Core-shell Hybrid Research Articles

Triazine‐Based Large‐Sized Single‐Crystalline Two‐Dimensional Covalent Organic Framework for High‐Performance Lithium‐Ion Batteries

AbstractA large‐sized single crystalline 2D COFs with excellent crystallinity and stability was prepared through the traditional thermal solvent method. The electrochemical performance can be significantly enhanced using a straightforward hybrid approach that involves in situ growth of the 2D COFs on multi‐walled carbon nanotubes (MWCNTs). Both the advantages of COFs and CNTs are mutually enhanced. The single‐crystalline feature of the obtained COFs improves the structural integrity and brings excellent chemical and electrochemical stabilities for lithium‐ion battery applications. The resultant COF‐CNT core–shell hybrids greatly improved the conductivity and demonstrated excellent lithium‐ion storage performance with a high capacity of 228 mAh g−1 (0.2 A g−1).

Triazine-Based Large-Sized Single-Crystalline Two-Dimensional Covalent Organic Framework for High-Performance Lithium-Ion Batteries.

A large-sized single crystalline 2D COFs with excellent crystallinity and stability was prepared through the traditional thermal solvent method. The electrochemical performance can be significantly enhanced using a straightforward hybrid approach that involves in situ growth of the 2D COFs on multi-walled carbon nanotubes (MWCNTs). Both the advantages of COFs and CNTs are mutually enhanced. The single-crystalline feature of the obtained COFs improves the structural integrity and brings excellent chemical and electrochemical stabilities for lithium-ion battery applications. The resultant COF-CNT core-shell hybrids greatly improved the conductivity and demonstrated excellent lithium-ion storage performance with a high capacity of 228 mAh g-1 (0.2 A g-1).

Facile One Pot Synthesis of Hybrid Core-Shell Silica-Based Sensors for Live Imaging of Dissolved Oxygen and Hypoxia Mapping in 3D Cell Models.

Fluorescence imaging allows for noninvasively visualizing and measuring key physiological parameters like pH and dissolved oxygen. In our work, we created two ratiometric fluorescent microsensors designed for accurately tracking dissolved oxygen levels in 3D cell cultures. We developed a simple and cost-effective method to produce hybrid core-shell silica microparticles that are biocompatible and versatile. These sensors incorporate oxygen-sensitive probes (Ru(dpp) or PtOEP) and reference dyes (RBITC or A647 NHS-Ester). SEM analysis confirmed the efficient loading and distribution of the sensing dye on the outer shell. Fluorimetric and CLSM tests demonstrated the sensors' reversibility and high sensitivity to oxygen, even when integrated into 3D scaffolds. Aging and bleaching experiments validated the stability of our hybrid core-shell silica microsensors for 3D monitoring. The Ru(dpp)-RBITC microparticles showed the most promising performance, especially in a pancreatic cancer model using alginate microgels. By employing computational segmentation, we generated 3D oxygen maps during live cell imaging, revealing oxygen gradients in the extracellular matrix and indicating a significant decrease in oxygen level characteristics of solid tumors. Notably, after 12 h, the oxygen concentration dropped to a hypoxic level of PO2 2.7 ± 0.1%.

Enhancing barrier properties: Practical analysis of transport of solvents and gases in natural rubber/graphene oxide‐silica core shell Hybrid Nanocomposites.

Enhancing barrier properties: Practical analysis of transport of solvents and gases in natural rubber/graphene oxide‐silica core shell Hybrid Nanocomposites.

Inorganic/organic hybrid interfacial internal electric field modulated charge separation of resorcinol-formaldehyde resin for boosting photocatalytic H2O2 production

The strategy of inorganic/organic semiconductor material hybridization is of great significance for the development of highly active photocatalysts. Resorcinol-formaldehyde (RF) resin with a special donor-acceptor (D-A) structure shows excellent performance in the photocatalytic production of H2O2. However, the lack of an internal driving force for the separation and transfer of photogenerated electrons and holes in RF resin greatly limits the performance of H2O2 production. Herein, an inorganic/organic hybrid core-shell structure ZnS@RF photocatalyst was prepared by directionally induced coating of RF resin shells of different thicknesses on the surface of monodisperse ZnS nanospheres. Consequently, the photocatalytic H2O2 performance of ZnS@RF with the optimal RF resin shell thickness reaches 367.9 μmol L−1, which is 69 and 2 times that of ZnS and HRF, respectively. Density functional theory (DFT) calculations and related characterization results collectively demonstrate that the excellent photocatalytic H2O2 production performance of ZnS@RF photocatalyst is mainly attributed to the internal electric field (IEF) formed at the hybrid interface of ZnS and RF heterojunction and the optimization of RF shell thickness, which significantly enhances the separation and transfer of photogenerated carriers and modulates the interfacial catalytic reaction kinetics. This work opens up an avenue for designing inorganic/organic hybrid heterojunction photocatalyst materials with excellent photocatalytic activity.

In Situ growth of high-crystallinity MOF@CTF core-shell hybrid heterostructures and their application in photoelectrochemical sensing of vancomycin

Vancomycin is a first-line drug for the treatment of methicillin-resistant Staphylococcus aureus (MRSA) and multidrug-resistant bacterial infections. It is of great significance to develop rapid detection methods for vancomycin in different matrices. In this work, a novel method for the in-situ preparation of MOF@CTF core-shell hybrid heterogeneous structures was proposed and applied to the photoelectrochemical detection of vancomycin. The insolubility of the imine precursor structure in homogeneous solvents and the Lewis acidic centers in the MOF structure induced the initial arrangement of CTF on the surface of PCN-224. By encapsulating a layer of highly crystalline CTF structure onto the initial morphology of PCN-224, a MOF@CTF heterogeneous structure was formed. Importantly, the introduction of anthracene-based electron-donating groups into the CTF structure and the formation of a donor-acceptor system with triazine rings enhanced the photoconversion efficiency of the heterogeneous structure by establishing a continuous separated built-in electric field within the core-shell structure. The successful in-situ synthesis of the core-shell hybrid heterogeneous structure was confirmed through microscopic morphology, PXRD, XPS, and FT-IR. Furthermore, investigations into the semiconductor properties of the heterogeneous structure, including semiconductor type, bandgap, and photo-voltage, were conducted. Results showed that the heterogeneous structure exhibited a doubled photocurrent density compared to the original PCN-224. Additionally, a molecularly imprinted photoelectrochemical sensor (MIPECS) for vancomycin was constructed. Under optimized conditions, the sensor demonstrated a superior concentration response range (0.1 nM - 1 μM) and detection limit (0.031 nM, 3σ/S, n = 11). Simultaneously, the potential applicability of the sensor in animal-derived foods, serum, and environmental water samples was evaluated, yielding satisfactory results.

Constructing core-shell structured Mott–Schottky heterojunction towards remarkable hydrogen production from water/seawater splitting

Green hydrogen production through electrocatalytic water/seawater splitting has recently received significant attention. However, the practical utilization for this technique is still limited due to the poor performance and stability of electrocatalysts. Herein, a heterogeneous core-shell hybrid, containing Ni3S2 nanorod arrays and CoFe layered double hydroxide (LDH) nanosheets, has been fabricated via a developed two-step hydrothermal and electrodeposition method. The build-in electronic field in the as-formed Mott–Schottky barrier endows the efficient electron transfer from CoFe LDH to Ni3S2, subsequently enhancing the reaction kinetics. The as-prepared Ni3S2@CoFe catalyst exhibits exceptional performance for oxygen evolution reaction (OER, η10 = 222 and 237 mV) and hydrogen evolution reaction (HER, η10 = 83 and 109 mV) in 1 M KOH as well as alkaline seawater environments, respectively. Notably, it only requires a cell voltage of 1.51 and 1.55 V to achieve a current density of 10 mA cm2 for overall seawater and water splitting, respectively, outperforming the commercial benchmark Pt/C||RuO2 (1.56 V). This work paves a solid way for construction of Mott–Schottky catalysts for green hydrogen production and its beyond.

Constructing novel Sn-Mo bimetallic sulfide heterostructures for enhanced catalytic performance towards the hydrogen evolution reaction

Understanding the design principles of efficient electrocatalysts using the structure–activity relationship is crucial for the advancement of energy-related applications, and specifically the hydrogen evolution reaction (HER). Non-precious electrocatalysts with low overpotentials are essential for driving the HER and achieving high energy efficiency. In this study, we synthesized and thoroughly investigated various heterostructures combining Mo and Sn sulfides, ranging from complete phase-separated hybrids to homogeneous mixtures: SnS@MoS2 core–shell structures, SnS/MoS2 with edge-rich Mo and (SnxMo1-x)S with uniformly distributed Sn-Mo. Our findings reveal that the SnS@MoS2 structure exhibited relatively high intrinsic activity characterized by a high electrochemical active surface area and rapid charge transfer kinetics, thereby enhancing the HER catalytic performance. The presence of fluffy MoS2 layers provided an abundance of optimized sites for HER, potentially due to strain and defects such as S vacancies, known as active catalytic sites. The optimal structure facilitated efficient charge transfer from the core to the shell, improving conductivity and catalytic activity. Our research highlights the advantages of a core–shell hybrid structure, offering guiding principles for the development of an optimal SnS@MoS2 catalyst.

Sensing of nitrate/nitrite ions in aqueous medium using poly(m-aminophenol)/silver core–shell hybrid modified graphite electrode

A very facile methodology was developed for reliable sensing of nitrate/nitrite ions in the aqueous medium using poly(m-aminophenol)/silver core–shell hybrid coated graphite electrode. The hybrid consisting of a uniform silver nanoparticle core coated with a polymer shell, was synthesized by the thermal reduction of poly(meta-aminophenol) complex with silver mono-positive ions. This core–shell hybrid was fabricated on the tip of the graphite electrode by the drop-casting method and was used as a working electrode in a two electrode setup to study the sensing performance of nitrate/nitrite ions in aqueous medium. The sensitivity and limit of detection (LOD) of the sensor were determined as ∼ 190 mA mM-1cm−2 and ∼ 0.02 mM, respectively for the nitrate/nitrite anions. Very good selective response of poly(m-aminophenol)/silver core–shell hybrid towards nitrate/nitrite ions were also confirmed over the other common tested anions/cations. The mechanism of selective sensing of nitrate/nitrite by the core–shell hybrid has been explained on the basis of selective dipole interaction as well as hydrogen bonding interaction. A reliable result was verified with an accuracy of ∼ 99 ± 4 % for nitrate/nitrite ions in real water samples.

New insight into multi-functional MOG@COP/SA beads for co-adsorption and mono-detection in CTC-Cr(Ⅵ) co-contamination system and efficient anti-counterfeiting

Co-contamination of antibiotics and heavy metals in water environment has provoked considerable toxicological concerns. Meantime, residue detection of heavy metals as well as national anti-counterfeiting safety also have driven attempts in wastewater treatment. In this paper, a core–shell hybrid MOG@COP is designed with behaviors superior to pristine components by combining a Zr-based metal–organic gel and a guanidine-based covalent organic polymer, for co-adsorption and mono-detection in chlortetracycline hydrochloride (CTC)-Cr(Ⅵ) co-contamination system and efficient anti-counterfeiting. In single/binary system, the adsorption capacities of CTC and Cr(Ⅵ) behave as 133.69 and 63.45 mg·g−1/181.82 and 64.47 mg·g−1, and the high sensitivity and low detection limit of Cr(Ⅵ) render as 1.46*105 M−1 and 0.20 μM/1.49*102 M−1 and 0.63 mM, respectively. In addition, to solve the powder shortcomings of easy agglomeration and difficult recycling, MOG@COP is fixed into sodium alginate (SA) matrix to fabricate MOG@COP/SA beads, yielding reinforced adsorption performance of CTC/Cr(Ⅵ) in both single system (152.91/92.25 mg·g−1) and binary system (174.83/75.30 mg·g−1). More importantly, a self-constructed adsorption-detection-anti-counterfeiting (ADA) platform is ingeniously developed with the MOG@COP/SA beads as the backfills for continuously processing CTC-Cr(Ⅵ) co-contaminated water, realizing real-time visualization of Cr(Ⅵ) adsorption process and optical anti-counterfeiting protection. In conclusion, this work is expected to not only trigger the reasonable design of the core–shell hybrid MOG@COP/SA beads with versatile performances of simultaneous luminescence monitor, capture and anti-counterfeiting, but also allow the original exploration for all-in-one platform.

Hydrogel-chitosan and polylactic acid-polycaprolactone bioengineered scaffolds for reconstruction of mandibular defects: a preclinical in vivo study with assessment of translationally relevant aspects.

Background: Reconstruction of mandibular bone defects is a surgical challenge, and microvascular reconstruction is the current gold standard. The field of tissue bioengineering has been providing an increasing number of alternative strategies for bone reconstruction. Methods: In this preclinical study, the performance of two bioengineered scaffolds, a hydrogel made of polyethylene glycol-chitosan (HyCh) and a hybrid core-shell combination of poly (L-lactic acid)/poly ( -caprolactone) and HyCh (PLA-PCL-HyCh), seeded with different concentrations of human mesenchymal stromal cells (hMSCs), has been explored in non-critical size mandibular defects in a rabbit model. The bone regenerative properties of the bioengineered scaffolds were analyzed by in vivo radiological examinations and ex vivo radiological, histomorphological, and immunohistochemical analyses. Results: The relative density increase (RDI) was significantly more pronounced in defects where a scaffold was placed, particularly if seeded with hMSCs. The immunohistochemical profile showed significantly higher expression of both VEGF-A and osteopontin in defects reconstructed with scaffolds. Native microarchitectural characteristics were not demonstrated in any experimental group. Conclusion: Herein, we demonstrate that bone regeneration can be boosted by scaffold- and seeded scaffold-reconstruction, achieving, respectively, 50% and 70% restoration of presurgical bone density in 120days, compared to 40% restoration seen in spontaneous regeneration. Although optimization of the regenerative performance is needed, these results will help to establish a baseline reference for future experiments.

Evaluation of photocatalytic properties of TiO2/g-C3N4 core-shell hybrid catalyst supported on Sr4Al14O25:eu,dy phosphor

TiO2/g-C3N4 hybrid compounds were supported as core-shell catalyst on Sr4Al14O25:Eu,Dy phosphor powder by a 2-step hydrothermal and solvothermal self-assembly method. Surface and chemical characterizations confirmed that the phosphor substrate and the hybrid catalysts co-existed as a multi-composite material. Where nano spherical TiO2 particles were dominant as core/shell catalyst. Diffuse reflectance spectra were shifted toward the visible light region (400 nm to 600 nm) in composites with g-C3N4 as shell-catalyst. X-ray photon spectroscopy (XPS) confirmed the chemical integrity and binding of g-C3N4 on phosphor/TiO2 material. When g-C3N4 was coated as shell-catalyst on phosphor/TiO2, superior photocatalytic performances of above 90% efficiency were obtained in comparison to where TiO2 was coated as shell-catalyst under both ultraviolet and visible light illumination. Thus, g-C3N4 is more active as shell-catalyst owing to its lower band gap of 2.7 eV than core TiO2 (3.2 eV).

Ultra-Mild Fabrication of Highly Concentrated SWCNT Dispersion Using Spontaneous Charging in Solvated Electron System.

The efficient dispersion of single-walled carbon nanotubes (SWCNTs) has been the subject of extensive research over the past decade. Despite these efforts, achieving individually dispersed SWCNTs at high concentrations remains challenging. In this study, we address the limitations associated with conventional methods, such as defect formation, excessive surfactant use, and the use of corrosive solvents. Our novel dispersion method utilizes the spontaneous charging of SWCNTs in a solvated electron system created by dissolving potassium in hexamethyl phosphoramide (HMPA). The resulting charged SWCNTs (c-SWCNTs) can be directly dispersed in the charging medium using only magnetic stirring, leading to defect-free c-SWCNT dispersions with high concentrations of up to 20 mg/mL. The successful dispersion of individual c-SWCNT strands is confirmed by their liquid-crystalline behavior. Importantly, the dispersion medium for c-SWCNTs exhibits no reactivity with metals, polymers, or other organic solvents. This versatility enables a wide range of applications, including electrically conductive free-standing films produced via conventional blade coating, wet-spun fibers, membrane electrodes, thermal composites, and core-shell hybrid microparticles.

Broadband PM6Y6 coreshell hybrid composites for photocurrent improvement and light trapping

Our research focuses on enhancing the broadband absorption capability of organic solar cells (OSCs) by integrating plasmonic nanostructures made of Titanium nitride (TiN). Traditional OSCs face limitations in absorption efficiency due to their thickness, but incorporating plasmonic nanostructures can extend the path length of light within the active material, thereby improving optical efficiency. In our study, we explore the use of refractory plasmonics, a novel type of nanostructure, with TiN as an example of a refractory metal. TiN offers high-quality localized surface plasmon resonance in the visible spectrum and is cost-effective, readily available, and compatible with CMOS technology. We conducted detailed numerical simulations to optimize the design of nanostructured OSCs, considering various shapes and sizes of nanoparticles within the active layer (PM6Y6). Our investigation focused on different TiN plasmonic nanostructures such as nanospheres, nanocubes, and nanocylinders, analyzing their absorption spectra in a polymer environment. We assessed the impact of their incorporation on the absorbed power and short-circuit current (Jsc) of the organic solar cell.

TiO2-Mesoporous Ceria Carrier Modified with Sodium Benzoate: An Innovative Polyurethane Matrix for Enhanced Corrosion Protection of steel

An advanced corrosion protection system, distinguished by multilevel corrosion inhibition, was developed by integrating modified hybrid carriers strategically reinforced within a polyurethane (PU) matrix. For this purpose, mesoporous ceria (mCeO2) was synthesized via a hydrothermal hydrolysis process and incorporated with titanium butoxide to synthesize a hybrid core-shell titania mesoporous ceria (TiO2/mCeO2) carrier system. The TiO2/mCeO2 carrier system was modified with sodium benzoate (SB used as a corrosion inhibitor) to develop a modified TiO2/mCeO2-SB system. The synthesized modified particles were then reinforced into the polyurethane-based matrix to study the corrosion inhibition performance. Benefitting the corrosion-inhibiting properties of modified polyurethane-based coatings, the reinforcement of these modified TiO2/mCeO2 particles resulted in a notably improved anti-corrosion performance in the coating after immersion in 3.5 wt. % NaCl solution for four weeks, the impedance was estimated to be 96.65 GΩ.cm2, which is nearly four orders of magnitude than that of blank PU coatings. This is attributed to the synergistic anti-corrosion performance of TiO2 and SB. The protective layer formed due to the interaction of titania and hydroxyl ions resulted in the formation of Ti(OH)4 and SB absorbed on the steel surface, making iron unavailable for further electrochemical reaction. This work reports on the strategy to build a corrosion inhibition coating system, which introduces a new perspective for extending the lifespan of metals.

Carbon-Based Composites for Oxygen Evolution Reaction Electrocatalysts: Design, Fabrication, and Application.

The four-electron oxidation process of the oxygen evolution reaction (OER) highly influences the performance of many green energy storage and conversion devices due to its sluggish kinetics. The fabrication of cost-effective OER electrocatalysts via a facile and green method is, hence, highly desirable. This review summarizes and discusses the recent progress in creating carbon-based materials for alkaline OER. The contents mainly focus on the design, fabrication, and application of carbon-based materials for alkaline OER, including metal-free carbon materials, carbon-based supported composites, and carbon-based material core-shell hybrids. The work presents references and suggestions for the rational design of highly efficient carbon-based OER materials.

Chiroptical Enhancement in Hybrid Core–Shell Nanoresonators

Chiroptical Enhancement in Hybrid Core–Shell Nanoresonators

Frequency-Selective Radar-Absorbing Composites Using Hybrid Core-Shell Spheres.

Radar-absorbing materials (RAMs) covering the exterior surfaces of installed parts and assembled devices are crucial in absorbing most incident electromagnetic (EM) waves. This absorption minimizes reflected energy, thereby enhancing pilot safety and the stability of operating electronic devices without interference. Particularly, active stealth aircraft require effective protection from near- and far-field EM radiation across a wide spectrum of frequencies from both highly integrated electronic components and advanced enemy radars. Studies of RAMs often prioritize absorption over crucial tunability in frequency selectivity, revealing a research gap. In this study, we propose smart RAMs with frequency-selective absorption capabilities. Our approach involves incorporating two types of core-shell spheres in a polymer matrix, which feature shells of either wave-diffuse reflecting metal or wave-absorbing graphene. The key innovation lies in the ability to tailor absorption frequencies in the X-band range (8.2-12.4 GHz) by adjusting the interstitial spaces between the metallic spheres while the scattered waves are efficiently attenuated by graphene networks in the composites. On a metal substrate, a 2 mm-thick composite with an optimized structural composition and ratio of the two types of spheres exhibits a maximum absorption efficiency of 99.3%, effectively trapping and extinguishing incident waves. Combined with the structural tunability and frequency-selective properties of spherical fillers, our approach provides a scalable and effective method for creating functional isotropic coverings on various metallic surfaces.

Self-Powering Gas Sensing System Enabled by Double-Layer Triboelectric Nanogenerators Based on Poly(2-vinylpyridine)@BaTiO3 Core-Shell Hybrids with Superior Dispersibility and Uniformity.

Current core-shell hybrids used in diverse energy-related applications possess limited dispersibility and film uniformity that govern their overall performances. Herein, we showcase superdispersible core-shell hybrids (P2VP@BaTiO3) composed of a poly(2-vinylpyridine) (P2VP) (5-20 wt %) and a barium titanate oxide (BaTiO3), maximizing dielectric constants by forming the high-quality uniform films. The P2VP@BaTiO3-based triboelectric nanogenerators (TENGs), especially the 10 wt % P2VP (P2VP10@BaTiO3)-based one, deliver significantly enhanced output performances compared to physically mixed P2VP/BaTiO3 counterparts. The P2VP10@BaTiO3-based double-layer TENG exhibits not only an excellent transferred charge density of 281.7 μC m-2 with a power density of 27.2 W m-2 but also extraordinary device stability (∼100% sustainability of the maximum output voltage for 54,000 cycles and ∼68.7% voltage retention even at 99% humidity). Notably, introducing the MoS2/SiO2/Ni-mesh layer into this double-layer TENG enables ultrahigh charge density of up to 1228 μC m-2, which is the top value reported for the TENGs so far. Furthermore, we also demonstrate a near-field communication-based sensing system for monitoring CO2 gas using our developed self-powered generator with enhanced output performance and robustness.

Highly efficient Cu(II) capture by salicylaldoxime functionalized magnetic polydopamine core-shell hybrids: Behavior and mechanism

Functionalized magnetic nanocomposites were considered as promising adsorbents owing to their abundant functional groups and ease of separation properties. Herein, we combined the solvothermal method with molecular copolymerization to synthesize a salicylaldoxime-grafted magnetic polydopamine (SMP) core-shell hybrid and exploited it for Cu(II) adsorption. The physicochemical properties of SMP were comprehensively studied by SEM, TEM, XRD, FT-IR, TGA, XPS, and VSM measurements. The results manifested that polydopamine acts as a bridge connecting magnetic iron oxide and salicylaldoxime to fabricated core-shell hybrids with rich functional groups. The batch experimental results showed that the Cu(II) adsorption was consumingly pH-reliant behavior, while adsorption data fitted the pseudo-second-order kinetic model and Langmuir isothermal model well, and the adsorption process achieved equilibrium within 60 min. Moreover, SMP exhibited remarkable anti-interference and can be recycled for 5 times with an inconspicuous decrease in adsorption performance. Importantly, salicylaldoxime functionalization endowed SMP with maximum Cu(II) adsorption capacity of 141.24 mg/g at pH 6.0 and 25 °C as compared with pure MP. Based on FT-IR and XPS study, the main adsorption mechanisms were proposed with a synergistic effect including a strong chemical chelation and partial Cu(II) reduction. Importantly, this strategy can be extended to multifunctional magnetic composites for Cu-contaminated wastewater cleanup.