Tetravalent Manganese Feroxyhyte: A Novel Nanoadsorbent Equally Selective for As(III) and As(V) Removal from Drinking Water

The development of a single-phase Fe/Mn oxy-hydroxide (δ-Fe_0.76Mn_0.24OOH), highly efficient at adsorbing both As­(III) and As­(V), is reported. Its synthesis involves the coprecipitation of FeSO₄ and KMnO₄ in a kilogram-scale continuous process, in acidic and strongly oxidizing environments. The produced material was identified as a manganese feroxyhyte in which tetravalent manganese is homogeneously distributed into the crystal unit, whereas a second-order hollow spherical morphology is favored. According to this structuration, the oxy-hydroxide maintains the high adsorption capacity for As­(V) of a single Fe oxy-hydroxide combined with enhanced As­(III) removal based on the oxidizing mediation of Mn­(IV). Ion-exchange between arsenic species and sulfates as well as the strongly positive surface charge further facilitate arsenic adsorption. Batch adsorption tests performed in natural-like water indicate that Mn­(IV)-feroxyhyte can remove 11.7 μg As­(V)/mg and 6.7 μg As­(III)/mg at equilibrium pH 7, before residual concentration overcomes the regulation limit of 10 μg As/L for drinking water. The improved efficiency of this material, its low cost, and the possibility for scaling-up its production to industry indicate the high practical impact and environmental importance of this novel adsorbent

Acetate-Induced Disassembly of Spherical Iron Oxide Nanoparticle Clusters into Monodispersed Core–Shell Structures upon Nanoemulsion Fusion

It has been long known that the physical encapsulation of oleic acid-capped iron oxide nanoparticles (OA–IONPs) with the cetyltrimethylammonium (CTA⁺) surfactant induces the formation of spherical iron oxide nanoparticle clusters (IONPCs). However, the behavior and functional properties of IONPCs in chemical reactions have been largely neglected and are still not well-understood. Herein, we report an unconventional ligand-exchange function of IONPCs activated when dispersed in an ethyl acetate/acetate buffer system. The ligand exchange can successfully transform hydrophobic OA–IONP building blocks of IONPCs into highly hydrophilic, acetate-capped iron oxide nanoparticles (Ac–IONPs). More importantly, we demonstrate that the addition of silica precursors (tetraethyl orthosilicate and 3-aminopropyltriethoxysilane) to the acetate/oleate ligand-exchange reaction of the IONPs induces the disassembly of the IONPCs into monodispersed iron oxide–acetate–silica core–shell–shell (IONPs@acetate@SiO₂) nanoparticles. Our observations evidence that the formation of IONPs@acetate@SiO₂ nanoparticles is initiated by a unique micellar fusion mechanism between the Pickering-type emulsions of IONPCs and nanoemulsions of silica precursors formed under ethyl acetate buffered conditions. A dynamic rearrangement of the CTA⁺–oleate bilayer on the IONPC surfaces is proposed to be responsible for the templating process of the silica shells around the individual IONPs. In comparison to previously reported methods in the literature, our work provides a much more detailed experimental evidence of the silica-coating mechanism in a nanoemulsion system. Overall, ethyl acetate is proven to be a very efficient agent for an effortless preparation of monodispersed IONPs@acetate@SiO₂ and hydrophilic Ac–IONPs from IONPCs

Band Engineered Epitaxial 3D GaN-InGaN Core–Shell Rod Arrays as an Advanced Photoanode for Visible-Light-Driven Water Splitting

3D single-crystalline, well-aligned GaN-InGaN rod arrays are fabricated by selective area growth (SAG) metal–organic vapor phase epitaxy (MOVPE) for visible-light water splitting. Epitaxial InGaN layer grows successfully on 3D GaN rods to minimize defects within the GaN-InGaN heterojunctions. The indium concentration (In ∼ 0.30 ± 0.04) is rather homogeneous in InGaN shells along the radial and longitudinal directions. The growing strategy allows us to tune the band gap of the InGaN layer in order to match the visible absorption with the solar spectrum as well as to align the semiconductor bands close to the water redox potentials to achieve high efficiency. The relation between structure, surface, and photoelectrochemical property of GaN-InGaN is explored by transmission electron microscopy (TEM), electron energy loss spectroscopy (EELS), Auger electron spectroscopy (AES), current–voltage, and open circuit potential (OCP) measurements. The epitaxial GaN-InGaN interface, pseudomorphic InGaN thin films, homogeneous and suitable indium concentration and defined surface orientation are properties demanded for systematic study and efficient photoanodes based on III-nitride heterojunctions

3D Visualization of the Iron Oxidation State in FeO/Fe₃O₄ Core–Shell Nanocubes from Electron Energy Loss Tomography

The physicochemical properties used in numerous advanced nanostructured devices are directly controlled by the oxidation states of their constituents. In this work we combine electron energy-loss spectroscopy, blind source separation, and computed tomography to reconstruct in three dimensions the distribution of Fe²⁺ and Fe³⁺ ions in a FeO/Fe₃O₄ core/shell cube-shaped nanoparticle with nanometric resolution. The results highlight the sharpness of the interface between both oxides and provide an average shell thickness, core volume, and average cube edge length measurements in agreement with the magnetic characterization of the sample

Insights into Interfacial Changes and Photoelectrochemical Stability of In_<i>x</i>Ga_1–<i>x</i>N (0001) Photoanode Surfaces in Liquid Environments

The long-term stability of InGaN photoanodes in liquid environments is an essential requirement for their use in photoelectrochemistry. In this paper, we investigate the relationships between the compositional changes at the surface of n-type In_<i>x</i>Ga_1–<i>x</i>N (<i>x</i> ∼ 0.10) and its photoelectrochemical stability in phosphate buffer solutions with pH 7.4 and 11.3. Surface analyses reveal that InGaN undergoes oxidation under photoelectrochemical operation conditions (i.e., under solar light illumination and constant bias of 0.5 V_RHE), forming a thin amorphous oxide layer having a pH-dependent chemical composition. We found that the formed oxide is mainly composed of Ga–O bonds at pH 7.4, whereas at pH 11.3 the In–O bonds are dominant. The photoelectrical properties of InGaN photoanodes are intimately related to the chemical composition of their surface oxides. For instance, after the formation of the oxide layer (mainly Ga–O bonds) at pH 7.4, no photocurrent flow was observed, whereas the oxide layer (mainly In–O bonds) at pH 11.3 contributes to enhance the photocurrent, possibly because of its reported high photocatalytic activity. Once a critical oxide thickness was reached, especially at pH 7.4, no significant changes in the photoelectrical properties were observed for the rest of the test duration. This study provides new insights into the oxidation processes occurring at the InGaN/liquid interface, which can be exploited to improve InGaN stability and enhance photoanode performance for biosensing and water-splitting applications