Magnetically Recoverable Core–Shell Nanocomposites with Enhanced Photocatalytic Activity

Core–shell structured Fe₃O₄/SiO₂/TiO₂ nanocomposites with enhanced photocatalytic activity that are capable of fast magnetic separation have been successfully synthesized by combining two steps of a sol–gel process with calcination. The as‐obtained core–shell structure is composed of a central magnetite core with a strong response to external fields, an interlayer of SiO₂, and an outer layer of TiO₂ nanocrystals with a tunable average size. The convenient control over the size and crystallinity of the TiO₂ nanocatalysts makes it possible to achieve higher photocatalytic efficiency than that of commercial photocatalyst Degussa P25. The photocatalytic activity increases as the thickness of the TiO₂ nanocrystal shell decreases. The presence of SiO₂ interlayer helps to enhance the photocatalytic efficiency of the TiO₂ nanocrystal shell as well as the chemical and thermal stability of Fe₃O₄ core. In addition, the TiO₂ nanocrystals strongly adhere to the magnetic supports through covalent bonds. We demonstrate that this photocatalyst can be easily recycled by applying an external magnetic field while maintaining their photocatalytic activity during at least eighteen cycles of use.     

Oxide‐Supported IrNiOx Core–Shell Particles as Efficient,Cost‐Effective,and Stable Catalysts for Electrochemical Water Splitting

Active and highly stable oxide‐supported IrNiO_x core–shell catalysts for electrochemical water splitting are presented. IrNi_x@IrO_x nanoparticles supported on high‐surface‐area mesoporous antimony‐doped tin oxide (IrNiO_x /Meso‐ATO) were synthesized from bimetallic IrNi_x precursor alloys (PA‐IrNi_x /Meso‐ATO) using electrochemical Ni leaching and concomitant Ir oxidation. Special emphasis was placed on Ni/NiO surface segregation under thermal treatment of the PA‐IrNi_x /Meso‐ATO as well as on the surface chemical state of the particle/oxide support interface. Combining a wide array of characterization methods, we uncovered the detrimental effect of segregated NiO phases on the water splitting activity of core–shell particles. The core–shell IrNiO_x /Meso‐ATO catalyst displayed high water‐splitting activity and unprecedented stability in acidic electrolyte providing substantial progress in the development of PEM electrolyzer anode catalysts with drastically reduced Ir loading and significantly enhanced durability.     

Strain‐Enhanced Metallic Intermixing in Shape‐Controlled Multilayered Core–Shell Nanostructures: Toward Shaped Intermetallics

Controlling the surface composition of shaped bimetallic nanoparticles could offer precise tunability of geometric and electronic surface structure for new nanocatalysts. To achieve this goal, a platform for studying the intermixing process in a shaped nanoparticle was designed, using multilayered Pd‐Ni‐Pt core–shell nanocubes as precursors. Under mild conditions, the intermixing between Ni and Pt could be tuned by changing layer thickness and number, triggering intermixing while preserving nanoparticle shape. Intermixing of the two metals is monitored using transmission electron microscopy. The surface structure evolution is characterized using electrochemical methanol oxidation. DFT calculations suggest that the low‐temperature mixing is enhanced by shorter diffusion lengths and strain introduced by the layered structure. The platform and insights presented are an advance toward the realization of shape‐controlled multimetallic nanoparticles tailored to each potential application.     

Selected‐Control Fabrication of Multifunctional Fluorescent–Magnetic Core–Shell and Yolk–Shell Hybrid Nanostructures

The selected‐control preparation of uniform core–shell and yolk–shell architectures, which combine the multiple functions of a superparamagnetic iron oxide (SPIO) core and europium‐doped yttrium oxide (Y₂O₃:Eu) shell in a single material with tunable fluorescence and magnetic properties, has been successfully achieved by controlling the heat‐treatment conditions. Furthermore, the shell thickness and interior cavity of SPIO@Y₂O₃:Eu core–shell and yolk–shell nanostructures can be precisely tuned. Importantly, as‐prepared SPIO@Y₂O₃:Eu yolk–shell nanocapsules (NCs) modified with amino groups as cancer‐cell fluorescence imaging agents are also demonstrated. To the best of our knowledge, this is the first report on the selected‐control fabrication of uniform SPIO@Y₂O₃:Eu core–shell nanoparticles and yolk–shell NCs. The combined magnetic manipulation and optical monitoring of magnetic–fluorescent SPIO@Y₂O₃:Eu yolk–shell NCs will open up many exciting opportunities in dual imaging for targeted delivery and thermal therapy.     

Pd@Pt Core–Shell Nanoparticles with Branched Dandelion‐like Morphology as Highly Efficient Catalysts for Olefin Reduction

A facile synthesis based on the addition of ascorbic acid to a mixture of Na₂PdCl₄, K₂PtCl₆, and Pluronic P123 results in highly branched core–shell nanoparticles (NPs) with a micro–mesoporous dandelion‐like morphology comprising Pd core and Pt shell. The slow reduction kinetics associated with the use of ascorbic acid as a weak reductant and suitable Pd/Pt atomic ratio (1:1) play a principal role in the formation mechanism of such branched Pd@Pt core–shell NPs, which differs from the traditional seed‐mediated growth. The catalyst efficiently achieves the reduction of a variety of olefins in good to excellent yields. Importantly, higher catalytic efficiency of dandelion‐like Pd@Pt core–shell NPs was observed for the olefin reduction than commercially available Pt black, Pd NPs, and physically admixed Pt black and Pd NPs. This superior catalytic behavior is not only due to larger surface area and synergistic effects but also to the unique micro–mesoporous structure with significant contribution of mesopores with sizes of several tens of nanometers.     

The Electrochemical Characterization of Single Core–Shell Nanoparticles

We report the direct solution‐phase characterization of individual gold‐core silver‐shell nanoparticles through an electrochemical means, with selectivity achieved between the core and shell components based on their different redox activities. The electrochemically determined core–shell sizes are in excellent agreement with electron microscopy‐based results, successfully demonstrating the electrochemical characterization of individual core–shell nanoparticles.     

One‐Step Synthesis of Metal@Titania Core–Shell Materials for Visible‐Light Photocatalysis and Catalytic Reduction Reaction

Metal@TiO₂ composites with a core–shell structure possess multifunctional properties. The demonstrated protocols for synthesizing such materials involve multiple steps, requiring precise control over the particle uniformity of the core and shell thickness, as well as complex surface modification. A simple approach to synthesizing metal@TiO₂ hybrid nanostructures remains a great challenge. Herein, we report on a one‐step method for the preparation of metal@TiO₂ core–shell nanospheres, which exhibited excellent performance in photocatalytic degradation of recalcitrant organic pollutants under visible light irradiation, and in catalytic reduction of nitrophenol in water. The simple method described here represents a sustainable approach to preparing core–shell materials at low cost, involving fewer chemicals, and requiring less energy, which will make a significant contribution toward large‐scale synthesis of high‐performance hybrid materials for photocatalytic applications.     

Boronic Acid Functionalized Core–Shell Polymer Nanoparticles Prepared by Distillation Precipitation Polymerization for Glycopeptide Enrichment

The boronic acid‐functionalized core–shell polymer nanoparticles, poly(N,N‐methylenebisacrylamide‐co‐methacrylic acid)@4‐vinylphenylboronic acid (poly(MBA‐co‐MAA)@VPBA), were successfully synthesized for enriching glycosylated peptides. Such nanoparticles were composed of a hydrophilic polymer core prepared by distillation precipitation polymerization (DPP) and a boronic acid‐functionalized shell designed for capturing glycopeptides. Owing to the relatively large amount of residual vinyl groups introduced by DPP on the core surface, the VPBA monomer was coated with high efficiency, working as the shell. Moreover, the overall polymerization route, especially the use of DPP, made the synthesis of nanoparticles facile and time‐saving. With the poly(MBA‐co‐MAA)@VPBA nanoparticles, 18 glycopeptides from horseradish peroxidase (HRP) digest were captured and identified by MALDI‐TOF mass spectrometric analysis, relative to eight glycopeptides enriched by using commercially available meta‐aminophenylboronic acid agarose under the same conditions. When the concentration of the HRP digest was decreased to as low as 5 nmol, glycopeptides could still be selectively isolated by the prepared nanoparticles. Our results demonstrated that the synthetic poly(MBA‐co‐MAA)@VPBA nanoparticles might be a promising selective enrichment material for glycoproteome analysis.     

Adsorbate‐Induced Surface Segregation for Core–Shell Nanocatalysts

Coming to the surface : The surface composition of carbon‐supported Pt₃Co catalyst particles changes upon a CO‐annealing treatment. Platinum atoms segregate to the particle surface so that nanoparticles with a platinum shell surrounding an alloy core are formed. This modified catalyst has a superior activity in the oxygen reduction reaction compared to both a plain platinum catalyst and the untreated alloy particles.

     

Atom‐Precise Polyoxometalate–Ag2S Core–Shell Nanoparticles

Atomically precise polyoxometalate–Ag₂S core–shell nanoparticles were generated in a top‐down approach under solvothermal conditions and structurally confirmed by X‐ray single‐crystal diffraction as an interesting core–shell structure comprising an in situ generated Mo₆O₂₂^8? polyoxometalate core and a mango‐like Ag₅₈S₃₈ shell. This result demonstrates the possibility to integrate polyoxometalate and Ag₂S nanoparticles into a core–shell heteronanostructure with precisely controlled atomical compositions of both core and shell.     

Sequential Chemistry Toward Core–Shell Structured Metal Sulfides as Stable and Highly Efficient Visible‐Light Photocatalysts

A universal sequential synthesis strategy in aqueous solution is presented for highly uniform core–shell structured photocatalysts, which consist of a metal sulfide light absorber core and a metal sulfide co‐catalyst shell. We show that the sequential chemistry can drive the formation of unique core–shell structures controlled by the constant of solubility product of metal sulfides. A variety of metal sulfide core–shell structures have been demonstrated, including CdS@CoS_x, CdS@MnS_x, CdS@NiS_x, CdS@ZnS_x, CuS@CdS, and more complexed CdS@ZnS_x@CoS_x. The obtained strawberry‐like CdS@CoS_x core–shell structures exhibit a high photocatalytic H₂ production activity of 3.92 mmol h^?1 and an impressive apparent quantum efficiency of 67.3 % at 420 nm, which is much better than that of pure CdS nanoballs (0.28 mmol h^?1), CdS/CoS_x composites (0.57 mmol h^?1), and 5 %wt Pt‐loaded CdS photocatalysts (1.84 mmol h^?1).     

Dual‐Pore Mesoporous Carbon@Silica Composite Core–Shell Nanospheres for Multidrug Delivery

Monodispersed mesoporous phenolic polymer nanospheres with uniform diameters were prepared and used as the core for the further growth of core–shell mesoporous nanorattles. The hierarchical mesoporous nanospheres have a uniform diameter of 200 nm and dual‐ordered mesopores of 3.1 and 5.8 nm. The hierarchical mesostructure and amphiphilicity of the hydrophobic carbon cores and hydrophilic silica shells lead to distinct benefits in multidrug combination therapy with cisplatin and paclitaxel for the treatment of human ovarian cancer, even drug‐resistant strains.     

Core–Shell Crystals of Porous Organic Cages

The first examples of core–shell porous molecular crystals are described. The physical properties of the core–shell crystals, such as surface hydrophobicity, CO₂ /CH₄ selectivity, are controlled by the chemical composition of the shell. This shows that porous core–shell molecular crystals can exhibit synergistic properties that out‐perform materials built from the individual, constituent molecules.     

Facile Preparation of Core–Shell Magnetic Metal–Organic Framework Nanospheres for the Selective Enrichment of Endogenous Peptides

Facile preparation of core–shell magnetic metal–organic framework nanospheres by a layer‐by‐layer approach is presented. The nanospheres have high surface area (285.89 cm² g^?1), large pore volume (0.18 cm³ g^?1), two kinds of mesopores (2.50 and 4.72 nm), excellent magnetic responsivity (55.65 emu g^?1), structural stability, and good dispersibility. The combination of porosity, hydrophobicity, and uniform magnetism was exploited for effective enrichment of peptides with simultaneous exclusion of high molecular weight proteins. The nanospheres were successfully applied in the selective enrichment of endogenous peptides in human serum.