Photo-corrosion inhibition of Ag₃PO₄ by polyaniline coating

<p>In this paper, polyaniline-coated silver phosphate has been successfully prepared via a facile chemisorption method in order to improve the stability of Ag₃PO₄ under light irradiation. The crystalline phase, band gap energy, and microstructure of the obtained PANI/Ag₃PO₄ composites were characterized by X-ray diffraction, UV–vis diffuse reflection spectroscopy, scanning electron microscopy, and transmission electron microscopy, respectively. The photocatalytic degradation of methlylene blue was performed to test the activities of PANI/Ag₃PO₄ composites with different coating amounts and the results indicate that the stabilities of PANI/Ag₃PO₄ composites were successfully enhanced. The correlation between photocatalytic performance and the properties of PANI/Ag₃PO₄ composites is discussed in detail.</p

Multiscale Interfacial Strategy to Engineer Mixed Metal-Oxide Anodes toward Enhanced Cycling Efficiency

Interconnected macro/mesoporous structures of mixed metal oxide (MMO) are developed on nickel foam as freestanding anodes for Li-ion batteries. The sustainable production is realized via a wet chemical etching process with bio-friendly chemicals. By means of divalent iron doping during an in situ recrystallization process, the as-developed MMO anodes exhibit enhanced levels of cycling efficiency. Furthermore, this atomic-scale modification coherently synergizes with the encapsulation layer across a micrometer scale. During this step, we develop a quasi-gel-state tri-copolymer, i.e., F127–resorcinol–melamine, as the N-doped carbon source to regulate the interfacial chemistry of the MMO electrodes. Electrochemical tests of the modified Fe<i>_x</i>Ni_1–<i>x</i>O@NC–NiF anode in both half-cell and full-cell configurations unravel the favorable suppression of the irreversible capacity loss and satisfactory cyclability at the high rates. This study highlights a proof-of-concept modification strategy across multiple scales to govern the interfacial chemical process of the electrodes toward better reversibility

Anomalous Magnetic Properties of Nanoparticles Arising from Defect Structures: Topotaxial Oxidation of Fe_1–<i>x</i>O|Fe_3−δO₄ Core|Shell Nanocubes to Single-Phase Particles

Here we demonstrate that the anomalous magnetic properties of iron oxide nanoparticles are correlated with defects in their interior. We studied the evolution of microstructure and magnetic properties of biphasic core|shell Fe_1–<i>x</i>O|Fe_3−δO₄ nanoparticles synthesized by thermal decomposition during their topotaxial oxidation to single-phase nanoparticles. Geometric phase analysis of high-resolution electron microscopy images reveals a large interfacial strain at the core|shell interface and the development of antiphase boundaries. Dark-field transmission electron microscopy and powder X-ray diffraction concur that, as the oxidation proceeds, the interfacial strain is released as the Fe_1–<i>x</i>O core is removed but that the antiphase boundaries remain. The antiphase boundaries result in anomalous magnetic behavior, that is, a reduced saturation magnetization and exchange bias effects in single-phase nanoparticles. Our results indicate that internal defects play an important role in dictating the magnetic properties of iron oxide nanoparticles

Iron Doping in Spinel NiMn₂O₄: Stabilization of the Mesoporous Cubic Phase and Kinetics Activation toward Highly Reversible Li⁺ Storage

Quaternary oxide structures with a three-dimensional macro/mesoporous network are synthesized via a facile nanocasting method followed by a calcination process. Structural engineering integrates multiscale pores by using a hydrophilic membrane with tunable-porosity as the sacrificial template. Through tailoring the metal precursor ratio, the tetragonal sites of spinel oxide are preferentially occupied by iron, resulting in a stabilized mesoporous cubic phase. Crystal field theory together with compositional characterizations from energy-dispersive spectrometry (EDS), X-ray photoelectron spectroscopy (XPS), Mössbauer, and electron energy loss spectroscopy (EELS) direct our detailed analysis of the cation distribution in the spinel structures. Galvanostatic tests based on the best performing electrode exhibits a robust cycle life stable for 1200 cycles at a high current density of 1500 mA g^–1. This good Li⁺ storage performance could be attributed to the mutually beneficial synergy of the optimal level of iron doping which improves the electrical conductivity and structural robustness, as well as the presence of extended, hierarchical macro/mesoporous network. Finally, we demonstrate three feasible surface modification strategies for the oxide anodes toward better reversibility of Li⁺ storage

Integrated Heterogeneous Metal/Enzymatic Multiple Relay Catalysis for Eco-Friendly and Asymmetric Synthesis

Organic synthesis is in general performed using stepwise transformations where isolation and purification of key intermediates is often required prior to further reactions. Herein we disclose the concept of integrated heterogeneous metal/enzymatic multiple relay catalysis for eco-friendly and asymmetric synthesis of valuable molecules (e.g., amines and amides) in one-pot using a combination of heterogeneous metal and enzyme catalysts. Here reagents, catalysts, and different conditions can be introduced throughout the one-pot procedure involving multistep catalytic tandem operations. Several novel cocatalytic relay sequences (reductive amination/amidation, aerobic oxidation/reductive amination/amidation, reductive amination/kinetic resolution and reductive amination/dynamic kinetic resolution) were developed. They were next applied to the direct synthesis of various biologically and optically active amines or amides in one-pot from simple aldehydes, ketones, or alcohols, respectively

Investigation of the Structural and Electrochemical Properties of Mn₂Sb₃O₆Cl upon Reaction with Li Ions

The structural and electrochemical properties of a quaternary layered compound with elemental composition Mn₂Sb₃O₆Cl have been investigated upon reaction with lithium in Li half cells. Operando XRD was used to investigate the potential impact of this particular layered structure on the lithiation process. Although the results suggest that the material is primarily reacted through a conventional conversion mechanism, they also provide some hints that the space between the slabs may act as preferential entry points for lithium ions but not for the larger sodium ions. Cyclic voltammetry, galvanostatic cycling, HRTEM, SAED, and EELS analyses were performed to unravel the details of the reaction mechanism with the lithium ions. It is found that two pairs of reactions are mainly responsible for the reversible electrochemical cycling of this compound, namely, the alloying of Li–Sb and the conversion of Mn_<i>x</i>O_<i>y</i> to metallic Mn⁰ with concomitant formation of Li₂O upon lithium uptake. A moderate cycling stability is achieved with a gravimetric capacity of 467 mAh g^–1 after 100 cycles between 0.05 and 2.2 V vs Li⁺/Li despite the large particle sizes of the active material and its nonoptimal inclusion into composite coatings. The electrochemical activity of the title compound was also tested in Na half cells between 0.05 and 2 V vs Na⁺/Na. It was found that a prolonged period of electrochemical milling is required to fully gain access to the active material, after which the cell delivers a capacity of 350 mAh g^–1. These factors are demonstrated to clearly limit the ultimate performances for these electrodes

Synthesis of Palladium/Helical Carbon Nanofiber Hybrid Nanostructures and Their Application for Hydrogen Peroxide and Glucose Detection

We report on a novel sensing platform for H₂O₂ and glucose based on immobilization of palladium-helical carbon nanofiber (Pd-HCNF) hybrid nanostructures and glucose oxidase (GOx) with Nafion on a glassy carbon electrode (GCE). HCNFs were synthesized by a chemical vapor deposition process on a C₆₀-supported Pd catalyst. Pd-HCNF nanocomposites were prepared by a one-step reduction free method in dimethylformamide (DMF). The prepared materials were characterized by transmission electron microscopy (TEM), X-ray diffraction (XRD), scanning electron microscopy (SEM), and Raman spectroscopy. The Nafion/Pd-HCNF/GCE sensor exhibits excellent electrocatalytic sensitivity toward H₂O₂ (315 mA M^–1 cm^–2) as probed by cyclic voltammetry (CV) and chronoamperometry. We show that Pd-HCNF-modified electrodes significantly reduce the overpotential and enhance the electron transfer rate. A linear range from 5.0 μM to 2.1 mM with a detection limit of 3.0 μM (based on the S/N = 3) and good reproducibility were obtained. Furthermore, a sensing platform for glucose was prepared by immobilizing the Pd-HCNFs and glucose oxidase (GOx) with Nafion on a glassy carbon electrode. The resulting biosensor exhibits a good response to glucose with a wide linear range (0.06–6.0 mM) with a detection limit of 0.03 mM and a sensitivity of 13 mA M^–1 cm^–2. We show that small size and homogeneous distribution of the Pd nanoparticles in combination with good conductivity and large surface area of the HCNFs lead to a H₂O₂ and glucose sensing platform that performs in the top range of the herein reported sensor platforms

Clearing Up Discrepancies in 2D and 3D Nickel Molybdate Hydrate Structures

When electrocatalysts are prepared, modification of the morphology is a common strategy to enhance their electrocatalytic performance. In this work, we have examined and characterized nanorods (3D) and nanosheets (2D) of nickel molybdate hydrates, which previously have been treated as the same material with just a variation in morphology. We thoroughly investigated the materials and report that they contain fundamentally different compounds with different crystal structures, chemical compositions, and chemical stabilities. The 3D nanorod structure exhibits the chemical formula NiMoO4·0.6H2O and crystallizes in a triclinic system, whereas the 2D nanosheet structures can be rationalized with Ni3MoO5–0.5x(OH)x·(2.3 – 0.5x)H2O, with a mixed valence of both Ni and Mo, which enables a layered crystal structure. The difference in structure and composition is supported by X-ray photoelectron spectroscopy, ion beam analysis, thermogravimetric analysis, X-ray diffraction, electron diffraction, infrared spectroscopy, Raman spectroscopy, and magnetic measurements. The previously proposed crystal structure for the nickel molybdate hydrate nanorods from the literature needs to be reconsidered and is here refined by ab initio molecular dynamics on a quantum mechanical level using density functional theory calculations to reproduce the experimental findings. Because the material is frequently studied as an electrocatalyst or catalyst precursor and both structures can appear in the same synthesis, a clear distinction between the two compounds is necessary to assess the underlying structure-to-function relationship and targeted electrocatalytic properties

Clearing Up Discrepancies in 2D and 3D Nickel Molybdate Hydrate Structures

When electrocatalysts are prepared, modification of the morphology is a common strategy to enhance their electrocatalytic performance. In this work, we have examined and characterized nanorods (3D) and nanosheets (2D) of nickel molybdate hydrates, which previously have been treated as the same material with just a variation in morphology. We thoroughly investigated the materials and report that they contain fundamentally different compounds with different crystal structures, chemical compositions, and chemical stabilities. The 3D nanorod structure exhibits the chemical formula NiMoO4·0.6H2O and crystallizes in a triclinic system, whereas the 2D nanosheet structures can be rationalized with Ni3MoO5–0.5x(OH)x·(2.3 – 0.5x)H2O, with a mixed valence of both Ni and Mo, which enables a layered crystal structure. The difference in structure and composition is supported by X-ray photoelectron spectroscopy, ion beam analysis, thermogravimetric analysis, X-ray diffraction, electron diffraction, infrared spectroscopy, Raman spectroscopy, and magnetic measurements. The previously proposed crystal structure for the nickel molybdate hydrate nanorods from the literature needs to be reconsidered and is here refined by ab initio molecular dynamics on a quantum mechanical level using density functional theory calculations to reproduce the experimental findings. Because the material is frequently studied as an electrocatalyst or catalyst precursor and both structures can appear in the same synthesis, a clear distinction between the two compounds is necessary to assess the underlying structure-to-function relationship and targeted electrocatalytic properties

Amorphous Calcium Carbonate Constructed from Nanoparticle Aggregates with Unprecedented Surface Area and Mesoporosity

Amorphous calcium carbonate (ACC), with the highest reported specific surface area of all current forms of calcium carbonate (over 350 m² g^–1), was synthesized using a surfactant-free, one-pot method. Electron microscopy, helium pycnometry, and nitrogen sorption analysis revealed that this highly mesoporous ACC, with a pore volume of ∼0.86 cm³ g^–1 and a pore-size distribution centered at 8–9 nm, is constructed from aggregated ACC nanoparticles with an estimated average diameter of 7.3 nm. The porous ACC remained amorphous and retained its high porosity for over 3 weeks under semi-air-tight storage conditions. Powder X-ray diffraction, large-angle X-ray scattering, infrared spectroscopy, and electron diffraction exposed that the porous ACC did not resemble any of the known CaCO₃ structures. The atomic order of porous ACC diminished at interatomic distances over 8 Å. Porous ACC was evaluated as a potential drug carrier of poorly soluble substances in vitro. Itraconazole and celecoxib remained stable in their amorphous forms within the pores of the material. Drug release rates were significantly enhanced for both drugs (up to 65 times the dissolution rates for the crystalline forms), and supersaturation release of celecoxib was also demonstrated. Citric acid was used to enhance the stability of the ACC nanoparticles within the aggregates, which increased the surface area of the material to over 600 m² g^–1. This porous ACC has potential for use in various applications where surface area is important, including adsorption, catalysis, medication, and bone regeneration