Core-shell Nanocubes Research Articles

Plasmonic Nanocubes with a Controllable "Crescent Arc" Facet: Tunable Hotspot Engineering for Highly Reliable and Sensitive SERS Detection.

The fine control of the nanogap and morphology of metal nanoparticles (NPs) has always been an obstacle, hindering the development and application of surface-enhanced Raman scattering (SERS) quantitative detection. Here, Au/4-mercaptobenzoic acid@Ag@Au-Ag bimetal core-shell nanocubes (NCs) with a "crescent arc" facet (C-Au/4MBA@Ag NCs) as a highly reliable and sensitive surface-enhanced Raman scattering SERS substrate is proposed for the first time. The bifunctional internal standard (IS) molecules (4MBA) govern the morphology of metal shells to maintain cubic configuration and provide calibration for SERS signals' flotation. In parallel, the controllable curvature of the C-Au/4MBA@Ag NCs is directly modulated by adjusting the relative rates of the galvanic replacement and co-reduction reaction, which generates a controllable interparticle nanogap to offer large depositing spaces for analytes and improve authoritative SERS signals' enhancement. The proposed C-Au/4MBA@Ag NCs exhibit an enhancement factor of up to 4.8 × 1010 and contribute to the ultralow RSD (7.9%). These C-Au/4MBA@Ag NCs also enable the detection of hazardous pesticide residues such as methamidophos and thiram in herbal plants with a complex matrix, with an average detection accuracy of up to 96%. In summary, this study achieves a fine control strategy of the "crescent arc" surface for improving SERS performance and explores the practical application potential for accurate and sensitive Raman detection of hazardous substances.

Core-shell Ru@Co2P synergistic catalyst as polysulfides adsorption-catalytic conversion mediator with enhanced redox kinetics in lithium-sulfur batteries

Lithium-sulfur batteries (LSBs) have emerged as the research hotspot due to their compelling merits, including high specific capacity (1675 mAh g−1), theoretical energy density (2600 Wh kg−1), environmental friendliness, and economic advantages. However, challenges still exist for further application due to their inherent issues such as the natural insulation, shuttle effect, and volume expansion of sulfur cathode during the continuous cycle processes. These factors obstruct the lithium ions (Li+) transfer process and sulfur utilization, resulting in significant impedance and inducing inferior battery performance. Herein, the core–shell nanocube anchoring ruthenium atoms and dicobalt phosphate (Ru@Co2P@NC) were fabricated as the effective catalyst and inhibited barrier for LSBs. On the one hand, the core–shell structure offers numerous channels to expedite Li+ diffusion. On the other hand, ruthenium (Ru) and dicobalt phosphate (Co2P) active sites facilitate the chemical capture of lithium polysulfides (LiPSs), accelerating sluggish kinetics. Ru@Co2P@NC modified cells not only exhibited a high initial specific capacity (1609.35 mAh g−1) at 0.5C and enduring stability with high specific capacity retention of 906.60 mAh g−1 at 0.5C after 400 cycles but also possessed low capacity attenuation rate of 0.07 % per cycle after 600 cycles (1C, Sulfur loading: 1.2 mg). Interestingly, the modified cells demonstrated a high specific capacity and long-cycle stability with high sulfur loading (from 1.984 to 3.137 mg), which provides a promising research approach for high-performance LSBs.

Nanocube-shaped In2O3@TiO2 core-shell based chemiresistive-type sensors for formaldehyde detection at room temperature

In2O3@TiO2 core-shell nanocubes were successfully prepared via hydrothermal method and subsequent water bath method. The characterization results show that the size of the In2O3@TiO2 nanocomposites is 250–350 nm. The In2O3@TiO2 nanocomposites based sensor presents excellent sensing response to formaldehyde at ppb level. The response of In2O3@TiO2 nanocomposites based sensor to 1 ppm formaldehyde is about 5.3 at room temperature under UV activation, which is three times higher than that of the pure In2O3 based sensor. The response/recovery time of In2O3@TiO2 nanocomposites based sensor are 24 s and 52 s, respectively. The involved chemical reactions activated by UV had been investigated by in-situ diffuse reflectance Fourier transform infrared spectroscopy (DRIFTS). This work proves that core-shell nanocubes combined with UV activation could significantly enhance the sensing properties of the sensors.

Synthesis of Au@Ag core-shell nanocubes with finely tuned shell thicknesses for surface-enhanced Raman spectroscopic detection.

In this work, we describe a facile method for generating monodisperse Au@Ag core-shell nanocubes with well-controlled size and fine-tuned Ag shell thicknesses. In this synthesis method, Au nanocubes were prepared via the seed-mediated growth method. Then, Au@Ag nanocubes with the core-shell structure were prepared separately by reducing AgNO3 with AA using as-prepared Au nanocubes as seeds. The thickness of Ag shells could be finely tuned from 3.6 nm to 10.0 nm by varying the concentration of the AgNO3 precursor. By investigating the localized surface plasmon resonance (LSPR) properties of Au@Ag nanocubes in relation to the thickness of the Ag shell, we found that the intensity of the characteristic peak of Ag gradually increases and that of Au gradually decreases as the thickness of the Ag shell increases. Additionally, surface-enhanced Raman scattering (SERS) properties of Au@Ag core-shell nanocubes were evaluated using rhodamine 6G (R6G) as the probe molecule. Interestingly, Au@Ag nanocubes exhibit efficient SERS intensities compared to the Au nanocubes, and Ag shell with a thickness of about 8.4 nm exhibits the optimal SERS activity. In addition, our results also demonstrated that Au@Ag nanocubes with an Ag shell thickness of 8.4 nm exhibited high SERS sensitivity and are capable of probing the analyte down to 10-12 M. The results obtained here suggest that Au@Ag core-shell nanocubes might serve as a nanoprobe for SERS-based analytical and biosensing applications.

Kinetics of spontaneous phase transitions from wüstite to magnetite in superparamagnetic core-shell nanocubes of iron oxides.

Iron oxide nanoparticles with a wüstite structure have been prepared by thermal decomposition. In air, they undergo a spontaneous transition into a thermodynamically more stable magnetite structure that grows from the surface. The thickness of this magnetite shell increases with time, thereby producing a series of core-shell nanoparticles. We investigated the kinetics of this phase transition in 23 nm nanocubes using time-resolved XRD, from which the fractions of individual phases were determined by the Rietveld refinement. This kinetics is described theoretically using three coupled reaction-diffusion master equations for the concentrations of oxygen, wüstite, and magnetite, in which both the diffusion of oxygen and its reaction with wüstite are thermally activated. The coefficients of these terms were adjusted so that the predictions of the model reproduce the XRD data at 298 K and 353 K, whereas the predictive capability of the model was assessed by comparing its predictions with measurements at 403 K.

CdS/ZnSnO3 Hollow Core–Shell Nanocubes for Photocatalytic Hydrogen Evolution and Degradation of Ciprofloxacin

CdS/ZnSnO₃ Hollow Core–Shell Nanocubes for Photocatalytic Hydrogen Evolution and Degradation of Ciprofloxacin

Synthesis of BaTiO3-CaTiO3 and BaTiO3-SrTiO3 Core-Shell Nanocubes via the Surface Reconstruction of BaTiO3 Nanocubes.

BaTiO3-CaTiO3 and SrTiO3-BaTiO3 core-shell nanocubes were synthesized through the surface reconstruction of BaTiO3 nanocubes, which involved the reaction of titanium oxide with Ca(OH)2, Sr(OH)2, or Sr(OH)2·8H2O in water at 100 °C. The core-shell structure comprised a BaTiO3 nanocube core and a CaTiO3 or SrTiO3 shell. The outermost layer with a perovskite structure also comprised CaTiO3 or SrTiO3, and its thickness was several hundred picometers. The thinnest layer was constructed of only one layer of CaTiO3 or SrTiO3. This is the first presented work on a core-shell nanocube with the outermost layer consisting of only CaTiO3 or SrTiO3 surrounding the BaTiO3 nanocube. The shells of CaTiO3 and SrTiO3 comprise a layer thickness of only one unit cell of ∼0.4 nm (400 pm). Thus, we demonstrate new research on nanocube surfaces on the picometer scale.

A microfluidic platform for minute-scale synthesizing Au@Ag nanocubes

Noble metal nanoparticles are enduring primarily because of their unique Localized Surface Plasmon Resonance (LSPR) properties, which make them exciting for medical testing, biosensing, and other applications. The LSPR properties of nanoparticles with different shapes and different structures vary. The sharp edges of the cubic structure enable stronger LSPR performance making it more versatile for diverse applications. However, the fast and stable controlled synthesis of cubes, an anisotropic nanoparticle, has been an obstacle for researchers. Microfluidics has a reaction space that matches the scale of the nanoparticles, and the efficient heat and mass transfer capability in the tiny confined space ensures that the synthesis reaction proceeds more efficiently and reliably. Herein, we designed a microfluidic platform for the controlled synthesis of Au@Ag nanocubes, which can synthesize core-shell nanocubes of uniform shape and size in 15 min. Moreover, both Raman probe methylene blue and antibiotic sulfadiazine were detected using this material as a substrate for SERS detection, obtaining satisfactory results (10−10 M and 10−7 M, separately).

Construction of quantum well surface from an Nb surface–doped core-shell La-SrTiO3 nanocubes for photocatalytic hydrogen production

Construction of quantum well surface from an Nb surface–doped core-shell La-SrTiO3 nanocubes for photocatalytic hydrogen production

Synergistically Enhanced Oxidase-like Property of Core-Shell MOF Nanozymes by Decorating Au and Ag/AgCl Nanoparticles for l-Cysteine Colorimetric Sensing.

Monitoring l-cysteine (l-Cys) is of importance for human health and food safety. Herein, we designed a novel strategy for bimetallic Au and Ag/AgCl anchoring on Ni-doped ZIF-67 to form core-shell nanocubes (Ni-ZIF-67/AuAg/AgCl) using the galvanic replacement processes. The unique properties of ZIF-67 nanocubes were conducive to generating strong synergistic catalytic effects with Au and Ag/AgCl, particularly when Ni-ZIF-67/AuAg/AgCl composites were employed as oxidase mimics for catalyzing the oxidation of 3,3',5,5'-tetramethylbenzidine (TMB). The Ni-ZIF-67/AuAg/AgCl composites displayed strong affinity toward TMB, displaying a lower Michaelis constant Km value of 0.25 mM and a higher maximum initial rate Vmax of 9 × 10-8 M s-1. By virtue of the nanozyme, the colorimetric sensor was constructed for l-Cys detection with a relatively low detection limit of 0.051 μM. The superior catalytic performance of the as-prepared Ni-ZIF-67/AuAg/AgCl composites can be ascribed to the core-shell structure, large specific surface area, and strong synergistic catalytic effects, which are beneficial for exposing more active sites and enhancing the conductivity to further boost their catalytic activity.

Heterostructured hollow cobalt-nickel core-shell hexacyanoferrate nanocubes for enhanced electrocatalytic oxidation of urea molecules in alkaline electrolyte

The hollow cobalt-nickel core-shell hexacyanoferrate (CoNiHCF) nanocube is prepared by forming a thin nickel hexacyanoferrate (NiHCF) shell on a hollow cobalt hexacyanoferrate (CoHCF) nanocube as a synergistic catalyst for urea oxidation reaction (UOR). The CoNiHCF reduces the peak-to-peak separation of the cyclic voltammograms for Ni2+/Ni3+ couple, which favors the reversible regeneration of active Ni3+ species. NiHCF, a kind of Prussian blue analogue, has greater UOR kinetics than nickel foam and CoHCF, due to its open framework structure with redox-active nickel and iron species. The hollow core-shell architecture affords numerous pathways for fast electron and electrolyte transport, enhancing the adsorption and oxidation of urea molecules on the catalytic Ni3+ sites. Electrochemical impedance spectroscopy reveals superior UOR kinetics of CoNiHCF compared to the NiHCF catalyst, reflected by its low electrical resistance, charge-transfer resistance, and direct UOR resistance. The CoHCF core in the CoNiHCF provides a conductive host to immobilize the nickel-rich catalyst shell to promote the formation of high-valence species Ni3+ to boost the electrocatalytic activity of the CoNiHCF. The CoNiHCF catalyst exhibits a high oxidation current (175 mA cm−2 at 1.570 V), small onset potential (1.335 V), and remarkable durability, rendering it a highly promising catalyst material for UOR.

Facile Synthesis of Ru Nanoboxes with a Hexagonal Close-Packed Structure by Templating with Ag Nanocubes and Their Catalytic Properties.

Noble-metal nanoboxes offer an attractive form of nanomaterials for catalytic applications owing to their open structure and highly efficient use of atoms. Herein, we report the facile synthesis of Ag-Ru core-shell nanocubes and then Ru nanoboxes with a hexagonal close-packed (hcp) structure, as well as evaluation of their catalytic activity toward a model hydrogenation reaction. By adding a solution of Ru(acac)3 in ethylene glycol (EG) dropwise to a suspension of silver nanocubes in EG at 170 °C, Ru atoms are generated and deposited onto the entire surface of a nanocube. As the volume of the RuIII precursor is increased, Ru atoms are also produced through a galvanic replacement reaction, generating Ag-Ru nanocubes with a hollow interior. The released Ag+ ions are then reduced by EG and deposited back onto the nanocubes. By selectively etching away the remaining Ag with aqueous HNO3 , the as-obtained Ag-Ru nanocubes are transformed into Ru nanoboxes, whose walls are characterized by an hcp structure and an ultrathin thickness of a few nanometers. Finally, we evaluated the catalytic properties of the Ru nanoboxes with two different wall thicknesses by using a model hydrogenation reaction; both samples showed excellent performance.

Strain and Shell Thickness Engineering in Pd3 Pb@Pt Bifunctional Electrocatalyst for Ethanol Upgrading Coupled with Hydrogen Production.

The ethanol oxidation reaction (EOR) is an attractive alternative to the sluggish oxygen evolution reaction in electrochemical hydrogen evolution cells. However, the development of high-performance bifunctional electrocatalysts for both EOR and hydrogen evolution reaction (HER) is a major challenge. Herein, the synthesis of Pd3 Pb@Pt core-shell nanocubes with controlled shell thickness by Pt-seeded epitaxial growth on intermetallic Pd3 Pb cores is reported. The lattice mismatch between the Pd3 Pb core and the Pt shell leads to the expansion of the Pt lattice. The synergistic effects between the tensile strain and the core-shell structures result in excellent electrocatalytic performance of Pd3 Pb@Pt catalysts for both EOR and HER. In particular, Pd3 Pb@Pt with three Pt atomic layers shows a mass activity of 8.60 A mg-1 Pd+Pt for ethanol upgrading to acetic acid and close to 100% of Faradic efficiency for HER. An EOR/HER electrolysis system is assembled using Pd3 Pb@Pt for both the anode and cathode, and it is shown that low cell voltage of 0.75V is required to reach a current density of 10mA cm-2 . The present work offers a promising strategy for the development of bifunctional catalysts for hybrid electrocatalytic reactions and beyond.

Femtomolar endogenous adenosine triphosphate-responded photoelectrochemical biosensor based on Au@Cu2O core-shell nanocubes for the ultrasensitive determination of Escherichia coli O157:H7 in foods

Sensitive and precise determination of virulent foodborne pathogens is significant for food safety. Herein, an ultrasensitive photoelectrochemical (PEC) bioanalysis was developed using the endogenous adenosine triphosphate (ATP)-responded Au@Cu2O core-shell nanocubes (Au@Cu2O NCs) to measure Escherichia coli O157: H7 (E. coli O157:H7) in food. Briefly, the phage-functionalized gold wire was used to specifically recognize the target pathogen. With the bacteriolysis of lysozyme, the endogenous ATP molecules were emitted from the captured target bacteria and enriched by another ATP aptamer-modified gold wire. Following the exchange with complementary DNA (cDNA) chains, the bonded ATP would be released. It could simultaneously etch the Au@Cu2O NCs and compete with external circuit electrons to combine photogenerated holes on the Au@Cu2O NCs-modified screen-printed electrode. With the synergy of the two signal amplification mechanisms, a significant attenuation of photocurrent signal appeared even with femtomolar ATP. Therefore, the purpose of ultrasensitive determination of E. coli O157:H7 was realized, which depended on the endogenous ATP rather than exogenous signal probes. The proposed biosensor presented a good analysis performance within 10–106 CFU/mL with a detection limit of 5 CFU/mL. Besides, its specificity, repeatability, and stability were also investigated and acceptable. The detection results for food samples matched well with the results detected by the plate counting method. This work gives an innovative and sensitive signal amplification strategy for PEC bioassays in foodborne pathogens detection.

Thermal Behavior of Silver–Gold Core–Shell Nanocubes: In Situ X-ray Diffraction and In Situ Electron Microscopy (SEM and TEM)

Thermal Behavior of Silver–Gold Core–Shell Nanocubes: In Situ X-ray Diffraction and In Situ Electron Microscopy (SEM and TEM)

Dynamically Metasurface-Modulated Electrochemiluminescence Polarization Coupling Angle Strategy for miR-142-3p Detection.

The combination of the electrochemiluminescence (ECL) technique with nanophotonics research can spark new analytical and sensing applications. Herein, we developed a novel modulation strategy of the ECL polarization angle based on the dynamically tunable few-layer metasurface. The bilayer metasurface consisted of a fixed Au-Ag core-shell nanocube array (Au@Ag NCA) layer with strong plasmonic hot spots and different amounts of the Au nanoparticles@MoS2 heterostructure nanosheet (0D-2D HNS) layer with strong metal-support interaction. Due to the interference and near-field coupling between layers, the bilayer metasurface can strongly redistribute the local electromagnetic field and energy in the ECL system, which not only significantly amplified the ECL signal but also modulated the polarization coupling angle. Therefore, the novel ECL polarization angle-resolved sensing strategy has been developed, which was beneficial to improve the sensitivity and resolution of ECL sensing. A dynamically tunable metasurface-based ECL biosensor was successfully used to detect the asthma-related miRNA-142-3p (miR-142-3p). Moreover, the simulation calculations of the electromagnetic field revealed the unique optical activity of the metasurface. This study brought the insightful understanding of the metasurface-modulated optical signal and provided a new idea to construct novel sensing platforms.

Glutathione-Mediated Synthesis of Yolk-Shell AuAg Nanostructures Containing a Spherical Core and Cuboctahedral Skeletons and Their Applications in Plasmonic Catalysis.

Frame/skeleton-like nanostructures are of great value in plasmonic catalysis as a result of the synergetic structural advantages arising from both maximized surface atomic exposure and efficient incident light absorptions. Herein, we report the size-tunable fabrication of yolk-shell AuAg nanoparticles containing a spherical core and cuboctahedral skeletons (AuAg YSCNSs), together with the exploration of their applications for assisting the reduction of 4-nitrophenol (4-NP) under ultraviolet-visible (UV-vis) light irradiation. The use of glutathione (GSH) at an appropriate amount to mediate the galvanic replacement reaction between Au@Ag core-shell nanocubes and HAuCl4 is found to be crucial in regulating the shape evolution. Their sizes could be readily tuned by altering the edge lengths of Au@Ag core-shell nanocubes. When working as the photocatalyst assisting the reduction of 4-NP, the AuAg YSCNSs exhibit a higher apparent rate constant under UV-vis light irradiation. The current work demonstrates the feasibility to create skeleton-like noble metal nanocrystals with the shape largely deviated from that of the original template via the "top-down" carving strategy by introducing non-metallic surface doping, which could be potentially extended to other noble metals or alloys.

Asymmetric Heterodimer-Regulated Surface Plasmon Coupling ECL Polarization Strategy for MiRNA-182 Detection.

In this work, a novel plasmonic heterodimer with controllable hot spot was designed and applied to regulate surface plasmon coupling electrochemiluminescence (SPC-ECL) polarization sensing system. The heterodimer nanostructure consisted of individual Au-Ag core-shell nanocubes (Au@Ag NC) and Au nanospheres (Au NS), which were precisely assembled by thiol-DNA and biotin-streptavidin. The asymmetric nanostructure can significantly modulate the ECL intensity and emission polarization angle based on the synergy of the surface plasmon coupling (SPC) effect and the lightning rod effect with extraordinary field enhancement in the hot spot region. As a result, the isotropic ECL signal of zinc-doped nitrogen dots (Zn-N dots) was regulated in the directional emission. Furthermore, the SPC-ECL biosensor was successfully applied to detect miRNA-182 in triple-negative breast cancer (TNBC) tissues. The research on the established relationship between ECL polarization analysis and plasmonic heterodimers can provide a new pathway for the development of ECL sensing platforms.

Synthesis of Pd@Rh nanocubes with well-defined {100} surface and controlled shell thicknesses for the fabrication of Rh nanocages

We report a facile synthesis of Pd@Rh core–shell nanocubes with ultrathin Rh shell and well-defined, smooth {100} facets for the production of Rh cubic nanocages. Under carefully optimized conditions, the deposition and diffusion rates of Rh adatoms on Pd cubic seeds can be tuned to a suitable level to enable the layer-by-layer growth of Rh overlayers. Specifically, the reaction temperature, type of Rh precursor, injection rate of the precursor solution, in addition to the size of the Pd seeds, all play an important role in establishing the desired growth mode while preventing island growth and homogeneous nucleation. The Rh shell not only endows the nanocrystals with significantly enhanced shape stability against thermally activated transformation under heating up to 500 °C, but also enables the production of Rh nanocages with ultrathin walls and well-preserved {100} facets, which to our knowledge has not been reported in literature.

Preparation of a Three-Dimensional Composite Structure Based on a Periodic Au@Ag Core-Shell Nanocube with Ultrasensitive Surface-Enhanced Raman Scattering for Rapid Detection.

The absorption and scattering frequencies of surface plasmon resonance can be selectively adjusted by changing the morphology, size, structure, arrangement, and gap between noble metal nanoparticles so that the local electromagnetic field on the substrate surface can be further enhanced. This change will promote and popularize surface-enhanced Raman spectroscopy. This paper reports the research results and improvement scheme of surface enhanced Raman scattering (SERS) activity of silver-coated gold nanocubed/organism (Au@Ag/CW NCs) prepared by three-phase self-assembly. In the experiment, the uppermost oil phase in the three-phase self-assembly process was optimized as ethanol and n-hexane solution containing a specific concentration of a probe molecule rhodamine 6G or aspartame. The probe molecules were directly self-assembled on the surface of the composite substrate to avoid the possible loss and pollution during immersion and preservation and achieve the purpose of rapid detection. The results show that the Au@Ag/CW NC array substrate is a periodic cubic ring structure. The sensitivity, uniformity, reproducibility, and stability of composite Au@Ag/CW NC array substrates are verified by comparing the Raman activities of various substrates. The feasibility of using the substrate to realize rapid SERS detection, compared with the advantages and disadvantages of the traditional soaking method, proved that the prepared substrate and improvement direction have excellent potential for application and development prospects in the field of rapid food additive detection.