagnetic wave absorption with core‐shell structured SiO_(2)@MXene@MoS_(2) nanospheres

Material composition and structural design are important factors influencing the electromagnetic wave(EMW)absorption performance of materials.To alleviate the impedance mismatch attributed to the high dielectric constant of Ti_(3)C_(2)T_(x)MXene,we have successfully synthesized core‐shell structured SiO_(2)@MXene@MoS_(2)nanospheres.This architecture,comprising SiO_(2) as the core,MXene as the intermediate layer,and MoS_(2) as the outer shell,is achieved through an electrostatic self‐assembly method combined with a hydrothermal process.This complex core‐shell structure not only provides a variety of loss mechanisms that effectively dissipate electromagnetic energy but also prevents self‐aggregation of MXene and MoS_(2) nanosheets.Notably,the synergistic combination of SiO_(2) and MoS_(2) with highly conductive MXene enables the suitable dielectric constant of the composites,ensuring optimal impedance matching.Therefore,the core‐shell structured SiO_(2)@MXene@MoS_(2) nanospheres exhibit excellent EMW absorption performance,featuring a remarkable minimum reflection loss(RL_(min))of−52.11 dB(2.4 mm).It is noteworthy that these nanospheres achieve an ultra‐wide effective absorption bandwidth(EAB)of 6.72 GHz.This work provides a novel approach for designing and synthesizing high‐performance EMW absorbers characterized by“wide bandwidth and strong reflection loss.”

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.

Control and vibration analyses of a sandwich doubly curved micro-composite shell with honeycomb,truss,and corrugated cores based on the fourth-order shear deformation theory

Curved shells are increasingly utilized in applied engineering due to their shared characteristics with other sandwich structures,flexibility,and attractive appearance.However,the inability of controlling and regulating vibrations and destroying them afterward is a challenge to scientists.In this paper,the curve shell equations and a linear quadratic regulator are adopted for the state feedback design to manage the structure vibrations in state space forms.A five-layer sandwich doubly curved micro-composite shell,comprising two piezoelectric layers for the sensor and actuator,is modeled by the fourth-order shear deformation theory.The core(honeycomb,truss,and corrugated)is analyzed for the bearing of transverse shear forces.The results show that the honeycomb core has a greater effect on the vibrations.When the parameters related to the core and the weight percentage of graphene increase,the frequency increases.The uniform distribution of graphene platelets results in the lowest natural frequency while the natural frequency increases.Furthermore,without taking into account the piezoelectric layers,the third-order shear deformation theory(TSDT)and fourth-order shear deformation theory(FOSDT)align closely.However,when the piezoelectric layers are incorporated,these two theories diverge significantly,with the frequencies in the FOSDT being lower than those in the TSDT.

Heterostructural NiFeW disulfide and hydroxide dual‐trimetallic core‐shell nanosheets for synergistically effective water oxidatio

A stable and highly active core‐shell heterostructure electrocatalyst is essential for catalyzing oxygen evolution reaction(OER).Here,a dual‐trimetallic core‐shell heterostructure OER electrocatalyst that consists of a NiFeWS_(2) inner core and an amorphous NiFeW(OH)_(z)outer shell is designed and synthesized using in situ electrochemical tuning.The electrochemical measurements of different as‐synthesized catalysts with a similar mass loading suggest that the core‐shell Ni_(0.66)Fe_(0.17)W_(0.17)S_(2)@amorphous NiFeW(OH)_(z) nanosheets exhibit the highest overall performance compared with that of other bimetallic reference catalysts for the OER.Additionally,the nanosheet arrays were in situ grown on hydrophilic‐treated carbon paper to fabricate an integrated three‐dimensional electrode that affords a current density of 10 mA cm^(−2) at a small overpotential of 182 mV and a low Tafel slope of 35 mV decade^(−1) in basic media.The Faradaic efficiency of core‐shell Ni_(0.66)Fe_(0.17)W_(0.17)S_(2)@amorphous NiFeW(OH)_(z) is as high as 99.5% for OER.The scanning electron microscope,transmission electron microscope,and X‐ray photoelectron spectroscopy analyses confirm that this electrode has excellent stability in morphology and elementary composition after long‐term electrochemical measurements.Importantly,density functional theory calculations further indicate that the core‐shell heterojunction increased the conductivity of the catalyst,optimized the adsorption energy of the OER intermediates,and improved the OER activity.This study provides a universal strategy for designing more active core‐shell structure electrocatalysts based on the rule of coordinated regulation between electronic transport and active sites.

Investigations on multi-photon emissions of Nd^3＋-sensitized core/shell nanoparticles

The past few years witnessed extensive emergence of short-wavelength upconversion（UC） emission stimulated photoactivation studies. However, low efficiency of multi-photon process greatly limits further applications. Here, ultraviolet（UV） upconversion emissions originated from multi-photon process of Tm^3＋ were studied with Nd^3＋-sensitized NaGdF4：Yb,Tm@NaYF4：Nd,Yb core/shell nanoparticles. Crucial factors, including the contents of sensitizers Nd^3＋, Yb^3＋ and activator Tm^3＋, as well as the excitation power density were investigated based on the UV emission. Spectral results showed that high contents of Nd^3＋ in shell region up to 50%（molar fraction hereafter） and Yb^3＋ of 10% were essential to mediate the energy transfer via the core/shell interface and facilitate multi-photon UV emissions. Compared with segregated activator and sensitizer, a core/shell strategy with isolated Nd^3＋ in the shell was important for higher UV emission. Although the upconverting process was initiated with Nd^3＋→Yb^3＋, the short-wavelength emissions were intrinsically coming from four- and five-photon process. The optimized nanoparticles were found to be able to manipulate the configuration transition of azobenzene molecules, and it could be promising for near infrared（NIR） triggered optical switches applications.

Regulating surface In–O in In@InO_(x) core‐shell nanoparticles for boosting electrocatalytic CO_(2) reduction to formate

To solve the excessive emission of CO_(2) caused by the excessive use of fossil fuels and the corre‐sponding environmental problems,such as the greenhouse effect and climate warming,electrocat‐alytic CO_(2) reduction to liquid fuel with high selectivity is of huge significance for energy conversion and storge.Indium has been considered as a promising and attractive metal for the reduction of CO_(2) to formate.However,the current issues,such as low selectivity and current activity,largely limit the industrial application for electrocatalytic CO_(2) reduction,the design optimization of the catalyst structure and composition is extremely important.Herein,we develop a facile strategy to regulate surface In–O of In@InO_(x) core‐shell nanoparticles and explore the structure‐performance relation‐ship for efficient CO_(2)‐to‐formate conversion though air calcination and subsequent in situ electro‐chemical reconstruction,discovering that the surface In–O is beneficial to stabilize the CO_(2) interme‐diate and generate formate.The optimized AC‐In@InO_(x)‐CNT catalyst exhibits a C1 selectivity up to 98%and a formate selectivity of 94%as well as a high partial formate current density of 32.6 mA cm^(-2).Furthermore,the catalyst presents an excellent stability for over 25 h with a limited activity decay,outperforming the previously reported In‐based catalysts.These insights may open up op‐portunities for exploiting new efficient catalysts by manipulating their surface.

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.

Preparation of novel core-shell nanoparticles by electrochemical synthesis

Nanostructural gold/polyaniline core/shell composite particles on conducting electrode ITO were successfully prepared via electrochemical polymerization of aniline based on 4-aminothiophenol (4-ATP) capped Au nanoparticles. The new approach to the fabrication included three steps: preparation of gold nanoparticles as core by pulse electrodeposition; formation of ATP monolayer on the gold particle surface, which served as a binder and an initiator; polymerization of aniline monomer initiated by ATP molecules under controlled voltage lower than the voltammetric threshold of aniline polymerization, which assured the formation of polyaniline shell film occurred on gold particles selectively. Topographic images were also studied by AFM, which indicated the diameter of gold nanoparticles were around 250 nm. Coulometry characterization confirmed the shell thickness of polyaniline film was about 30 nm. A possible formation mechanism of the Au/polyaniline core-shell nanocomposites was also proposed. The novel as-prepared core-shell nanoparticles have potential application in constructing biosensor when bioactive enzymes are absorbed or embedded in polyaniline shell film.

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.

Synthesis of Ni@Au Core-shell Nanoparticles and Its Applications in Ullmann Reaction as a Synergistic Catalyst

The Ni@Au core-shell nanoparticles had been successfully synthesized from aqueous solution by one-step route at room temperature. The Ni@Au nanoparticles can be an excellent catalyst for Ullmann reaction. The advantage of Ni@Au is that the catalyst does not need additional reducing agents. The Au shell can effectively protect the Ni core from oxidation. The Ni core and Au shell have both composited in structure and cooperated in function.

Preparation and Characterization of Nano-Sized (Mg_(x)Fe_(1–x)O/SiO₂) (x = 0.1) Core-Shell Nanoparticles by Chemical Precipitation Method

Magnetic core-shell nanoparticles have been widely studied because of their excellent and convenient magnetic and electrical properties.In this present work core-shell magneticnanoparticles (MNPs) were synthesized by simple chemical precipitation method. Firstly Mg(x)Fe(1–x)O (magnesiwuestite) nano powder samples were synthesised by low temperature chemical combustion method. Secondly the as synthesised Mg(x)Fe(1–x)O nanoparticles are used to synthesis magnetic core-shell Nano particles byusing 2-propanol, poly ethylene glycol (PEG), ammonia solution 30 wt%, tetraethyl orthosilicate (TEOS). Separation of the core-shell magnetic nanoparticles from the aqueous suspension using a centrifuge. The synthesised MNPs and core shell MNP were characterized by X-ray diffraction (XRD), Thermal gravimetric-differential thermal analyzer (TG-DTA), Transmission electron microscopy (TEM), scanning electron microscopy (SEM), (EDAX) for structural, thermal and morphological respectively. It is observed that the particle size of spherical sampleis 32.5 nm.

Shell-driven Fine Structure Transition of Core Materials in Co@Au Core-shell Nanoparticles

Co@Au core shell nanoparticles(NPs) of different shell thicknesses were fabricated by a combination of the displacement process and the reduction-deposition process in a microfluidic reactor. The effect of the shell thickness on the fine structures(local atom arrangement) of core materials was investigated by X-ray Absorption Near Edge Structure(XANES) and Extended X-ray Absorption Fine Structure(EXAFS).The results indicate that the shell thickness affects the fine structure of the core materials by causing atomic re-arrangement between the hexagonal close pack(hcp) and the face centered cubic(fcc) structure, and forming Co-Au bonds in the core-shell interface.

Photochemical synthesis of bimetallic Au-Ag nanoparticles with “core-shell” type structure by seed mediated catalytic growth

The colloidal Au core/Ag shell structure composite nanoparticles were synthesized in PEG-acetone solution by photochemical route. The monodispersed Au nanoparticles with average diameter of 3.9 nm were used as growth seeds. The optical property of colloids and the sizes of composite nanoparticles were characterized when the molar ratio of Au to Ag ranges from 4∶1 to 1∶4. The results show that a composite nanoparticle structure similar to strawberry shape is formed at the molar ratio of Au to Ag from 4∶1 to 1∶1; the composite nanoparticles consisting of a core of Au and shell of Ag were generated at the 1∶4 molar ratio, having a striking feature of forming (interconnected) network structure.

Synthesis of Ag@Al_2O_3 Core-shell Structure Nanoparticles and Their Enhancement Effect on Dielectric Properties for Ag@Al_2O_3/Polyimide Nanocomposites

A novel core-shell structure Ag@Al2O3 nano-particles were synthesized and doped into polyimide as conductive fillers to prepare the composite films with high dielectric properties and low dielectric loss. The morphology and structures of the Ag@Al2O3 nano-particles were characterized by transmission electron microscopy （TEM）, X-ray diffraction （XRD）, and UV-visible spectroscopy. All the results proved that the Ag@Al2O3 nano-parficles had a typical core-shell structure, for the Ag particles were coated by Al2O3 shell and the average sizes ofAg@Al2O3 particles were between 30 to 150 nm. The as-prepared Ag@Al2O3 nanoparticles were doped into the polyimide with different mass fractions to fabricate the Ag@Al2O3/PI composite films via in-situ polymerization process. SEM analysis of composite films showed that the Ag@Al2O3 nano- particles homogeneously dispersed in polyimide matrix with nanoseale. As dielectric materials for electronic packaging systems, the Ag@Al2O3/PI composites exhibited appropriate mechanical properties and erthaneed dielectric properties, including greatly enhanced dielectric constant and just a slight increase in dielectric loss. These improvements were attributed to the core-shell structure of fillers and their fine dispersion in the PI matrix.

Core@shell sulfur@polypyrrole nanoparticles sandwiched in graphene sheets as cathode for lithium–sulfur batteries

A nano sulfur-based composite cathode material featured by uniform core@shell-structured sulfur@polypyrrole nanoparticles sandwiched in three-dimensional graphene sheets conductive network（S@PPy/GS） is fabricated via a facile solution-based method. The S@PPy nanoparticles are synthesized by in situ chemical oxidative polymerization of pyrrole on the surface of sulfur particles,and then graphene sheets are covered outside the S@PPy nanoparticles,forming a three-dimensional conductive network. When evaluating the electrochemical performance of S@PPy/GS in a lithium–sulfur battery,it delivers large discharge capacity,excellent cycle stability,and good rate capability. The initial discharge capacity is up to 1040 m Ah/g at 0.1 C,the capacity can remain 537.8 m Ah/g at 0.2 C after 200 cycles,even at a higher rate of 1 C,the specific capacity still reaches 566.5 m Ah/g. The good electrochemical performance is attributed to the unique structure of S@PPy/GS,which can not only provide an excellent transport of lithium and electron ions within the electrodes,but also retard the shuttle effect of soluble lithium polysulfides effectively,thus plays a positive role in building better lithium-sulfur batteries.

Raman scattering in In/InOx core-shell structured nanoparticles

The properties of Raman phonons are very important due to the fact that they can availably reflect some important physical information. An abnormal Raman peak is observed at about 558 cm-1 in In film composed of In/InOx core-shell structured nanoparticles, and the phonon mode stays very stable when the temperature changes. Our results indicate that this Raman scattering is attributed to the existence of incomplete indium oxide in the oxide shell.

Memory Effect up to Room-temperature in Ni/Ni_2P Core-shell Structured Nanoparticles

Memory effect has been studied in the system using magnetic nanoparticles with Ni nanocore encapsulated by non-magnetic and oxidation-resistant Ni2P nanoshell acquired through surface-phosphatizing Ni nanoparticles. The self-assembled array with interparticle spacing of about 6 nm shows memory effect up to 200 K below its average blocking temperature of 260 K. And reducing the interparticle spacing of the self-assembled array via annealing can further enlarge the temperature range of memory effect up to room-temperature. The memory effect can be understood based on the thermal relaxation theory of single-domain magnetic nanoparticles. Furthermore, the read-write magnetic coding is realized based on the temperature changes, using the memory effect up to room-temperature, which may be useful for future memory devices.

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.