Full Protection for Graphene‐Incorporated Micro‐/Nanocomposites Containing Ultra‐small Active Nanoparticles: the Best Li‐Storage Properties

In recent years, graphene‐incorporated micro‐/nanocomposites represent one of the hottest developing directions for the composite materials. However, a large number of active nanoparticles (NPs) are still in the unprotected state in most constructed graphene‐containing designs, which will seriously impair the effects of the graphene additives. Here, a fully protected Fe₃O₄‐based micro‐/nanocomposite (G/Fe₃O₄@C) is rationally developed by carbon‐boxing the common graphene/Fe₃O₄ microparticulates (G/Fe₃O₄). The processes and results of full protection are tracked in detail and characterized by X‐ray diffraction, X‐ray photoelectron spectroscopy, and nitrogen absorption–desorption isotherms, as well as scanning and transition electron microscopy. When used as the anode for lithium‐ion batteries, the fully protected G/Fe₃O₄@C exhibits the best lithium‐storage properties in terms of the highest rate capabilities and the longest cycle life compared to the common G/Fe₃O₄ composites and commercial Fe₃O₄ products. These much improved properties are mainly attributed to its novel structural features including complete protection of active Fe₃O₄ nanoparticles by the surface carbon box, a robust conductive network composed of nitrogen‐doped graphene nanosheets, ultra‐small Fe₃O₄ NPs of 4–5 nm, abundant mesopores to accommodate the volume variation during cycling, and micrometer‐sized secondary particles.     

Thermomagnetically Responsive γ‐Fe2O3@Wax@SiO2 Sub‐Micrometer Capsules

A three steps synthesis route is proposed to generate thermosensitive and magnetically responsive γ‐Fe₂O₃@Wax@SiO₂ sub‐micrometer capsules with a paraffinic core and a solid and brittle shell. The process integrates Pickering‐based emulsions, inorganic and sol–gel chemistries to promote monodisperse in size wax droplets, γ‐Fe₂O₃ nanoparticles and mineralization of the wax/water interfaces. Hybrid capsules are obtained with an average size around 800 nm, representing the first example of sub‐micrometer capsules generated employing Pickering emulsions as templates. Cetyltrimethylammonium bromide (CTAB) cationic surfactant added during mineralization at concentrations between 0.17 and 1.0 wt% impacts the shell density. The shell density seems to improve its mechanical strength while affording a low wax expansion volume without breaking for CTAB concentrations above 1.0 wt%. At lower CTAB concentration (0.17 wt%), the silica shell becomes less bulky and cannot resist the wax dilatation induced by the solid‐to‐liquid phase transition imposed by hyperthermia. The magnetically induced heating provided by the internal magnetic moments is sufficient to melt the wax core, expanding its volume, inducing thereby the surrounding silica shell rupture. Such γ‐Fe₂O₃@Stearic Acid@Wax@SiO₂ sub‐micrometer capsules allow a sustained wax release with time, whereby 20% of the wax is released after 50 min of alternating magnetic field treatment.     

The growth of the passive film on iron in 0.05 M NaOH studied in situ by Raman micro‐spectroscopy and electrochemical polarisation. Part I: near‐resonance enhancement of the Raman spectra of iron oxide and oxyhydroxide compounds

Raman spectroscopy, in principle, is an excellent technique for the study of molecular species developed on metal surfaces during electrochemical investigations. However, the use of the more common laser wavelengths such as the 514.5‐nm line results in spectra of less than optimal intensity, particularly for iron oxide compounds. In the present work, near‐resonance enhancement of the Raman spectra was investigated for the iron oxide and iron oxyhydroxide compounds previously reported to be present in the passive film on iron, using a tuneable dye laser producing excitation wavelengths between 560 and 637 nm. These compounds were hematite (α‐Fe₂O₃), maghemite (γ‐Fe₂O₃), magnetite (Fe₃O₄), goethite (α‐FeOOH), akaganeite (β‐FeOOH), lepidocrocite (γ‐FeOOH) and feroxyhyte (δ‐FeOOH). Optimum enhancement, when compared to that with the 514.5‐nm line, was obtained for all the iron oxide and oxyhydroxide standard samples in the low wavenumber region (<1000 cm⁻¹) using an excitation wavelength of 636.4 nm. Particularly significant enhancement was obtained for lepidocrocite, hematite and goethite. Copyright © 2010 John Wiley & Sons, Ltd.     

Facile Synthesis of Gd(OH)3‐Doped Fe3O4 Nanoparticles for Dual‐Mode T1‐ and T2‐Weighted Magnetic Resonance Imaging Applications

The facile hydrothermal synthesis of polyethyleneimine (PEI)‐coated iron oxide (Fe₃O₄) nanoparticles (NPs) doped with Gd(OH)₃ (Fe₃O₄‐Gd(OH)₃‐PEI NPs) for dual mode T₁‐ and T₂‐weighted magnetic resonance (MR) imaging applications is reported. In this approach, Fe₃O₄‐Gd(OH)₃‐PEI NPs are synthesized via a hydrothermal method in the presence of branched PEI and Gd(III) ions. The PEI coating onto the particle surfaces enables further modification of poly(ethylene glycol) (PEG) in order to render the particles with good water dispersibility and improved biocompatibility. The formed Fe₃O₄‐Gd(OH)₃‐PEI‐PEG NPs have a Gd/Fe molar ratio of 0.25:1 and a mean particle size of 14.4 nm and display a relatively high r₂ (151.37 × 10^?3m ^?1 s^?1) and r₁ (5.63 × 10^?3m ^?1 s^?1) relaxivity, affording their uses as a unique contrast agent for T₁‐ and T₂‐weighted MR imaging of rat livers after mesenteric vein injection of the particles and the mouse liver after intravenous injection of the particles, respectively. The developed Fe₃O₄‐Gd(OH)₃‐PEI‐PEG NPs may hold great promise to be used as a contrast agent for dual mode T₁‐ and T₂‐weighted self‐confirmation MR imaging of different biological systems.     

Deposition of ZnO Nanocrystals on Fe3O4 Nanocubes and Their Special Luminescent and Magnetic Properties

With increasing miniaturization, it is extremely important to maintain the magnetization stability at small scale. Herein, more efforts and interests focus on the interface of magnetic core and semiconductor shell to obtain desired magnetic and/or luminescent properties. Here, Fe₃O₄ nanocubes are synthesized via a thermal decomposition followed by coating ZnO nanocrystals. To create a large interface, large Fe₃O₄ nanocubes with 78 ± 3 nm average side‐length are synthesized through adjusting the ratio of iron precursor to stabilizer. The average diameter of the particular ZnO nanostructures coated on the nanocubic Fe₃O₄ is around 10 ± 2 nm. In addition to the photoluminescent properties of the ZnO‐coated nanostructures, core‐shell Fe₃O₄@ZnO nanostructures demonstrate enhanced UV absorption at 360 nm, which has a 20 nm blueshift compared to bulk ZnO. The superparamagnetic properties of Fe₃O₄@ZnO core–shell hybrid nanocrystals at room temperature are dominated by the ferromagnetic properties when the temperature is lower than the Blocking temperature, 235.7 K. The observed exchange bias and temperature‐dependent magnetization can result from the interfacial interphase between ZnO and Fe₃O₄. The anisotropy contributed by the interfacial interphase allows the nanostructures to maintain stable magnetization in miniaturized devices.     

Fabrication,structure, and properties of Fe<Subscript>3</Subscript>O<Subscript>4</Subscript>@C encapsulated with YVO<Subscript>4</Subscript>:Eu<Superscript>3+</Superscript> composites

The use of carbon shells offers many advantages in surface coating or surface modification due to their surface with activated carboxyl and carbonyl groups. In this study, the Fe₃O₄@C@YVO₄:Eu³⁺ composites were prepared through a simple sol–gel process. Reactive carbon interlayer was introduced as a key component, which separates lanthanide-based luminescent component from the magnetite, more importantly, it effectively prevent oxidation of the Fe₃O₄ core during the whole preparation process. The morphology, structure, magnetic, and luminescent properties of the composites were characterized by transmission electron microscopy (TEM), high-resolution TEM, X-ray diffraction, X-ray photoelectron spectra, VSM, and photoluminescent spectrophotometer. As a result, the Fe₃O₄@C/YVO₄:Eu³⁺ composites with well-crystallized and core–shell structure were prepared and the YVO₄:Eu³⁺ luminescent layer decorating the Fe₃O₄@C core–shell microspheres are about 10 nm. In addition, the Fe₃O₄@C@YVO₄:Eu³⁺ composites have the excellent magnetic and luminescent properties, which allow them great potential for bioapplications such as magnetic bioseparation, magnetic resonance imaging, and drug/gene delivery.     

Multifunctional Plasmonic Co‐Doped Fe2O3@polydopamine‐Au for Adsorption,Photocatalysis, and SERS‐based Sensing

A new type of multifunctional plasmonic nanoparticles, cobalt‐doped Fe₂O₃@polydopamine‐Au (Co‐Fe₂O₃@PDA‐Au), is fabricated via coating PDA through self‐polymerization onto Co‐Fe₂O₃ and further loading gold nanoparticles by in situ reduction onto the surface of PDA shell. Benefiting from the universal adhesive ability of PDA and negative zeta potetntial of the composite, the Co‐Fe₂O₃@PDA‐Au shows strong adsorptivity for cationic dyes. The presence of gold nanoparticle with the diameter of 15 nm in the Co‐Fe₂O₃@PDA‐Au system promotes surface‐enhanced Raman scattering (SERS) activity with an impressive detection limit of 1 × 10^?6 m . Thanks to the synergistic effect of the light harvesting of PDA, the surface plasmon resonance of Au, and the electron conductibility of PDA and Au, the Co‐Fe₂O₃@PDA‐Au exhibits an enhanced photocatalytic activity comparing with unmodified Co‐Fe₂O₃. All the above‐mentioned functions enable Co‐Fe₂O₃@PDA‐Au to be a multifunctional material system for various applications toward environmental pollutants.     

Magnetically separable Fe<Subscript>3</Subscript>O<Subscript>4</Subscript>@C/BiOBr heterojunction for the enhanced visible light-driven photocatalytic performance

In this study, the magnetically recyclable Fe₃O₄@C/BiOBr heterojunction with enhanced visible light-driven photocatalytic ability was obtained by two-step solvothermal method. The phase, morphology, and structure of the samples were investigated by XRD, FESEM, HRTEM, and XPS. The Fe₃O₄@C/BiOBr heterojunction was composed of Fe₃O₄@C sphere and BiOBr microsphere with diameters of 200 nm and 1000 nm, respectively. The photocatalytic performance of Fe₃O₄@C/BiOBr composite for RhB was examined under visible light irradiation. The photocatalytic activity of Fe₃O₄@C/BiOBr composite was much higher than that of pure BiOBr and Fe₃O₄@C. After 35 min of irradiation, 97% of RhB could be removed with the Fe₃O₄@C/BiOBr photocatalyst. Based on radical trapping experiments of active species, the mechanism of enhanced photocatalytic performance was proposed. In addition, the superparamagnetic property of the photocatalyst not only allows its easy recyclability by an external magnetic field but also maintains high photocatalytic activity after five cyclic experiments.

Open image in new window

Graphical abstract ?

     

Phase transformations in CaCO3/iron oxide composite induced by thermal treatment and laser irradiation

Calcium carbonate (CaCO₃)/iron oxide composites were synthesized through a simple one‐step impregnation procedure by mixing iron oxide nanoparticles (γ‐Fe₂O₃ and Fe₃O₄) of about 6 nm in size and CaCO₃ microparticles (Φ = 2 µm–8 µm, vaterite phase). The morphology and structural properties of CaCO₃, iron oxide nanoparticles and CaCO₃/iron oxide composites were characterized as a function of low iron content (0 %w to 3.2 %w) by scanning electron microscopy and transmission electron microscopy, X‐ray diffraction and ⁵⁷Fe Mössbauer spectrometry. The phase transformations induced by thermal treatment and laser irradiation were investigated in situ by X‐ray thermodiffraction (XRTD) and Raman spectroscopy. We have shown that the phase transformations observed by XRTD are also observed under laser irradiation as a consequence of the absorption of the laser irradiation by iron oxide nanoparticles. Copyright © 2012 John Wiley & Sons, Ltd.     

Photoelectrochemical properties of texture‐controlled nanostructured α‐Fe2O3 thin films prepared by AACVD

Nanostructured α‐Fe₂O₃ thin film electrodes were deposited by aerosol‐assisted chemical vapour deposition (AACVD) for photoelectrochemical (PEC) water splitting on conducting glass substrates using 0.1 M methanolic solution of Fe(acac)₃. The XRD analysis confirmed that the films are highly crystalline α‐Fe₂O₃ and free from other iron oxide phases. The highly reproducible electrodes have an optical bandgap of ～2.15 eV and exhibit anodic photocurrent. The current–voltage characterization of the electrodes reveals that the photocurrent density strongly depended on the film morphology and deposition temperature. Scanning electron microscopy (SEM) analysis showed a change in the surface morphology with the change in deposition temperature. The films deposited at 450 °C have nanoporous structures which provide a maximum electrode/electrolyte interface. The maximum photocurrent density of 455 µA/cm² was achieved at 0.25 V vs. Ag/AgCl/3M KCl (～1.23 V vs. RHE) and the incident photon to electron conversion efficiency (IPCE) was 23.6% at 350 nm for the electrode deposited at 450 °C. (© 2014 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

Surface‐enhanced Raman scattering of 4‐mercaptopyridine on sub‐monolayers of α‐Fe2O3 nanocrystals (sphere,spindle, cube)

We report surface‐enhanced Raman scattering (SERS) spectra from 4‐mercaptopyridine (4‐Mpy) adsorbed on sub‐monolayers of α‐Fe₂O₃ nanocrystals (sphere, spindle, cube). The maximum enhancement factor has been estimated to be about 10⁴ compared to that of 4‐Mpy in solution. A possible mechanism has been proposed that the charge transfer between the α‐Fe₂O₃ nanocrystals and the 4‐Mpy molecules is most likely responsible for the observed enhancement of Raman intensity of adsorbed 4‐Mpy molecules as surface plasmon resonances have not occurred. Copyright © 2009 John Wiley & Sons, Ltd.     

A Multifunctional Magnetic Composite Material as a Drug Delivery System and a Magnetic Resonance Contrast Agent

Magnetic iron oxide coated in hydrogenation silica (Fe₃O₄@HSiO₂) is constructed as both a tumor drug carrier and a magnetic resonance (MR) contrast agent. Colchicine (COLC) is loaded in Fe₃O₄@HSiO₂ with the highest amount of 28.3 wt% at pH 9. The release performance of COLC can be controlled by pH, as the porous HSiO₂ shell can partially shed at pH below 3.0 to facilitate the release of COLC. MR imaging (MRI) tests prove that Fe₃O₄@HSiO₂ at pH 3.0 (H⁺‐Fe₃O₄@HSiO₂) shows a stronger MR contrast enhancement than Fe₃O₄. Cytotoxicity experiment indicates that Fe₃O₄@HSiO₂ has excellent biocompatibility and magnetic targeting performance. Additionally, COLC‐loaded Fe₃O₄@HSiO₂ (Fe₃O₄@HSiO₂–COLC) displays a higher inhibition effect on tumor cells under a magnetic field than free COLC. The visibility upon MRI, high targeting, and pH‐controlled release characteristics of Fe₃O₄@HSiO₂–COLC are favorable to achieve the aim of reducing side effects to normal tissues, making Fe₃O₄@HSiO₂–COLC an attractive drug delivery system for nanomedicine.     

Highly Ligand‐Directed and Size‐Dependent Photothermal Properties of Magnetite Particles

The development of cancer photothermal therapies, many of which rely on photothermal agents, has received significant attention in recent years. In this work, various ligands‐stabilized magnetite (Fe₃O₄) particles are fabricated and utilized as a photothermal agents for in vivo tumor‐imaging‐guided photothermal therapy. Fe₃O₄ particles stabilized by macromolecular ligands as, e.g. polyethylene glycol (PEG), exhibit a superior and more stable photothermal effect compared to Fe₃O₄ particles stabilized by small molecules like citrate, due to their stronger ability of antioxidation. In addition, the photothermal effect of Fe₃O₄ particles is revealed to increase with size, which is attributed to the redshift of Vis‐NIR spectra. Fe₃O₄ particles injected intravenously into mice can be accumulated in the tumor by the application of an external magnetic field, as revealed by magnetic resonance imaging. In vivo photothermal therapy test of PEG‐stabilized Fe₃O₄ further achieves better tumor ablation effect. Overall, this study demonstrates efficient imaging‐guided photothermal therapy of cancer that is based on Fe₃O₄ particles of optimized size and with optimized ligands. It is expected that the ligand‐directed and size‐dependent photothermal effect will provide more approaches in the design of novel materials.     

Clean and reproducible SERS substrates for high sensitive detection by solid phase synthesis and fabrication of Ag‐coated Fe3O4 microspheres

The solid‐phase synthesis of Ag‐coated Fe₃O₄ microsphere was elaborated under argon atmosphere. This straightforward process utilized neither reducing agents nor electric current and involved the dry mixing of a precursor of CH₃COOAg with Fe₃O₄ microspheres followed by heating in an inert atmosphere. Ag nanoparticles with diameters of 30–50 nm were well‐decorated on the surfaces of Fe₃O₄ microspheres. The as‐synthesized Ag‐coated Fe₃O₄ microspheres were assembled into a surface‐enhanced Raman scattering (SERS) substrate holding clean and reproducible properties under an externally exerted magnetic force. Using these nanoprobes, analyte molecules can be easily captured, magnetically concentrated, and analyzed by SERS. This clean SERS substrate was used to detect 4‐aminothiophenol, even at a concentration as low as1.0 × 10^–12 M. In particular, the Ag‐coated Fe₃O₄ microspheres, acting as reproducible SERS substrates, were applied to detect methyl‐parathion and 4‐mercaptopyridine. Strong SERS signals were obtained with the analytes at a concentration of 1.0 × 10^–6 M. The unique, clean, and reproducible properties indicate a new route in eliminating the single‐use problem of traditional SERS substrates and show promising applications for detecting other organic pollutants. Similarly, this work may provide a new model system to a series of metal–Fe₃O₄ decorating reactions for a reproducible utilization. Copyright © 2012 John Wiley & Sons, Ltd.     

Mössbauer spectroscopy study of mechanically alloyed Fe2O3–(Al, Co and WC) systems

Mössbauer spectroscopy revealed that a central hyperfine interaction doublet and an additional sextet characterized the appearance of new phases in the mechanically alloyed Fe₂O₃–Al and Fe₂O₃–Co systems. In the Fe₂O₃–Al system, the intensity of the central super paramagnetic doublet which represents small particles of iron, increased with increasing milling time from 5 to 30 h of mechanical alloying. The magnetic sextet characterizing hematite vanished in the room temperature Mössbauer spectra of samples produced after 25 h of mechanically alloying the 50% Fe₂O₃ and 50% Al system. In general XRD peak broadening was observed as a result of extensive material structural distortion and formation of small particles. Fe, Al₂O₃ and mixed iron–aluminium oxide phases were identified in the XRD patterns with a small persistence of the iron oxide up to 20 h of mechanically alloying the 1:1 system Al–Fe₂O₃. In the 50% Co–50% Fe₂O₃ system, a 55% abundant new phase CoFe₂O₄ was observed, from the Mössbauer spectra of the system. The presence of this new phase was confirmed by the XRD analysis. The high energy ball milling of WC–Fe₂O₃ revealed a more effective grinding compared to hematite alone. The hematite particles were reduced to nanosized particles.     

具有介孔结构的MnSiO3@Fe3O4@C纳米粒子的制备以及作为pH响应的T1-T2*双模MRI造影剂的研究应用

本文通过一个简单的、温和的方案制备了平均尺寸为120 nm,介孔结构的纳米粒子MnSiO₃@Fe₃O₄@C. 粒子的细胞毒性微小,可以用作T₁-T₂^*双模MRI造影剂. 酸性条件下MnSiO₃@Fe₃O₄@C释放出大量的Mn²⁺缩短T₁弛豫时间,提高成像分辨率. 超顺磁性的Fe₃O₄可以增强T₂对比成像,检测病变组织. 类似于肿瘤微环境/细胞器的酸性PBS(pH=5.0)中Mn²⁺的释放率达到31.66%,约为中性条件(pH=7.4)下的7倍. 释放的Mn²⁺通过内吞作用被细胞摄取,经肾脏排出,细胞毒性实验表明,MnSiO₃@Fe₃O₄@C具有低的细胞毒性,即使高浓度的200 ppm MnSiO₃@Fe₃O₄@C对HeLa细胞的毒性也相对较小. 对荷瘤小鼠静脉注射定量MnSiO₃@Fe₃O₄@C后,可以观察到一个快速增强的对比成像,给药24 h后,T₁MRI信号显著增强,达到132%,而T₂信号则明显降低至53.8%,活体MR成像证明了MnSiO₃@Fe₃O₄@C可以同时作为阳性和阴性造影剂. 此外,得益于介孔MnSiO₃优秀的酸敏感性,MnSiO₃@Fe₃O₄@C可以作为一种潜在的药物载体,实现肿瘤的诊疗一体化.     

Near‐Infrared‐Light‐Induced Fast Drug Release Platform: Mesoporous Silica‐Coated Gold Nanoframes for Thermochemotherapy

Development of advanced theranostics for personalized medicine is of great interest. Herein, a multifunctional mesoporous silica‐based drug delivery carrier has been developed for efficient chemo/photothermal therapy. The unique Au nanoframes@mSiO₂ spheres are elaborately prepared by utilizing Ag@mSiO₂ yolk–shell spheres as the template through spatially confined galvanic replacement method. Compared with the Ag@mSiO₂ yolk–shell spheres, the resultant Au nanoframes@mSiO₂ spheres show a strong and broad near‐infrared (NIR) absorbance in the 550–1100 nm region, high surface areas, and good biocompatibility. When irradiated with a NIR laser with a power intensity of 1 W cm^?2 at 808 nm, they can become highly localized heat sources through the photothermal effect. Moreover, the photothermal effect of the Au nanoframes can significantly promote the fast release of doxorubicin. The in vitro studies show obvious synergistic effects combining photothermal therapy and chemotherapy in the Au nanoframes@mSiO₂ spheres against Hela cells. It is believed that the as‐obtained multifunctional vehicles provide a promising platform for the combination of hyperthermia and chemotherapy for cancer treatment application.     

Large scale synthesis of pinhole‐free shell‐isolated nanoparticles (SHINs) using improved atomic layer deposition (ALD) method for practical applications

Shell‐isolated nanoparticle‐enhanced Raman spectroscopy (SHINERS) as a new member of Raman technique garnered great attention among scientific community. In this work, we used an improved experimental setup to float the bare silver nanoparticles in air with the help of extraneous airflow, and used atomic layer deposition (ALD) method to coat ultra‐thin inert shell without pinholes. Under optimal conditions, we successfully prepared three kinds of SHINERS NPs (Ag@Al₂O₃, Ag@SiO₂ and Ag@TiO₂) in large quantity without pinholes. The ultra‐thin inert shell maintains the SERS activity of silver nanoparticles for long period of time. Transmission electron microscopy (TEM) images confirm the uniform coating of shell material on silver nanoparticles. Finally, the as‐prepared SHINs have been applied to detect various samples to demonstrate the applications. The presented ALD method offers a unique way to coat ultrathin shell (1–10 nm) on metal nanoparticles in large quantity (1–10 g) for practical applications. Copyright © 2015 John Wiley & Sons, Ltd.     

Amphiphilic Core–Shell Nanocomposite Particles for Enhanced Magnetic Resonance Imaging

A scalable synthesis of magnetic core–shell nanocomposite particles, acting as a novel class of magnetic resonance (MR) contrast agents, has been developed. Each nanocomposite particle consists of a biocompatible chitosan shell and a poly(methyl methacrylate) (PMMA) core where multiple aggregated γ‐Fe₂O₃ nanoparticles are confined within the hydrophobic core. Properties of the nanocomposite particles including their chemical structure, particle size, size distribution, and morphology, as well as crystallinity of the magnetic nanoparticles and magnetic properties were systematically characterized. Their potential application as an MR contrast agent has been evaluated. Results show that the nanocomposite particles have good stability in biological media and very low cytotoxicity in both L929 mouse fibroblasts (normal cells) and HeLa cells (cervical cancer cells). They also exhibited excellent MR imaging performance with a T₂ relaxivity of up to 364 mM_Fe^?1 s^?1. An in vivo MR test performed on a naked mouse bearing breast tumor indicates that the nanocomposite particles can localize in both normal liver and tumor tissues. These results suggest that the magnetic core–shell nanocomposite particles are an efficient, inexpensive and safe T₂‐weighted MR contrast agent for both liver and tumor MR imaging in cancer therapy.     

Design of Enhanced Catalysts by Coupling of Noble Metals (Au,Ag) with Semiconductor SnO2 for Catalytic Reduction of 4‐Nitrophenol

The reduction of 4‐nitrophenol (Nip) into 4‐aminophenol (Amp) by NaBH₄, which is catalyzed by both binary and ternary yolk–shell noble‐metal/SnO₂ heterostructures, is reported. The binary heterostructures contain individual Au or Ag nanoparticles (NPs) and the ternary heterostructures contain both Au and Ag NPs. The Au@SnO₂ yolk–shell NPs are synthesized via a silica seeds‐mediated hydrothermal method. Subsequently, the Au@SnO₂@Ag and Au@SnO₂@Au yolk–shell–shell (YSS) NPs are synthesized, whereby SnO₂ is located between the Au and Ag NPs. The morphology, composition, and optical properties of the as‐prepared samples are analyzed. For the binary heterostructures, the rate of the reduction reaction increases with decreasing particle size. The catalytic results demonstrate the synergistic effect of Au and Ag in the ternary metal–semiconductor heterostructures, which is beneficial to the catalytic reduction of Nip into Amp. Both the binary and ternary heterostructures exhibit significantly better catalytic performances than the corresponding bare Au and Ag NPs. It is envisaged that the current synthesized strategy will promote further interest in the field of bimetal NP‐based catalysis.