Shell Nanoparticles Research Articles

Magnetically-manipulatable and self-cleaning lab-on-a-bubble Ag@TiO2@Fe3O4 hollow spheres and their application in SERS detection and photocatalytic degradation

In this study, an innovative highly sensitive self-cleaning Lab-on-a-bubble SERS substrate: Ag NPs@TiO2@Fe3O4 hollow spheres, was developed using spray pyrolysis and following depositions. The reusable and magnetically controllable substrate consists of iron oxide hollow spheres (Fe3O4) covered by a TiO2 shell and silver nanoparticles (Ag NPs) deposited on the outer surface. Experimental results show that this new composite SERS substrate exhibited a low limit of detection (LOD) down to 10-10M, and the enhancement factor (EF) reached 1.01 X107. It suffered only 3 % loss after 10 repeatable recycle tests if the self-cleaning under UV was performed after each test. This novel substrate possessed good photocatalytic degradation ability for methylene blue (MB) dyes even under visible light. In that case, MB can be dissociated up to 99.8 % and the reaction rate constant (K) reached 0.0271/min. Taking advantage of this, the feasibility of reusable SERS detection through self-cleaning under visible light was also demonstrated.

Poly(N‐Heterocyclic Carbene)‐Capped Alloy and Core‐Shell AuAg Bimetallic Nanoparticles

AbstractN‐Heterocyclic carbene (NHC)‐stabilized metal nanoparticles (NPs) have recently attracted considerable attention. While most efforts in the field have been devoted to the development of NHC‐tethered monometallic NPs and enhancing their stabilities under various conditions, their bimetallic counterparts are rare in the literature. Herein, we demonstrate that the covalent immobilization of Au and Ag atoms on polymerized NHCs is a powerful method to access bimetallic AuAg NPs. In addition, we show that while AuAg alloy NPs are often obtained via this method, the use of bimetallic polymeric substrates with lower Ag content, relative to Au, results in the formation of core–shell NPs with Au core and Ag shell. Application of these nanomaterials for oxygen reduction reaction is demonstrated with all materials exhibiting electrocatalytic activity. This work demonstrates for the first time that while bimetallic poly(NHC‐metal)s are viable substrates to access NHC‐stabilized bimetallic NPs, careful adjustment of metal content in the polymeric substrates can finetune the microstructure of the resulting NPs, i.e. alloy vs. core–shell.

Graphite–Si@TiO2 Core–Shell Nanoparticles as Composite Anode for Li‐Ion Batteries: Postcycling Analysis

Graphite–Si@TiO₂ Core–Shell Nanoparticles as Composite Anode for Li‐Ion Batteries: Postcycling Analysis

Spontaneous Emulsification of Organometallic Complexes Applied to the Synthesis of Nanocapsules Active for H2 Release from Ammonia-Borane.

Herein, we achieved spontaneous emulsification of organometallic precursors to elaborate subμm metal nanocapsules after interfacial reduction. Depending on the proportion of the three components, water, solvent, and the metal precursor, either thermodynamically stable "surfactant-free microemulsions" (SFME) or metastable Ouzo emulsions are formed. We investigated the catalytic transition metals Au, Pd, and Pt, individually or combined, and stabilized by various ligands. Upon reduction of the precursors, either shells of discrete nanoparticles (NPs) or continuous shells were obtained, for the SFME and Ouzo emulsions, respectively. The Au/Pd mixed emulsions lead to a unique structural morphology, in which the Au-Pd nanoparticles are embedded in a continuous submicronic metal shell. The AuNPs are available to grow larger particles within the NP shell using a seeded growth approach. The water-stable and surfactant-free nanocapsules are appealing as catalysts, and, as such, were evaluated for the hydrolysis of ammonia-borane as a promising catalytic strategy for H2 release from an H-high-content storage material. This work establishes for the first time a genuine activity of water-compatible gold colloids for this reaction.

Fe3O4@ZnO Core-Shell Nanoparticles—a novel facile fabricated magnetically separable photocatalyst

The current study proposes a simple and inexpensive technique to synthesise core–shell Fe3O4@ZnO as a promising photocatalyst. An easily scalable original procedure was developed based on sequential and simultaneous addition of Zn2+ and OH– ions to Fe3O4 cores, and preheating and subsequent heating of the reaction medium. The structure of Fe3O4@ZnO core–shell nanoparticles was found to be a sequence of layers including magnetite (Fe3O4), maghemite (γ-Fe2O3), goethite (α-FeOOH), and zinc oxide (ZnO) in (0001) orientation. This layer sequence ensures a smooth transition from the Fe3O4 of the core to the ZnO shell. The synthesis conditions affect layer density and thickness, which can be easily used in adjusting Fe3O4@ZnO properties.Photocatalytic degradation of a model persistent dye (naphthol green B) in the presence of Fe3O4@ZnO nanoparticles reached promising 77 % in 60 min under UV radiation, while Fe3O4 cores showed only 20 %. The wide-gap ZnO layer on the surface of the narrow-gap Fe3O4 provides charge separation and suppresses electron-hole recombination, which drastically increases photocatalytic activity of the material. Separation of the photocatalyst with a magnet showed the same result as that with a centrifuge. All of these findings lead to inexpensive fabrication, effective performance, low toxicity and simple separation of Fe3O4@ZnO.

Hierarchical, Porous Microspherical Lithium Iron Phosphate with Nanoparticle Shells for High-Rate Capacity and Stability Cathodes

Hierarchical, Porous Microspherical Lithium Iron Phosphate with Nanoparticle Shells for High-Rate Capacity and Stability Cathodes

Photothermally Reconfigurable Biomimetic Photonic Structures Prepared via Crystallization of Polydopamine‐Incorporated Core–Shell Nanoparticles

AbstractSome creatures have periodic nanostructures and chromophores in their flexible organs that allow them to control the color and shape of their skin. Artificial photonic structures that can mimic the aforementioned ability of these natural structures are researched extensively. In this study, polydopamine‐incorporated core–interlayer–shell (CIS‐PDA) nanoparticles capable of shape reconfiguration and expressing vivid structural colors are designed. These nanoparticles can be readily assembled to produce colloidal photonic crystals (CPhCs) and can exhibit vivid structural colors by virtue of their light‐absorbing capability. Soft CPhC films prepared with these nanoparticles undergo stable elastic deformation at 15% strain and exhibit mechanochromic properties. Specifically, the PDA in the CIS nanoparticles can absorb broadband light and exhibit a photothermal effect resembling that of melanosomes in living organisms, which enables self‐healing between multiple CPhC films. Due to their favorable properties, the CPhC films prepared in this study represent promising photothermally reconfigurable photonic materials. Moreover, arbitrarily shaped 2D or 3D surfaces are conformally coated with the films via microimprinting or vacuum wrapping, courtesy of the reconfigurability of these films. These findings suggest that CPhC films prepared with CIS‐PDA nanoparticles can be used as form‐free mechanochromic strain sensors and nonfading optical films for industrial products.

Pt nanoshells with a high NIR-II photothermal conversion efficiency mediates multimodal neuromodulation against ventricular arrhythmias

Autonomic nervous system disorders play a pivotal role in the pathophysiology of cardiovascular diseases. Regulating it is essential for preventing and treating acute ventricular arrhythmias (VAs). Photothermal neuromodulation is a nonimplanted technique, but the response temperature ranges of transient receptor potential vanilloid 1 (TRPV1) and TWIK-related K+ Channel 1 (TREK1) exhibit differences while being closely aligned, and the acute nature of VAs require that it must be rapid and precise. However, the low photothermal conversion efficiency (PCE) still poses limitations in achieving rapid and precise treatment. Here, we achieve a nearly perfect blackbody absorption and a high PCE in the second near infrared (NIR-II) window (73.7% at 1064 nm) via a Pt nanoparticle shell (PtNP-shell). By precisely manipulating the photothermal effect, we successfully achieve rapid and precise multimodal neuromodulation encompassing neural activation (41.0–42.9 °C) and inhibition (45.0–46.9 °C) in a male canine model. The NIR-II photothermal modulation additionally achieves multimodal reversible autonomic modulation and confers protection against acute VAs associated with myocardial ischemia and reperfusion injury in interventional therapy.

Structural Degradation of M‐N‐C (M=Co, Ni and Fe) Single‐Atom Electrocatalysts at Industrial‐Grade Current Density for Long‐Term Reduction

AbstractM‐N‐C single‐atom catalysts (SACs) are promising electrode materials for many electro‐reduction reactions. However, their stability is far from practical applications, and their deactivation mechanism has been rarely investigated. Herein, we demonstrate the structural degradation of M‐N‐C (M=Co, Ni, and Fe) at industrial‐grade current density for long‐term electro‐reduction. Both M‐N and N‐C bonds are broken, resulting in the gradual hydrogenation and dissolution of N in the form of ammonia. The residual M is finally converted to M‐containing core–shell nanoparticles after sequential dissolution, redeposition, and electro‐reduction. The destruction of the M‐N‐C structure and the formation of nanoparticles greatly affect the electrocatalytic performance. Our work highlights the structural degradation and deactivation mechanism of M‐N‐C‐type SACs under strong reductive conditions and provides useful information for inspiring researchers to develop new strategies to improve the electrocatalytic stability of similar types of materials.

Polypropylene nanocomposite film with enhanced energy storage performance via a continuous preparation

Dielectric polymers have been extensively employed in renewable energy conversion, hybrid electric vehicle, and high voltage direct current transmission systems, owing to their excellent electrical insulation, processability, and self-healing capability. However, the challenge lies in their relatively low dielectric constant (εr) and limited discharge energy density (Ue), which hinder the advancement of integrated power modules. Despite numerous efforts aimed at enhancing Ue, the fabrication of scalable dielectric film with both enhanced Ue and high charge–discharge efficiency (η) remains a major obstacle. Herein, the polypropylene-based films with BaTiO3@PP-g-MAH (BTO@PP-g-MAH) core–shell nanoparticles are prepared through a continuous melt extrusion process. The resulting nanocomposite film, incorporated with 5 wt% BTO@PP-g-MAH, exhibits an impressive Ue of 5.15 J cm−3 and achieves a high η of 93.2 % at 433 MV m−1, along with excellent cycle dielectric stability. Such enhancements in εr and Ue are ascribed to the improved interfacial polarization facilitated by BaTiO3 nanoparticles and the enhanced interface binding achieved through the PP-g-MAH shell layers. Furthermore, the enhancement of electric breakdown strength (Eb) is comprehensively investigated based on electrical breakdown mechanism and electromechanical breakdown model. This study demonstrates a novel strategy to prepare nanocomposite dielectric films that are compatible with commercial capacitor fabrication process.

Ferroelectricity‐Induced Surface Ferromagnetism in Core–Shell Magnetoelectric Nanoparticles

Magnetoelectric nanoparticles (NPs) present an important class of nanomaterials with a wide interest in piezocatalytic and biomedical applications. Herein, the results of magnetoelectric and magnetization measurements performed on core–shell NPs having magnetic core (MnFe2O4, MFO) and ferroelectric shell (Ba0.85Ca0.15Ti0.5Zr0.5O3, BCZT) synthesized by the microwave hydrothermal method are reported. Magnetic results are compared with the measurements on reference MFO NPs prepared under identical conditions. Detailed SQUID magnetometer measurements of the magnetization hysteresis loops M(H) down to 2 K reveal the existence of a clear exchange bias effect in pure MFO NPs attributed to the coexistence of ferromagnetic and antiferromagnetic short‐range interactions. When the magnetic core is covered by the thin ferroelectric BCZT shell, it is observed that 1) the shell suppresses the apparent bias effect and 2) induces an “extra” ferromagnetic magnetization at T < 20 K. The results indicate that this “extra” ferromagnetism has a 2D character and it is most likely related to the interface interactions between the MFO core and BCZT shell. Ferroelectric properties and strong magnetoelectric effect in core–shell NPs are revealed via piezoresponse force microscopy under magnetic field. The mechanisms of the observed effects are discussed.

Assembly of Gold Nanostar Cores Within Silica Shells and Its Impact on Solid-State SERS and Nonenzymatic Catalytic Sensing.

Metal core and dielectric shell nanoparticles (NPs) have garnered considerable attention for their multifaceted properties and extensive applications across diverse fields of nanoscience and nanotechnology. However, a literature gap exists regarding the impact of assembled metallic nanostar cores within a single shell, particularly concerning surface-enhanced Raman scattering (SERS) and electrochemical sensing. In this study, we have demonstrated the better performance of assemblies of gold nanostars (AuNSs) enclosed in single silica shell for SERS enhancement and electrocatalytic activity, particularly in the fields of ascorbic acid (AA) and glucose sensing. We have devised a method to isolate and passivate nanostar assemblies, ranging from 2 to 30 nanostars per assembly, with a functionalized silica (SiO2) shell, facilitating their preservation. The engineered thickness of the silica shell ensures unhindered optical measurements while elucidating the influence of multiple AuNS cores. Due to the formation of nanogaps and nanojunctions between AuNSs within assembly, we have achieved a maximum SERS enhancement factor (EF) of 1.416 × 1010 for the rhodamine 6G analyte. Utilizing assembled AuNS cores within a single silica shell, we have demonstrated AA (sensitivity of 5.278 × 10-5 μA μM-1 cm-2) and glucose (sensitivity of 7.519 × 10-4 μA μM-1 cm-2) sensing via a nonenzymatic electrochemical pathway.

Anti-OTC antibody-conjugated fluorescent magnetic/silica and fluorescent hybrid silica nanoparticles for oxytetracycline detection

Abstract This study presents two alternative fluorescent nanoparticle-based oxytetracycline (OTC) detection methods in milk samples. Rhodamine 6G-coated fluorescent hybrid silica nanoparticles and fluorescent magnetic/silica nanoparticles functionalized with anti-OTC antibodies were used in this test. The sandwich test format was utilized to compare anti-OTC antibody-conjugated fluorescent magnetic/silica nanoparticles with OTC/OTC antibody-conjugated fluorescent hybrid silica nanoparticles in an Eppendorf tube with magnetic separators. The magnetic separator helps to quickly retain all of the OTC captured by fluorescent magnetic core–shell nanoparticles in the milk sample. As a result, the assay time was dramatically shortened. The obtained linear range was 1.34 × 10−6 to 2.10 × 10−8 (M) (R 2 = 0.9954), the detection limit was 4.76 ng/mL, and the total assay time was 90 min. This approach was used to determine the OTC concentration in milk samples, and the maximum percentage (%) of interference was less than 3.0%, with a recovery rate of greater than 97.0%. This approach offers a high potential for residue detection in milk samples. With a total analysis period of less than 90 min, this approach provided the best way to determine the capture and detector nanoparticles’ response.

Carrier gradient core-double shell structure with heterojunction transition layer for significantly enhancing dielectric properties

In this work, to prohibit the undesirable large dielectric loss and electric-field distortion of the conductive fillers/polymer with a high dielectric constant, TiO2 (TO) and Al2O3 (AO) shells were successively coated on the surface of amorphous carbon (C) to prepare the C@TO@AO core-double shell nanoparticles. This novel design of gradually varying the multilayer hierarchical interface achieved the gradient reduction of carrier concentration from the C core to the TO and AO layers. And the introduction of the multilayer hierarchical interface was advantageous to the enhancement of interface polarization. Moreover, the excellent integrated dielectric properties could be effectively achieved by adjusting the layer thickness and crystal structure of the TO layer. It was worth noting that the TO transition layer with anatase and rutile heterojunctions (HTO) had a significant enhancement in the dielectric constant of the composites induced by the strength of interfacial polarization and built-in electric field inside the HTO layer. Furthermore, the simulated electric field distribution inside the composites was further investigated to reveal the mechanism of enhanced dielectric properties. This work exerts important guiding significance for the reasonable structure design and the elaborate regulation of the shell micro-structures to improve the dielectric properties of composites.

Superior Anodic Lithium Storage in Core–Shell Heterostructures Composed of Carbon Nanotubes and Schiff‐Base Covalent Organic Frameworks

Covalent organic frameworks (COFs) after undergoing the superlithiation process promise high‐capacity anodes while suffering from sluggish reaction kinetics and low electrochemical utilization of redox‐active sites. Herein, integrating carbon nanotubes (CNTs) with imine‐linked covalent organic frameworks (COFs) was rationally executed by in‐situ Schiff‐base condensation between 1,1′‐biphenyl]‐3,3′,5,5′‐tetracarbaldehyde and 1,4‐diaminobenzene in the presence of CNTs to produce core–shell heterostructured composites (CNT@COF). Accordingly, the redox‐active shell of COF nanoparticles around one‐dimensional conductive CNTs synergistically creates robust three‐dimensional hybrid architectures with high specific surface area, thus promoting electron transport and affording abundant active functional groups accessible for electrochemical utilization throughout the whole electrode. Remarkably, upon the full activation with a superlithiation process, the as‐fabricated CNT@COF anode achieves a specific capacity of 2324 mAh g−1, which is the highest specific capacity among organic electrode materials reported so far. Meanwhile, the superior rate capability and excellent cycling stability are also obtained. The redox reaction mechanisms for the COF moiety were further revealed by Fourier‐transform infrared spectroscopy in conjunction with X‐ray photoelectron spectroscopy, involving the reversible redox reactions between lithium ions and C=N groups and gradual electrochemical activation of the unsaturated C=C bonds within COFs.

Architecting ultra-thin SiO2 shell for high magnetic performance of Fe3O4 nanoparticles for biomedical applications

This research focuses on the architectural design of the silica shell on the Fe3O4 nanoparticle to precisely control and minimize its thickness, with the aim of achieving a final product with optimal saturation magnetization (Ms) for biomedical applications. A rapid and facile microwave-assisted synthesis method was developed for the synthesis of Fe3O4@SiO2 and Fe3O4@SiO2@NH2 core–shell nanoparticles with ultra-thin SiO2 shells and excellent magnetic performance. The particle size distribution of the Fe3O4@SiO2 nanoparticles was in the range of 15–35 nm, with a mean particle size of approximately 21 nm. The mean thickness of the SiO2 shells on the Fe3O4 cores was found to be 3 nm. FTIR analysis also confirmed the successful silica coating on Fe3O4 nanoparticles and the successful amino-functionalization of silica-coated Fe3O4 nanoparticles. The Ms of Fe3O4, Fe3O4@SiO2, and Fe3O4@SiO2@NH2 nanoparticles were found to be 64.4, 59.8, and 52.4 emu/g, respectively. It has been confirmed that the ultra-thin SiO2 coating has a negligible effect on the magnetic characteristics of the nanoparticles. The developed microwave-assisted synthesis method in this study not only provides an interesting, rapid, and facile synthesis route but also results in a product with a narrow particle size distribution, an ultra-thin SiO2 shell, favorable magnetic properties, and improved cell compatibility, which may be used in several different applications, particularly biomedical applications.

Vehicular and Core–Shell Nanoparticle Diffusion in Attractive Entangled Polymer Melts

Vehicular and Core–Shell Nanoparticle Diffusion in Attractive Entangled Polymer Melts

Synthesis of Au@Pd core–shell nanoparticles by ultrafine bubbles and ultrasound without capping and reducing agents

Abstract This paper, for the first time, reports on the synthesis of Au@Pd core–shell nanoparticles in the absence of any capping and reducing agents by ultrafine bubbles and ultrasound. The mean diameter of the bimetallic core–shell nanoparticles was controlled by the ultrafine bubble concentration during the synthesis. Pd’s shell thickness also varied with the concentration of Pd(II) ions. These Au@Pd core–shell nanoparticles showed excellent catalytic performance due to the pure surface without any capping and reducing agents.

State of the art on plasma-liquid route synthesis monometallic Au, bimetallic Au/Ag core–shell and alloy nanoparticles: Toxicological, сanalytical, antimicrobial activity for environmental control

Nanoparticles (Au monometallic, bimetallic structures Au-Ag alloy and Aucore – Agshell) were synthesized in aqueous solutions with traditional capping agent - sodium citrate, using a one-step (for monometalic and alloy structure) and two–step (for Aucore – Agshell NPs) liquid-phase anode type plasma process. The effects of parameters of synthesis: precursors concentration, the solution plasma process discharge time, molar contents Ag+/Au3+ for alloy NPs, and molar content of Ag+ for Au core NP to the characteristics of the synthesized NPs, including average size (the size distribution, polydispersity index), optical absorption properties ect.) were investigated. The synthesized nanoparticles have the following characteristics: Au NPs with λ=530–540 nm and d = 5–60 nm, the monometalic structure; Ag/Au with the λ=410–530 nm and d = 28–80 nm, bimatalic strucrure of alloy; NPs with significant blue-shift the λ=530→410 nm, depending the shell thickness (the thickness of the deposited Ag shells varied from ∼1–15 nm) and d = 21–35 nm for NPs core(Au)–shell(Ag). TEM images clearly confirm the effectiveness of a one- and two-step plasma-liquid treatment for the synthesis of monometallic Au NPs and the two different structures of the NPs (bimetallic structures Au-Ag alloy and Aucore@– Agshell). The effect of nanoparticle structure on antimicrobial and catalytic properties relative to their respective monometallic counterparts was demonstrated. Among the different investigated structure NPs only for bimetallic core−shell structured AucoreAgshell NPs was found strong synergistic effect for antimicrobial and catalytical activity.

Preparation and characterization of silicon nanoparticles (core) with gold nanoparticles (shell) configuration

Herein, we used a simple yet novel approach to create and characterize silicon nanoparticles Si NPs/core, gold nanoparticles AuNps/shell hybrid structure. The meso porous silicon layer was synthesized using a laser-supporting etching process with 50 mW/cm2 and 405 nm laser power density and illumination wavelength in a Teflon cell comprising a 1:3 volumetric ratio of 40 % HF in ethanol with etching current density of 25 mA/cm2 for 15 min. The SiNps/AuNps hybrid structure was synthesized by a simple ion reduction process of gold ions via dangling bonds of SiNps in an aqueous solution of HaUcl4 of 0.001 M for 5 min. The characterization of SiNps and SiNps/AuNps hybrid structure were investigated using FE-SEM, TEM, XRD and PL measurements. The results showed that the pores diameter ranged from 5 nm to 50 nm, while the average diameter of the SiNps core layer and AuNps shell layer are about 59.5 nm and 38 nm respectively. The surface morphology of the SiNps characterizes the synthesized hybrid structure; the PL emission of hybrid structure has a high intensity with blue shifting towards short wavelength compared with SiNps. Deposition of AuNps on SiNps led to synthesis more chemical stable hybrid structure with specific increase in the surface area.This resulting hybrid structure can be adoptedin various types of plasmonics and gas sensors in addition to optoelectronics devices.