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 const...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.”展开更多
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 ...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.展开更多
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 ...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.展开更多
Electrochemical nitrate reduction to ammonia(NRA) can realize the green synthesis of ammonia(NH3) at ambient conditions, and also remove nitrate contamination in water. However, the current catalysts for NRA still fac...Electrochemical nitrate reduction to ammonia(NRA) can realize the green synthesis of ammonia(NH3) at ambient conditions, and also remove nitrate contamination in water. However, the current catalysts for NRA still face relatively low NH3yield rate and poor stability. We present here a core-shell heterostructure comprising cobalt oxide anchored on copper oxide nanowire arrays(CuO NWAs@Co_(3)O_(4)) for efficient NRA. The CuO NWAs@Co_(3)O_(4)demonstrates significantly enhanced NRA performance in alkaline media in comparison with plain CuO NWAs and Co_(3)O_(4)flocs. Especially, at-0.23 V vs. RHE, NH_(3) yield rate of the CuO NWAs@Co_(3)O_(4)reaches 1.915 mmol h^(-1)cm^(-2),much higher than those of CuO NWAs(1.472 mmol h^(-1)cm^(-2)), Co_(3)O_(4)flocs(1.222 mmol h^(-1)cm^(-2)) and recent reported Cu-based catalysts.It is proposed that the synergetic effects of the heterostructure combing atom hydrogen adsorption and nitrate reduction lead to the enhanced NRA performance.展开更多
Wrinkles in flat graded elastic layers have been recently described as a timevarying Hamiltonian system by the energy method.Cylindrical core/shell structures can also undergo surface instabilities under the external ...Wrinkles in flat graded elastic layers have been recently described as a timevarying Hamiltonian system by the energy method.Cylindrical core/shell structures can also undergo surface instabilities under the external pressure.In this study,we show that by treating the radial direction as a pseudo-time variable,the graded core/shell system with radially decaying elastic properties can also be described within the symplectic framework.In combination with the shell buckling equation,the present paper addresses the surface wrinkling of graded core/shell structures subjected to the uniform external pressure by solving a series of ordinary differential equations with varying coefficients.Three representative gradient distributions are showcased,and the predicted critical pressure and critical wave number are verified by finite element simulations.The symplectic framework provides an efficient and accurate approach to understand the surface instability and morphological evolution in curved biological tissues and engineered structures.展开更多
This paper reports on the ablation process of a pure Ti solid target immersed in a C-enriched acetone solution, leading to the production of titanium carbide (TiC) and Ti-C core-shell nanostructures. The used route of...This paper reports on the ablation process of a pure Ti solid target immersed in a C-enriched acetone solution, leading to the production of titanium carbide (TiC) and Ti-C core-shell nanostructures. The used route of synthesis is generally called pulsed laser ablation in liquid (PLAL). The presence of carbon structures in the solution contributed to the carbon content in the produced Ti-based nanomaterials. The atomic composition of the produced nanostructures was analyzed using SEM-EDS, while TEM micrographs revealed the formation of spherical TiC and core-shell nanostructures ranging from 40 to 100 nm. The identification of atomic planes by HRTEM confirmed a 10 nm diameter C-shell with a graphite structure surrounding the Ti-core. Raman spectroscopy allowed for the identification of D and G peaks for graphite and a Raman signal at 380 and 600 cm<sup>−1</sup>, assigned to TiC. The results contribute to the state-of-the-art production of TiC and Ti-C core-shell nanostructures using the PLAL route.展开更多
AucoreCoshell nanoparticles with different shell thicknesses were prepared by using chemical reduction method and characterized by scanning electron microscopy(SEM) and cyclic voltammetry(CV). The results reveal t...AucoreCoshell nanoparticles with different shell thicknesses were prepared by using chemical reduction method and characterized by scanning electron microscopy(SEM) and cyclic voltammetry(CV). The results reveal that the prepared core-shell nanoparticles were covered by Co shell and exhibited the similar electrochemistry property with the Co nanoparticles surface. Surface enhanced Raman spectroscopy(SERS) activities of these nanoparticles were studied by using pyridine as a probe molecule. It was found that the SERS intensity depended on the Co shell thickness of the core-shell nanoparticles and was weakened with the increasing shell thickness. The SERS intensity of these AucoreCoshell nanoparticles is found to be about twenty times higher than that obtained on an electrochemically roughened cobalt electrode.展开更多
Core-shell nanostructures have been widely investigated to improve the electrocatalytic perfor-mance of platinum. However, organic precursors, surfactants or high temperature are usually nec-essary during the prepa...Core-shell nanostructures have been widely investigated to improve the electrocatalytic perfor-mance of platinum. However, organic precursors, surfactants or high temperature are usually nec-essary during the preparation procedure. Unfortunately, these requirements limit the application of these methods on a large scale. Herein, a Pdcore@ Pt shell nanostructure was fabricated through the reduction of fcPtCU by dissociated hydrogen at room temperature without the assistance o f either a surfactant or a high-boiling point solvent. The shell thickness of this nanostructure was successfully controlled by varying the amount of fcPtCU; core-shell nanoparticles with a shell thickness of 0.45, 0.75 and 0.90 nm w ere obtained, as determined by TEM. The remarkable crystallinity and epitaxial growth of the Pdcore@ Pt shell nanostructure were revealed by HRTEM and EDS. According to ICP and XPS, surface segregation of Pt was established. The impressive ORR performance was attributed to the weak adsorption strength of the OHads species, which resulted from the electron transfer impact between the Pdcore and Ptshell. The facile and clean preparation method can be used to prepare other core-shell nanostructures under a mild atmosphere.展开更多
We present a general approach to fabricate metal/TiO2 core/shell nanorod structures by twostep electrodeposition. Firstly, TiO2 nanotubes with uniform wall thickness are prepared in anodic aluminum oxide (AAO) membr...We present a general approach to fabricate metal/TiO2 core/shell nanorod structures by twostep electrodeposition. Firstly, TiO2 nanotubes with uniform wall thickness are prepared in anodic aluminum oxide (AAO) membranes by electrodeposition. The wall thickness of the nanotubes could be easily controlled by modulating the deposition time, and their outer diameter and length are only limited by the channel diameter and the thickness of the AAO membranes, respectively. The nanotubes' tops prepared by this method are open, while the bottoms are connected directly with the Au film at the back of the AAO membranes. Secondly, Pd, Cu, and Fe elements are filled into the TiO2 nanotubes to form core/shell structures. The core/shell nanorods prepared by this two-step process are high density and free-standing, and their length is dependent on the deposition time.展开更多
Herein, combining solverthermal route and electrodeposition, we grew unique hybrid nanosheet arrays consisting of Co_3O_4 nanosheet as a core, PPy as a shell. Benefiting from the PPy as conducting polymer improving an...Herein, combining solverthermal route and electrodeposition, we grew unique hybrid nanosheet arrays consisting of Co_3O_4 nanosheet as a core, PPy as a shell. Benefiting from the PPy as conducting polymer improving an electron transport rate as well as synergistic effects from such a core/shell structure, a hybrid electrode made of the Co_3O_4@PPy core/shell nanosheet arrays exhibits a large areal capacitance of 2.11 F cm-2at the current density of 2 m A cm^(-2), a *4-fold enhancement compared with the pristine Co_3O_4electrode; furthermore, this hybrid electrode also displays good rate capability(*65 % retention of the initial capacitance from 2 to 20 m A cm^(-2)) and superior cycling performance(*85.5 % capacitance retention after 5000 cycles). In addition, the equivalent series resistance value of the Co_3O_4@PPy hybrid electrode(0.238 X) is significantly lower than that of the pristine Co_3O_4electrode(0.319 X). These results imply that the Co_3O_4@PPy hybrid composites have a potential for fabricating next-generation energy storage and conversion devices.展开更多
A focus of the current nanotechnology has shifted from routine fabrication of nanostructures to designing functional electronic devices and realizing their immense potentials for applications. Due to infusion of multi...A focus of the current nanotechnology has shifted from routine fabrication of nanostructures to designing functional electronic devices and realizing their immense potentials for applications. Due to infusion of multi-functionality into a single system, the utilization of hetero-, core/shell and hierarchical nanostructures has become the key issue for building such devices. ZnS, due to its direct wide bandgap, high index of refraction, high transparency in the visible range and intrinsic polarity, is one of the most useful semiconductors for a wide range of electronics applications. This article provides a dense review of the state-of-the-art research activities in one-dimensional (1D) ZnS-based hetero-, core/shell and hierarchical nanostructures. The particular emphasis is put on their syntheses and applications.展开更多
In this study,a MnOx@TiO2 core‐shell catalyst prepared by a two‐step method was used for the low‐temperature selective catalytic reduction of NOx with NH3.The catalyst exhibits high activity,high stability,and exce...In this study,a MnOx@TiO2 core‐shell catalyst prepared by a two‐step method was used for the low‐temperature selective catalytic reduction of NOx with NH3.The catalyst exhibits high activity,high stability,and excellent N2 selectivity.Furthermore,it displays better SO2 and H2O tolerance than its MnOx,TiO2,and MnOx/TiO2 counterparts.The prepared catalyst was characterized systematically by transmission electron microscopy,high‐resolution transmission electron microscopy,X‐ray diffraction,Raman,BET,X‐ray photoelectron spectroscopy,NH3 temperature‐programmed desorption and H2 temperature‐programmed reduction analyses.The optimized MnOx@TiO2 catalyst exhibits an obvious core‐shell structure,where the TiO2 shell is evenly distributed over the MnOx nanorod core.The catalyst also presents abundant mesopores,Lewis‐acid sites,and high redox capability,all of which enhance its catalytic performance.According to the XPS results,the decrease in the number of Mn4+active centers after SO2 poisoning is significantly lower in MnOx@TiO2 than in MnOx/TiO2.The core‐shell structure is hence able to protect the catalytic active sites from H2O and SO2 poisoning.展开更多
Magnetically separable bismuth ferrite(BiFeO3)nanoparticles were fabricated by a citrate self‐combustion method and coated with titanium dioxide(TiO2)by hydrolysis of titanium butoxide(Ti(OBu)4)to form BiFeO3@TiO2cor...Magnetically separable bismuth ferrite(BiFeO3)nanoparticles were fabricated by a citrate self‐combustion method and coated with titanium dioxide(TiO2)by hydrolysis of titanium butoxide(Ti(OBu)4)to form BiFeO3@TiO2core-shell nanocomposites with different mass ratios of TiO2to BiFeO3.The photocatalytic performance of the catalysts was comprehensively investigated via photocatalytic oxidation of methyl violet(MV)under both ultraviolet and visible‐light irradiation.The BiFeO3@TiO2samples exhibited better photocatalytic performance than either BiFeO3or TiO2alone,and a BiFeO3@TiO2sample with a mass ratio of1:1and TiO2shell thickness of50-100nm showed the highest photo‐oxidation activity of the catalysts.The enhanced photocatalytic activity was ascribed to the formation of a p‐n junction of BiFeO3and TiO2with high charge separation efficiency as well as strong light absorption ability.Photoelectrochemical Mott-Schottky(MS)measurements revealed that both the charge carrier transportation and donor density of BiFeO3were markedly enhanced after introduction of TiO2.The mechanism of MV degradation is mainly attributed to hydroxyl radicals and photogenerated electrons based on energy band theory and the formation of an internal electrostatic field.In addition,the unique core-shell structure of BiFeO3@TiO2also promotes charge transfer at the BiFeO3/TiO2interface by increasing the contact area between BiFeO3and TiO2.Finally,the photocatalytic activity of BiFeO3@TiO2was further confirmed by degradation of other industrial dyes under visible‐light irradiation.展开更多
A simple sonochemical route for the surface coating of titanium dioxide on cadmium sulfide nanocrystal was reported. After 2 h ultrasonic irradiation treatment, the mixture of CdS nanocrystals and tetrabutyl titanate ...A simple sonochemical route for the surface coating of titanium dioxide on cadmium sulfide nanocrystal was reported. After 2 h ultrasonic irradiation treatment, the mixture of CdS nanocrystals and tetrabutyl titanate in an aqueous medium yielded CdS/TiO2 nanocrystals composites with core/shell structure. The thickness of TiO2 layer with smooth interface could be easily controlled via changing the concentration of the precursors and the time of irradiation. The core/shell nanocrysrals were characterized by X-ray diffraction, transmission electron microscope and UV-vis spectrometry techniques. The prepared semiconductor composites with particular band structure present appealing properties especially in photochemical activity.展开更多
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 ...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.展开更多
TiO2 microspheres containing carbon have been synthesized viaa one-pot hydrothermal process using CTAB as the mesoporous template and nanoparticle stabilizer and Ti(SO4)2and sucrose as titanium and carbon precursors,r...TiO2 microspheres containing carbon have been synthesized viaa one-pot hydrothermal process using CTAB as the mesoporous template and nanoparticle stabilizer and Ti(SO4)2and sucrose as titanium and carbon precursors,respectively. Through well designed calcinations, Ti O2 microspheres with various amounts of carbon-residue,such as core/shell C@TiO2, hollow neat H–TiO2, and hollow C/TiO2 composites, are obtained. When these microspheres are used as anode materials for lithium ion batteries, the lithium storage performance is significantly influenced by the structure and carbon-residue. With a thin shell of TiO2 nanoparticles and carbon-residue, the capacity of hollow C/TiO2 composites maintains at 143.3 m A·h·g-1at 0.5 C(83.5 m A·g-1) after 100 cycles.Moreover, after high rate charge/discharge cycles from 0.2 C to 20 C and back to 0.2 C again, the reversible capacity recovers atas high as 195.1 m A·h·g-1with respect to its initial value of 205.0 m A·h·g-1. The results of cycle voltammograms and electrochemical impedance spectroscopy further reveal that Li+insertion/extraction processes are reversible, and the diffusion coefficient of Li+in the hollow C/TiO2 composites is much higher than those of others, because the hollow structure can act as the ion-buffering reservoir and facilitate Li+transfer from both sides of the shell, and the carbon-residue in the shell improves the conductivity as well.展开更多
Nanowire-based photovoltaic devices have the advantages over planar devices in light absorption and charge transport and collection.Recently,a new strategy relying on type-Ⅱ band alignment has been proposed to facili...Nanowire-based photovoltaic devices have the advantages over planar devices in light absorption and charge transport and collection.Recently,a new strategy relying on type-Ⅱ band alignment has been proposed to facilitate efficient charge separation in core/shell nanowire solar cells.This paper reviews the type-Ⅱ heterojunction solar cells based on core/shell nanowire arrays,and specifically focuses on the progress of theoretical design and fabrication of type-Ⅱ Zn O/Zn Se core/shell nanowire-based solar cells.A strong photoresponse associated with the type-Ⅱ interfacial transition exhibits a threshold of 1.6 e V,which demonstrates the feasibility and great potential for exploring all-inorganic versions of type-Ⅱ heterojunction solar cells using wide bandgap semiconductors.Future prospects in this area are also outlooked.展开更多
Zinc-air batteries(ZABs)hold tremendous promise for clean and efficient energy storage with the merits of high theoretical energy density and environmental friendliness.However,the performance of practical ZABs is sti...Zinc-air batteries(ZABs)hold tremendous promise for clean and efficient energy storage with the merits of high theoretical energy density and environmental friendliness.However,the performance of practical ZABs is still unsatisfactory because of the inevitably decreased activity of electrocatalysts when assembly into a thick electrode with high mass loading.Herein,we report a hierarchical electrocatalyst based on carbon microtube@nanotube core-shell nanostructure(CMT@CNT),which demonstrates superior electrocatalytic activity for oxygen reduction reaction and oxygen evolution reaction with a small potential gap of 0.678 V.Remarkably,when being employed as air-cathode in ZAB,the CMT@CNT presents an excellent performance with a high power density(160.6 mW cm^−2),specific capacity(781.7 mAhgZn^−1)as well as long cycle stability(117 h,351 cycles).Moreover,the ZAB performance of CMT@CNT is maintained well even under high mass loading(3 mg cm−2,three times as much as traditional usage),which could afford high power density and energy density for advanced electronic equipment.We believe that this work is promising for the rational design of hierarchical structured electrocatalysts for advanced metal-air batteries.展开更多
基金Joint Fund of Research and Development Program of Henan Province,Grant/Award Number:222301420002National Natural Science Foundation of China,Grant/Award Number:U21A2064Scientific and Technological Innovation Talents in Colleges and Universities in Henan Province,Grant/Award Number:22HASTIT001。
文摘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.”
基金funding from the Ministry of Education,Culture,Research,and Technology,Indonesia,through the PDKN Research Grant with Contract No.041/E5/PG.02.00.PL/2023.
文摘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.
基金National Natural Science Foundation of China,Grant/Award Numbers:21978160,52003300,52373087Shaanxi Province Natural Science Foundation,Grant/Award Number:2024JC‐YBMS‐131。
文摘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.
基金the financial support from National Natural Science Foundation of China (No. 21972102)National Key Research and Development Program of China (2021YFA0910400)+3 种基金Natural Science Foundation of Jiangsu Province (BK20200991)Suzhou Science and Technology Planning Project (SS202016)the USTS starting fund (No.332012104)the Natural Science Foundation of Suzhou University of Science and Technology (No.342134401)。
文摘Electrochemical nitrate reduction to ammonia(NRA) can realize the green synthesis of ammonia(NH3) at ambient conditions, and also remove nitrate contamination in water. However, the current catalysts for NRA still face relatively low NH3yield rate and poor stability. We present here a core-shell heterostructure comprising cobalt oxide anchored on copper oxide nanowire arrays(CuO NWAs@Co_(3)O_(4)) for efficient NRA. The CuO NWAs@Co_(3)O_(4)demonstrates significantly enhanced NRA performance in alkaline media in comparison with plain CuO NWAs and Co_(3)O_(4)flocs. Especially, at-0.23 V vs. RHE, NH_(3) yield rate of the CuO NWAs@Co_(3)O_(4)reaches 1.915 mmol h^(-1)cm^(-2),much higher than those of CuO NWAs(1.472 mmol h^(-1)cm^(-2)), Co_(3)O_(4)flocs(1.222 mmol h^(-1)cm^(-2)) and recent reported Cu-based catalysts.It is proposed that the synergetic effects of the heterostructure combing atom hydrogen adsorption and nitrate reduction lead to the enhanced NRA performance.
基金Project supported by the National Natural Science Foundation of China(No.11972259)。
文摘Wrinkles in flat graded elastic layers have been recently described as a timevarying Hamiltonian system by the energy method.Cylindrical core/shell structures can also undergo surface instabilities under the external pressure.In this study,we show that by treating the radial direction as a pseudo-time variable,the graded core/shell system with radially decaying elastic properties can also be described within the symplectic framework.In combination with the shell buckling equation,the present paper addresses the surface wrinkling of graded core/shell structures subjected to the uniform external pressure by solving a series of ordinary differential equations with varying coefficients.Three representative gradient distributions are showcased,and the predicted critical pressure and critical wave number are verified by finite element simulations.The symplectic framework provides an efficient and accurate approach to understand the surface instability and morphological evolution in curved biological tissues and engineered structures.
文摘This paper reports on the ablation process of a pure Ti solid target immersed in a C-enriched acetone solution, leading to the production of titanium carbide (TiC) and Ti-C core-shell nanostructures. The used route of synthesis is generally called pulsed laser ablation in liquid (PLAL). The presence of carbon structures in the solution contributed to the carbon content in the produced Ti-based nanomaterials. The atomic composition of the produced nanostructures was analyzed using SEM-EDS, while TEM micrographs revealed the formation of spherical TiC and core-shell nanostructures ranging from 40 to 100 nm. The identification of atomic planes by HRTEM confirmed a 10 nm diameter C-shell with a graphite structure surrounding the Ti-core. Raman spectroscopy allowed for the identification of D and G peaks for graphite and a Raman signal at 380 and 600 cm<sup>−1</sup>, assigned to TiC. The results contribute to the state-of-the-art production of TiC and Ti-C core-shell nanostructures using the PLAL route.
文摘AucoreCoshell nanoparticles with different shell thicknesses were prepared by using chemical reduction method and characterized by scanning electron microscopy(SEM) and cyclic voltammetry(CV). The results reveal that the prepared core-shell nanoparticles were covered by Co shell and exhibited the similar electrochemistry property with the Co nanoparticles surface. Surface enhanced Raman spectroscopy(SERS) activities of these nanoparticles were studied by using pyridine as a probe molecule. It was found that the SERS intensity depended on the Co shell thickness of the core-shell nanoparticles and was weakened with the increasing shell thickness. The SERS intensity of these AucoreCoshell nanoparticles is found to be about twenty times higher than that obtained on an electrochemically roughened cobalt electrode.
基金supported by the National Major Research Project(2016YFB0101208)the National Natural Science Foundation of China(21576257)the Natural Science Foundation-Liaoning United Fund(U1508202)~~
文摘Core-shell nanostructures have been widely investigated to improve the electrocatalytic perfor-mance of platinum. However, organic precursors, surfactants or high temperature are usually nec-essary during the preparation procedure. Unfortunately, these requirements limit the application of these methods on a large scale. Herein, a Pdcore@ Pt shell nanostructure was fabricated through the reduction of fcPtCU by dissociated hydrogen at room temperature without the assistance o f either a surfactant or a high-boiling point solvent. The shell thickness of this nanostructure was successfully controlled by varying the amount of fcPtCU; core-shell nanoparticles with a shell thickness of 0.45, 0.75 and 0.90 nm w ere obtained, as determined by TEM. The remarkable crystallinity and epitaxial growth of the Pdcore@ Pt shell nanostructure were revealed by HRTEM and EDS. According to ICP and XPS, surface segregation of Pt was established. The impressive ORR performance was attributed to the weak adsorption strength of the OHads species, which resulted from the electron transfer impact between the Pdcore and Ptshell. The facile and clean preparation method can be used to prepare other core-shell nanostructures under a mild atmosphere.
基金This work is supported by the National Natural Science Foundation of China (No.10574122, No.50772110, No.50721091) and the National Basic Research Program of China (No.2011CB921400, No.2007CB925202, No.2009CB939901).
文摘We present a general approach to fabricate metal/TiO2 core/shell nanorod structures by twostep electrodeposition. Firstly, TiO2 nanotubes with uniform wall thickness are prepared in anodic aluminum oxide (AAO) membranes by electrodeposition. The wall thickness of the nanotubes could be easily controlled by modulating the deposition time, and their outer diameter and length are only limited by the channel diameter and the thickness of the AAO membranes, respectively. The nanotubes' tops prepared by this method are open, while the bottoms are connected directly with the Au film at the back of the AAO membranes. Secondly, Pd, Cu, and Fe elements are filled into the TiO2 nanotubes to form core/shell structures. The core/shell nanorods prepared by this two-step process are high density and free-standing, and their length is dependent on the deposition time.
基金financially supported by the National Natural Science Foundation of China(Grant No.2117103551472049 and 51302035)+7 种基金the Key Grant Project of Chinese Ministry of Education(Grant No.313015)the PhD Programs Foundation of the Ministry of Education of China(Grant No.20110075110008 and20130075120001)the National 863 Program of China(Grant No.2013AA031903)the Science and Technology Commission of Shanghai Municipality(Grant No.13ZR1451200)the Fundamental Research Funds for the Central Universitiesthe Program Innovative Research Team in University(IRT1221)the Shanghai Leading Academic Discipline Project(Grant No.B603)the Program of Introducing Talents of Discipline to Universities(No.111-2-04)
文摘Herein, combining solverthermal route and electrodeposition, we grew unique hybrid nanosheet arrays consisting of Co_3O_4 nanosheet as a core, PPy as a shell. Benefiting from the PPy as conducting polymer improving an electron transport rate as well as synergistic effects from such a core/shell structure, a hybrid electrode made of the Co_3O_4@PPy core/shell nanosheet arrays exhibits a large areal capacitance of 2.11 F cm-2at the current density of 2 m A cm^(-2), a *4-fold enhancement compared with the pristine Co_3O_4electrode; furthermore, this hybrid electrode also displays good rate capability(*65 % retention of the initial capacitance from 2 to 20 m A cm^(-2)) and superior cycling performance(*85.5 % capacitance retention after 5000 cycles). In addition, the equivalent series resistance value of the Co_3O_4@PPy hybrid electrode(0.238 X) is significantly lower than that of the pristine Co_3O_4electrode(0.319 X). These results imply that the Co_3O_4@PPy hybrid composites have a potential for fabricating next-generation energy storage and conversion devices.
基金World Premier International Research Center Initiative(WPI Initiative)on Materials Nanoarchitronics,MEXT,Japanthe Japan Society for the Promotion of Science (JSPS)for a support in the form of a fellowship tenable at the National Institute for Materials Science,Tsukuba,Japan.
文摘A focus of the current nanotechnology has shifted from routine fabrication of nanostructures to designing functional electronic devices and realizing their immense potentials for applications. Due to infusion of multi-functionality into a single system, the utilization of hetero-, core/shell and hierarchical nanostructures has become the key issue for building such devices. ZnS, due to its direct wide bandgap, high index of refraction, high transparency in the visible range and intrinsic polarity, is one of the most useful semiconductors for a wide range of electronics applications. This article provides a dense review of the state-of-the-art research activities in one-dimensional (1D) ZnS-based hetero-, core/shell and hierarchical nanostructures. The particular emphasis is put on their syntheses and applications.
文摘In this study,a MnOx@TiO2 core‐shell catalyst prepared by a two‐step method was used for the low‐temperature selective catalytic reduction of NOx with NH3.The catalyst exhibits high activity,high stability,and excellent N2 selectivity.Furthermore,it displays better SO2 and H2O tolerance than its MnOx,TiO2,and MnOx/TiO2 counterparts.The prepared catalyst was characterized systematically by transmission electron microscopy,high‐resolution transmission electron microscopy,X‐ray diffraction,Raman,BET,X‐ray photoelectron spectroscopy,NH3 temperature‐programmed desorption and H2 temperature‐programmed reduction analyses.The optimized MnOx@TiO2 catalyst exhibits an obvious core‐shell structure,where the TiO2 shell is evenly distributed over the MnOx nanorod core.The catalyst also presents abundant mesopores,Lewis‐acid sites,and high redox capability,all of which enhance its catalytic performance.According to the XPS results,the decrease in the number of Mn4+active centers after SO2 poisoning is significantly lower in MnOx@TiO2 than in MnOx/TiO2.The core‐shell structure is hence able to protect the catalytic active sites from H2O and SO2 poisoning.
基金supported by the Australian Research Council(ARC DP150103026)the National Natural Science Foundation of China(51278242)~~
文摘Magnetically separable bismuth ferrite(BiFeO3)nanoparticles were fabricated by a citrate self‐combustion method and coated with titanium dioxide(TiO2)by hydrolysis of titanium butoxide(Ti(OBu)4)to form BiFeO3@TiO2core-shell nanocomposites with different mass ratios of TiO2to BiFeO3.The photocatalytic performance of the catalysts was comprehensively investigated via photocatalytic oxidation of methyl violet(MV)under both ultraviolet and visible‐light irradiation.The BiFeO3@TiO2samples exhibited better photocatalytic performance than either BiFeO3or TiO2alone,and a BiFeO3@TiO2sample with a mass ratio of1:1and TiO2shell thickness of50-100nm showed the highest photo‐oxidation activity of the catalysts.The enhanced photocatalytic activity was ascribed to the formation of a p‐n junction of BiFeO3and TiO2with high charge separation efficiency as well as strong light absorption ability.Photoelectrochemical Mott-Schottky(MS)measurements revealed that both the charge carrier transportation and donor density of BiFeO3were markedly enhanced after introduction of TiO2.The mechanism of MV degradation is mainly attributed to hydroxyl radicals and photogenerated electrons based on energy band theory and the formation of an internal electrostatic field.In addition,the unique core-shell structure of BiFeO3@TiO2also promotes charge transfer at the BiFeO3/TiO2interface by increasing the contact area between BiFeO3and TiO2.Finally,the photocatalytic activity of BiFeO3@TiO2was further confirmed by degradation of other industrial dyes under visible‐light irradiation.
基金Funded by the National Natural Science Foundation of China (Nos.50532030 and 50625206)the Zhejiang Provincial Natural ScienceFoundation of China (No. Z4080021)
文摘A simple sonochemical route for the surface coating of titanium dioxide on cadmium sulfide nanocrystal was reported. After 2 h ultrasonic irradiation treatment, the mixture of CdS nanocrystals and tetrabutyl titanate in an aqueous medium yielded CdS/TiO2 nanocrystals composites with core/shell structure. The thickness of TiO2 layer with smooth interface could be easily controlled via changing the concentration of the precursors and the time of irradiation. The core/shell nanocrysrals were characterized by X-ray diffraction, transmission electron microscope and UV-vis spectrometry techniques. The prepared semiconductor composites with particular band structure present appealing properties especially in photochemical activity.
基金Supported by the National Natural Science Foundation of China(21676238)
文摘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.
基金Supported by the National Natural Science Foundation of China(21176066)the 111 Project of the Ministry of Education of China(B08021)the Fundamental Research Funds for the Central Universities
文摘TiO2 microspheres containing carbon have been synthesized viaa one-pot hydrothermal process using CTAB as the mesoporous template and nanoparticle stabilizer and Ti(SO4)2and sucrose as titanium and carbon precursors,respectively. Through well designed calcinations, Ti O2 microspheres with various amounts of carbon-residue,such as core/shell C@TiO2, hollow neat H–TiO2, and hollow C/TiO2 composites, are obtained. When these microspheres are used as anode materials for lithium ion batteries, the lithium storage performance is significantly influenced by the structure and carbon-residue. With a thin shell of TiO2 nanoparticles and carbon-residue, the capacity of hollow C/TiO2 composites maintains at 143.3 m A·h·g-1at 0.5 C(83.5 m A·g-1) after 100 cycles.Moreover, after high rate charge/discharge cycles from 0.2 C to 20 C and back to 0.2 C again, the reversible capacity recovers atas high as 195.1 m A·h·g-1with respect to its initial value of 205.0 m A·h·g-1. The results of cycle voltammograms and electrochemical impedance spectroscopy further reveal that Li+insertion/extraction processes are reversible, and the diffusion coefficient of Li+in the hollow C/TiO2 composites is much higher than those of others, because the hollow structure can act as the ion-buffering reservoir and facilitate Li+transfer from both sides of the shell, and the carbon-residue in the shell improves the conductivity as well.
基金supported by "973" Program (No.2012CB619301 and 2011CB925600)the National Natural Science Foundations of China (No.61227009,61106008,61106118,90921002,and 60827004)+1 种基金the Natural Science Foundations of Fujian Provincethe fundamental research funds for the central universities (No.2011121042 and 2011121026)
文摘Nanowire-based photovoltaic devices have the advantages over planar devices in light absorption and charge transport and collection.Recently,a new strategy relying on type-Ⅱ band alignment has been proposed to facilitate efficient charge separation in core/shell nanowire solar cells.This paper reviews the type-Ⅱ heterojunction solar cells based on core/shell nanowire arrays,and specifically focuses on the progress of theoretical design and fabrication of type-Ⅱ Zn O/Zn Se core/shell nanowire-based solar cells.A strong photoresponse associated with the type-Ⅱ interfacial transition exhibits a threshold of 1.6 e V,which demonstrates the feasibility and great potential for exploring all-inorganic versions of type-Ⅱ heterojunction solar cells using wide bandgap semiconductors.Future prospects in this area are also outlooked.
基金supported by the National Natural Science Foundation of China(21922501,21871021 and 21521005)the Beijing Natural Science Foundation(2192040)+1 种基金the National Key Research and Development Programme(2017YFA0206804)the Fundamental Research Funds for the Central Universities(XK1802-6 and 479 XK1803-05).
文摘Zinc-air batteries(ZABs)hold tremendous promise for clean and efficient energy storage with the merits of high theoretical energy density and environmental friendliness.However,the performance of practical ZABs is still unsatisfactory because of the inevitably decreased activity of electrocatalysts when assembly into a thick electrode with high mass loading.Herein,we report a hierarchical electrocatalyst based on carbon microtube@nanotube core-shell nanostructure(CMT@CNT),which demonstrates superior electrocatalytic activity for oxygen reduction reaction and oxygen evolution reaction with a small potential gap of 0.678 V.Remarkably,when being employed as air-cathode in ZAB,the CMT@CNT presents an excellent performance with a high power density(160.6 mW cm^−2),specific capacity(781.7 mAhgZn^−1)as well as long cycle stability(117 h,351 cycles).Moreover,the ZAB performance of CMT@CNT is maintained well even under high mass loading(3 mg cm−2,three times as much as traditional usage),which could afford high power density and energy density for advanced electronic equipment.We believe that this work is promising for the rational design of hierarchical structured electrocatalysts for advanced metal-air batteries.