Multicore Capsules: Thermo‐Stimulable Wax@Water@SiO2 Multicore‐Shell Capsules (Part. Part. Syst. Charact. 2/2013)

Complex wax@water@SiO₂ multicore capsules are synthesized by combining sol‐gel process and formulation of wax‐in‐water‐in‐oil double emulsions. The inner direct wax‐in‐water emulsion is stabilized with modified silica nanoparticles using limited coalescence occurring in Pickering emulsions. In a second step, this obtained liquid dispersion is emulsified in poly‐dimethylsiloxane (PDMS) using a non ionic surfactant to stabilize the second water/oil interface. Finally, a sol‐gel process is employed to mineralize the as‐generated double emulsions giving rise to wax@water@SiO₂ multicore capsules. Due to the wax volume expansion through melting, the as‐synthesized multicore capsules offer thermally stimulated release that is enhanced when surfactant is added in the surrounding continuous oil phase. In addition, the melted wax release can be tuned from a one‐step process to a more sequential dropping mode by varying the mineral precursor tetraethoxy‐orthosilane (TEOS) concentration in the oily phase during mineralization.     

Yolk–Shell‐Structured Cu/Fe@γ‐Fe2O3 Nanoparticles Loaded Graphitic Porous Carbon for the Oxygen Reduction Reaction

Core–shell Cu/γ‐Fe₂O₃@C and yolk–shell‐structured Cu/Fe@γ‐Fe₂O₃@C particles are prepared by a facile synthesis method using copper oxide as template particles, resorcinol‐formaldehyde as the carbon precursor, and iron nitrate solution as the iron source via pyrolysis. With increasing carbonization temperature and time, solid γ‐Fe₂O₃ cores are formed and then transformed into Fe@γ‐Fe₂O₃ yolk–shell‐structured particles via Ostwald ripening under nitrogen gas flow. The composition variations are studied, and the formation mechanism is proposed for the generation of the hollow and yolk–shell‐structured metal and metal oxides. Moreover, highly graphitic carbons can be obtained by etching the metal and metal oxide nanoparticles through an acid treatment. The electrocatalytic activity for oxygen reduction reaction is investigated on Cu/γ‐Fe₂O₃@C, Cu/Fe@γ‐Fe₂O₃@C, and graphitic carbons, indicating comparable or even superior performance to other Fe‐based nanocatalysts.     

New evidences of in situ laser irradiation effects on γ‐Fe2O3 nanoparticles: a Raman spectroscopic study

The nature of the physical mechanisms responsible for the structural modification of the γ‐Fe₂O₃ nanoparticles under laser irradiation has been investigated by Raman spectroscopy. In situ micro‐Raman measurements were carried out on as‐prepared γ‐Fe₂O₃ nanoparticles about 4 nm in size as a function of laser power and on annealed γ‐Fe₂O₃ particles. A baseline profile analysis clearly evidenced that the phase transition from maghemite into hematite is caused by local heating due to laser irradiation with an increase of grain size of nanoparticles. This increasing was clearly determined by X‐ray diffraction from 4 nm in nanoparticles up to more than 177 nm beyond 900 °C in a polycrystalline state. Copyright © 2010 John Wiley & Sons, Ltd.     

Structural Insight into Stabilization of Pickering Emulsions with Fe3O4@SiO2 Nanoparticles for Enzyme Catalysis in Organic Media

Encapsulation of enzymes with enhanced activity and recyclability in water‐in‐oil Pickering emulsions is a simple and efficient method for their immobilization; however, the effect produced by the structure of colloidal particles on the stabilization of the Pickering emulsion for enzyme catalysis has not been investigated in detail. In this study, four types of hydrophobic Fe₃O₄@SiO₂ nanoparticles (NPs) with similar chemical compositions, particle diameters, but different surface characteristics have been prepared and utilized for enzyme encapsulation in various water‐in‐oil magnetic Pickering emulsions, after which the relationship between NPs structure, size of emulsions droplets, and enzyme activity is examined. The obtained results indicate that (i) the more hydrophobic Fe₃O₄@SiO₂ NPs cause the higher enzyme activity; (ii) the higher hydrophobicity of oil phase also increases the enzyme activity, especially for Fe₃O₄@w‐SiO₂ NPs which form in the solvent of water. The results are mainly attributed to the higher specific surface area of emulsion droplets and interfacial mass transfer of substrates through the interfaces of droplets. The reported data provide new insights into the mechanism of stabilization of Pickering emulsions for enhancing enzyme activity and demonstrate efficient theoretical references for enzyme immobilization and synthesis of stable and active biocatalysts with high recyclability.     

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.     

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.     

Ultrasonic-assisted ultra-rapid synthesis of monodisperse meso-SiO2@Fe3O4 microspheres with enhanced mesoporous structure

A core–shell-type of meso-SiO₂@Fe₃O₄ microsphere was synthesized via an ultrasonic-assisted surfactant-templating process using solvothermal synthesized Fe₃O₄ as core, tetraethoxysilane (TEOS) as silica source, and cetyltrimethyl ammonium bromide (CTAB) as templates. The samples were characterized by FT-IR, XRD, TEM, N₂ adsorption–desorption technology, and vibrating sample magnetometer (VSM). The results show that as-prepared meso-SiO₂@Fe₃O₄(E) and meso-SiO₂@Fe₃O₄(C) microspheres, treated by acetone extraction and high temperature calcination, respectively, still maintain uniform core–shell structure with desirable mesoporous silica shell. Therein, the meso-SiO₂@Fe₃O₄(E) microspheres possess a distinct pore size distribution in 1.8–3.0 nm with large specific surface area (468.6 m²/g) and pore volume (0.35 cm³/g). Noteworthily, the coating period of this ultrasonic-assisted method (40 min) is much shorter than that of the conventional method (12–24 h). The morphology of microspheres and the mesoporous structure of silica shell are significantly influenced by initial concentration of CTAB (C_CTAB), ultrasonic irradiation power (P) and ultrasonic irradiation time (t). The acceleration roles of ultrasonic irradiation take effect during the whole coating process of mesoporous silica shell, including hydrolysis-condensation process of TEOS, co-assembly of hydrolyzed precursors and CTAB, and deposition of silica oligomers. In addition, the use of ultrasonic irradiation is favorable for improving the homogeneity of silica shell and the monodispersity of meso-SiO₂@Fe₃O₄ microspheres.     

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.     

Magnetization of Fe‐oxide based nanocomposite tuned by surface charging

Aiming at a voltage‐control of magnetism, the magnetization of a porous γ‐Fe₂O₃–Pt nanocomposite is studied under the influence of charging the surfaces of the porous structure in an electrolyte. Reversible variations of the magnetization of up to 10.4% could be achieved upon charging in the regime where electrochemical adsorption and desorption occurs. The observed variation of the magnetization with electrochemical charging is assigned to the γ‐Fe₂O₃ nanoparticles whereas the conductive network of Pt nanoparticles is necessary for charging. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Role of <Emphasis Type="Italic">N</Emphasis>-methyl-2-pyrrolidone for preparation of Fe<Subscript>3</Subscript>O<Subscript>4</Subscript>@SiO<Subscript>2</Subscript> controlled the shell thickness

We developed a simple and novel approach for the synthesis of Fe₃O₄@SiO₂ nanoparticles with controlled shell thickness, and studied the mechanism. The introduction of N-methyl-2-pyrrolidone (NMP) led to trapping of monomer nuclei in single shell and controlled the shell thickness. Fe₃O₄@SiO₂ controlled the shell thickness, showing a high magnetization value (64.47 emu/g). Our results reveal the role and change in the chemical structure of NMP during the core-shell synthesis process. NMP decomposed to 4-aminobutanoic acid in alkaline condition and decreased the hydrolysis rate of the silica coating process.     

Phase‐controlled epitaxial growth of iron oxide thin films on MgO(001) and LaAlO3(001) substrates

We have deposited epitaxial iron oxide thin films on MgO(001) and LaAlO₃(LAO)(001) substrates, resulting in different phase stabilities. Atomic force microscopy images revealed a smooth surface. Detailed X‐ray diffraction (XRD) measurements were performed to confirm the epitaxial growth and to analyze the atomic growth configuration. We found that (00l) oriented γ‐Fe₂O₃ was the stable phase on MgO(001) substrates, whereas $ (1\bar 102) $ oriented α‐Fe₂O₃ was stable on LAO(001). Magnetic hysteresis loop measurements revealed typical ferrimagnetic behavior for γ‐Fe₂O₃ on MgO, whereas the magnetization of α‐Fe₂O₃ on LAO was relatively small and consistent with an antiferromagnetic order. (© 2012 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

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.     

High‐Strength Sub‐Micrometer Spherical Particles Fabricated by Pulsed Laser Melting in Liquid

Sub‐micrometer spherical particles that are obtained by pulsed laser melting in liquid (PLML) are usually observed to be single crystalline, and it is suggested that they are mechanically very strong. In this study, fracture tests of various sub‐micrometer spherical particles are performed by compressive force application. The results indicate that B₄C and TiO₂ sub‐micrometer spherical particles exhibit brittle fracture behavior under tensile fracture mode at the center of the particles. The fracture strength of the sub‐micrometer spherical particles is larger than that of the bulk material reported in the literature by about one order of magnitude. TiO₂ sub‐micrometer spherical particles obtained by PLML are stronger than the commercially available TiO_x sub‐micrometer spherical particles with a porous structure. In addition, due to the single crystallinity of particles, smaller particles have larger fracture strength, becoming up to 10–40% of ideal tensile fracture strength calculated based on density functional theory. Thus, these results demonstrate that sub‐micrometer spherical particles obtained using PLML exhibit fairly strong and unique mechanical properties, and therefore they are very promising for various mechanical applications at the sub‐micrometer size scale.     

Highly Acid‐Resistant,Magnetically Steerable Acoustic Micromotors Prepared by Coating Gold Microrods with Fe3O4 Nanoparticles via pH Adjustment

There is mounting interest in designing magnetically steerable nano‐ and micromotors for next generation medical nanorobotics, which requires biocompatibility for each individual component. Although various magnetic materials (e.g., Ni, Co, and Fe₃O₄) have been incorporated into micromotors, their acid resistance remains largely unexplored. In this article, a simple one‐step method to prepare magnetic microrods via electrostatic attraction between paramagnetic magnetite nanoparticles (Fe₃O₄ NPs) and gold microrods at appropriate pH values is reported. The as‐prepared Fe₃O₄‐coated micromotors can be powered by MHz ultrasound and easily steered by external magnetic fields, and perform well in harsh working conditions such as high acidity, high viscosity, and high ionic strength. In particular, extended exposure to solution of pH as low as 0.9 has a minimal effect on the speed, steerability, or cargo‐transporting capability of micromotors coated with Fe₃O₄ NPs, in stark contrast with those containing Ni segments. Considering the many challenges of biomedical applications, acid‐resistant, magnetically steerable Fe₃O₄‐coated micromotors powered by MHz ultrasound can be a promising prototype for the future development of medical nano‐ and microrobotics.     

Synchrotron XANES and ED‐XRF analyses of fine‐paste ware from 13th to 14th century maritime Southeast Asia

The combination of energy dispersive X‐ray fluorescence (ED‐XRF) and synchrotron X‐ray absorption near‐edge structure (XANES) provides the detailed composition of fine‐paste ware (FPW) kendis, dated back to 13th–14th century maritime Southeast Asia. Sources of clay and production sites were classified according to Al₂O₃, SiO₂, α‐Fe₂O₃ and γ‐Fe₂O₃ as well as trace elements. The similarities based on these components provided another evidence of a trade route between Kota Cina in North Sumatra of Indonesia and Kok Moh on Satingphra Peninsula, a well‐known production area in present‐day Thailand. In additions, the uniquely large contribution of α‐Fe₂O₃ in XANES spectra suggests that Nakhon Si Thammarat province of Thailand could also be one of FPW production areas in maritime Southeast Asia. Copyright © 2017 John Wiley & Sons, Ltd.     

Multiple Emulsion Templating of Hybrid Ag/SiO2 Capsules for Antibacterial Applications

Silver nanoparticles (NPs) encapsulated in amorphous silica shells are synthesized and evaluated for their antibacterial action using the Gram‐negative Escherichia coli bacterium. These inorganic capsules are synthesized using a new approach that comprises the use of oil‐in‐water‐in‐oil (O/W/O) multiple emulsions to fabricate SiO₂ capsules incorporating organically capped Ag NPs. This strategy is explored as a mean to promote the bioadhesion of the microorganisms to the silica rough surfaces while still keeping the system with a high surface area for the active metal. The results have shown that the hybrid capsules enable a slow release of cationic silver from the interior of the silica microsphere to the external medium probably through the pore channels in the shell. The antibacterial activity against E. coli is mainly determined by the Ag⁺ ion release rate, suggesting that these particulates can be employed as a robust system for prolonged used as an antimicrobial material.     

X‐ray spectroscopy for chemistry in the 2‐4 keV energy regime at the XMaS beamline: ionic liquids,Rh and Pd catalysts in gas and liquid environments,and Cl contamination in γ‐Al2O3

The 2–4 keV energy range provides a rich window into many facets of materials science and chemistry. Within this window, P, S, Cl, K and Ca K‐edges may be found along with the L‐edges of industrially important elements from Y through to Sn. Yet, compared with those that cater for energies above ca. 4–5 keV, there are relatively few resources available for X‐ray spectroscopy below these energies. In addition, in situ or operando studies become to varying degrees more challenging than at higher X‐ray energies due to restrictions imposed by the lower energies of the X‐rays upon the design and construction of appropriate sample environments. The XMaS beamline at the ESRF has recently made efforts to extend its operational energy range to include this softer end of the X‐ray spectrum. In this report the resulting performance of this resource for X‐ray spectroscopy is detailed with specific attention drawn to: understanding electrostatic and charge transfer effects at the S K‐edge in ionic liquids; quantification of dilution limits at the Cl K‐ and Rh L₃‐edges and structural equilibria in solution; in vacuum deposition and reduction of [Rh^I(CO)₂Cl]₂ to γ‐Al₂O₃; contamination of γ‐Al₂O₃ by Cl and its potential role in determining the chemical character of supported Rh catalysts; and the development of chlorinated Pd catalysts in `green' solvent systems. Sample environments thus far developed are also presented, characterized and their overall performance evaluated.     

Spectroscopic and structural investigations of α‐, β‐, and γ‐AlH3 phases

With its reputation as a high‐energy density fuel, aluminum hydride (AlH₃) has received renewed attention as a material that is particularly suitable, not only for hydrogen storage but also for rocket propulsion. While the various phases of AlH₃ have been investigated theoretically, there is a shortage of experimental studies corroborating the theoretical findings. In response to this, we present here an investigation of these compounds based primarily on two research areas in which there is the greatest scarcity of information in the literature, namely Raman and infrared (IR) absorption analysis. To the authors' knowledge, this is the first report of experimental far‐IR absorption results on these compounds. Two different samples prepared by broadly similar ethereal reactions of AlCl₃ with LiAlH₄ were analyzed. Both Raman and IR absorption measurements indicate that one sample is purely γ‐AlH₃ and that the other is a mixture of α‐, β‐, and γ‐AlH₃ phases. X‐ray diffraction confirms the spectroscopic findings, most notably for the β‐AlH₃ phase, for which optical spectroscopic data are reported here for the first time. Copyright © 2010 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)     

Preparation and characterization of silica-coated Fe3O4 nanoparticles used as precursor of ferrofluids

Fe₃O₄ magnetic nanoparticles (MNPs) were synthesized by the co-precipitation of Fe³⁺ and Fe²⁺ with ammonium hydroxide. The sodium citrate-modified Fe₃O₄ MNPs were prepared under Ar protection and were characterized by Fourier transform infrared spectroscopy (FT-IR), transmission electron microscopy (TEM), X-ray powder diffraction (XRD) and vibrating sample magnetometer (VSM). To improve the oxidation resistance of Fe₃O₄ MNPs, a silica layer was coated onto the modified and unmodified MNPs by the hydrolysis of tetraethoxysilane (TEOS) at 50 °C and pH 9. Afterwards, the silica-coated Fe₃O₄ core/shell MNPs were modified by oleic acid (OA) and were tested by IR and VSM. IR results revealed that the OA was successfully grafted onto the silica shell. The Fe₃O₄/SiO₂ core/shell MNPs modified by OA were used to prepare water-based ferrofluids (FFs) using PEG as the second layer of surfactants. The properties of FFs were characterized using a UV-vis spectrophotometer, a Gouy magnetic balance, a laser particle size analyzer and a Brookfield LVDV-III+ rheometer.