Showing papers by "Miaofang Chi published in 2013"

Correlation Between Oxygen Vacancy, Microstrain, and Cation Distribution in Lithium-Excess Layered Oxides During the First Electrochemical Cycle

Abstract: Dynamic structural changes during the first electrochemical charge and discharge cycle in the Li-excess layered oxide compound, Li[Li1/5Ni1/5Mn3/5]O2, are studied with synchrotron X-ray diffraction (SXRD), aberration corrected scanning transmission electron microscopy (a-S/TEM), and electron energy loss spectroscopy (EELS). At different states of charge, we carefully examined the crystal structures and electronic structures within the bulk and have found that increased microstrain is accompanied with the cation migration and a second phase formation which occurs during the first cycle voltage plateau as well as into the beginning of the discharge cycle. The evidence indicates that the oxygen vacancy formation and activation may facilitate cation migration and results in the formation of a second phase. The EELS results reveal a Mn valence change from 4+ to 3+ upon oxygen vacancy formation and recovers back to 4+ at the discharge. The oxygen vacancy formation and activation at the partially delithiated sta...

Room-temperature multiferroic hexagonal LuFeO3 films.

Abstract: The crystal and magnetic structures of single-crystalline hexagonal LuFeO(3) films have been studied using x-ray, electron, and neutron diffraction methods. The polar structure of these films are found to persist up to 1050 K; and the switchability of the polar behavior is observed at room temperature, indicating ferroelectricity. An antiferromagnetic order was shown to occur below 440 K, followed by a spin reorientation resulting in a weak ferromagnetic order below 130 K. This observation of coexisting multiple ferroic orders demonstrates that hexagonal LuFeO(3) films are room-temperature multiferroics.

Ni/Pd core/shell nanoparticles supported on graphene as a highly active and reusable catalyst for Suzuki-Miyaura cross-coupling reaction

Abstract: Monodisperse Ni/Pd core/shell nanoparticles (NPs) have been synthesized by sequential reduction of nickel(II) acetate and palladium(II) bromide in oleylamine (OAm) and trioctylphosphine (TOP). The Ni/Pd NPs have a narrow size distribution with a mean particle size of 10 nm and a standard deviation of 5% with respect to the particle diameter. Mechanistic studies showed that the presence of TOP was essential to control the reductive decomposition of Ni-TOP and Pd-TOP, and the formation of Ni/Pd core/shell NPs. Using the current synthetic protocol, the composition of the Ni/Pd within the core/shell structure can be readily tuned by simply controlling the initial molar ratio of the Ni and Pd salts. The as-synthesized Ni/Pd core/shell NPs were supported on graphene (G) and used as catalyst in Suzuki-Miyaura cross-coupling reactions. Among three different kinds of Ni/Pd NPs tested, the Ni/Pd (Ni/Pd = 3/2) NPs were found to be the most active catalyst for the Suzuki-Miyaura cross-coupling of arylboronic acids with aryl iodides, bromides and even chlorides in a dimethylformamide/water mixture by using K2CO3 as a base at 110 °C. The G-Ni/Pd was also stable and reusable, providing 98% conversion after the 5th catalytic run without showing any noticeable Ni/Pd composition change. The G-Ni/Pd structure reported in this paper combines both the efficiency of a homogeneous catalyst and the durability of a heterogeneous catalyst, and is promising catalyst candidate for various Pd-based catalytic applications. Open image in new window

Probing the electrode/electrolyte interface in the lithium excess layered oxide Li1.2Ni0.2Mn0.6O2.

Abstract: A detailed surface investigation of the lithium-excess nickel manganese layered oxide Li1.2Ni0.2Mn0.6O2 structure was carried out using X-ray photoelectron spectroscopy (XPS), total electron yield and transmission X-ray absorption spectroscopy (XAS), and electron energy loss spectroscopy (EELS) during the first two electrochemical cycles. All spectroscopy techniques consistently showed the presence of Mn4+ in the pristine material and a surprising reduction of Mn at the voltage plateau during the first charge. The Mn reduction is accompanied by the oxygen loss revealed using EELS. Upon the first discharge, the Mn at the surface never fully recovers back to Mn4+. The electrode/electrolyte interface of this compound consists of the reduced Mn at the crystalline defect-spinel inner layer and an oxidized Mn species simultaneously with the presence of a superoxide species in the amorphous outer layer. This proposed model signifies that oxygen vacancy formation and lithium removal result in electrolyte decomposition and superoxide formation, leading to Mn activation/dissolution and surface layer-spinel phase transformation. The results also indicate that the role of oxygen is complex and significant in contributing to the extra capacity of this class of high energy density cathode materials.

Supported bimetallic PdAu nanoparticles with superior electrocatalytic activity towards methanol oxidation

Abstract: Monodispersed bimetallic PdAu nanoparticles with controlled composition are prepared by an emulsion-assisted synthetic strategy with ternary metal precursors in the surfactants of oleic acid and oleylamine. The PdAu nanoparticles are loaded on a carbon support, and their electrocatalytic activities are tested for methanol oxidation in alkaline media. The bimetallic PdAu nanoparticles show superior electrocatalytic activities for methanol oxidation compared with the pure Pd nanoparticles prepared by the same method. The most active Pd30Au70 nanoparticles, with significantly low Pd content, even show remarkably higher activities than the commercial Pt/C catalyst. Various characterization techniques such as TEM, XPS and UV-vis are applied to study the nature of the catalysts. It is concluded that the increased activity is dependant on the unique Pd-rich shell and Au-rich core structure of such bimetallic PdAu particles as well as the nature of the Pd species on the catalyst surface.

Phase transitions, phase coexistence, and piezoelectric switching behavior in highly strained BiFeO(3) films.

Abstract: Highly strained BiFeO3 films transition into a true tetragonal state at 430 °C but remain polar to much higher temperatures (∼800 °C). Piezoelectric switching is only possible up to 300 °C, i.e., at temperatures for which strain stabilizes the stripe-like coexistence of multiple polymorphs.

Controlled Synthesis of Nanosized Palladium icosahedra and Their Catalytic Activity towards Formic‐Acid Oxidation

Abstract: Pd icosahedra with sizes controlled in the range of 5-35 nm were synthesized in high purity through a combination of polyol reduction and seed-mediated growth. The Pd icosahedra were obtained with purity >94 % and uniform sizes controlled in the range of 5-17 nm by using ethylene glycol as both the reductant and solvent. The studies indicate that the formation of Pd nanocrystals with an icosahedral shape was very sensitive to the reaction kinetics. The success of this synthesis relies on the use of HCl to manipulate the reaction kinetics and thus control the twin structure and shape of the resultant nanocrystals. The size of the Pd icosahedra could be further increased up to 35 nm by seed-mediated growth, with 17 nm Pd icosahedra serving as seeds. The multiply twinned Pd icosahedra could grow into larger sizes, and their shape and multiply twinned structure were preserved. Thanks to the presence of twin defects, the Pd icosahedra showed a catalytic current density towards formic-acid oxidation that was 1.9 and 11.6 times higher than that of single-crystal Pd octahedra, which were also fully covered by {111} facets, and commercial Pd/C, respectively.

Epitaxial Nanosheet–Nanowire Heterostructures

Abstract: We demonstrate synthesis of a new type of heterostructures that comprise two-dimensional (2D) nanosheets (NSs) epitaxially grown at one-dimensional (1D) nanowires (NWs) The synthesis involves materials with a graphite-like layered structure in which covalently bonded layers are held by weak van der Waals forces GeS was used as a prototype material in this work The synthesis also involves a seeded-growth process, where GeS NWs are grown first as seeds followed by a seeded growth of NSs at the pre-grown NWs We observe that exposing the pre-grown NWs to air prior to the seeded growth is critical for the formation of NSs to yield NS–NW heterostructures Our experimental results suggest that this might be due to a mild oxidation at the NW surface caused by the air exposure, which could subsequently facilitate the nucleation of NSs at the NWs It also suggests that the surface oxidation needs to be controlled in a proper range in order to achieve optimized NS growths We believe that this synthetic strategy

A Perspective on Coatings to Stabilize High-Voltage Cathodes: LiMn1.5Ni0.5O4 with Sub-Nanometer Lipon Cycled with LiPF6 Electrolyte

Abstract: High voltage Li-ion cathodes push the limits of stability for both cathode and electrolyte. Here subnanometer coatings of an amorphous thin film electrolyte (Lipon) improved the room temperature and 60 C cycling stability of a LiMn1.5Ni0.5O4 spinel cathode when charged to 4.9V with a standard LiPF6 carbonate electrolyte. The cathodes delivered superior C-rate performances up to a 5C discharge, when compared to the uncoated cathodes. Enhanced performance extended for at least 100 cycles. Electrochemical impedance spectroscopy indicates that Lipon slows the increase of interface resistance. Thicker 1-3nm Lipon coatings are sufficiently insulating as to block electronic transport to the cathode particles. Thick coatings also slow Mn dissolution. Results suggest that Lipon may act to scavenge impurities or block active sites that promote electrolyte decomposition. While greatly improved by the Lipon coating, this cathode is not sufficiently stable for long cycle life applications. Further work is needed to assess if and what surface coatings will ultimately stabilize the high voltage cathodes. Comments include insight from other studies of Lipon coated cathodes and directions for future research.

Rational defect introduction in silicon nanowires.

Abstract: The controlled introduction of planar defects, particularly twin boundaries and stacking faults, in group IV nanowires remains challenging despite the prevalence of these structural features in other nanowire systems (e.g., II–VI and III–V). Here we demonstrate how user-programmable changes to precursor pressure and growth temperature can rationally generate both transverse twin boundaries and angled stacking faults during the growth of ⟨111⟩ oriented Si nanowires. We leverage this new capability to demonstrate prototype defect superstructures. These findings yield important insight into the mechanism of defect generation in semiconductor nanowires and suggest new routes to engineer the properties of this ubiquitous semiconductor.

Reciprocal Salt Flux Growth of LiFePO4 Single Crystals with Controlled Defect Concentrations

Abstract: Improved methods for the flux growth of single crystals of the important battery material LiFePO4 have been developed, allowing the facile preparation of single crystals up to 1 cm across with well-developed facets at relatively low temperatures. The structural characterization of these samples by both powder X-ray diffraction and single crystal diffraction (X-ray and neutron) indicates that the samples are typically stoichiometric with a very low concentration of Fe defects on the Li site, though crystals with larger concentrations of defects can be specifically grown using Fe-rich fluxes. These defects occur through the formation of a Fe-rich (Li1–2xFex)FePO4 partial solid solution, in contrast to the antisite defects more commonly discussed in the literature which would preserve the ideal LiFePO4 stoichiometry. The LiFePO4 defects are shown to be sarcopside-like (2 Li+ → Fe2+ + vacancy) based on compositions refined from single crystal diffraction data, the observed dependence of unit cell parameters o...

From Core–Shell to Alloys: The Preparation and Characterization of Solution-Synthesized AuPd Nanoparticle Catalysts

Abstract: This article describes the solution-phase synthesis of 4 nm gold nanoparticles with 0.7 atom-thick, 1.9 atom-thick, and 3.8 atom-thick layers of Pd on their surfaces. These well-defined core–shell nanoparticles were deposited on a silica support, calcined, and reduced at 300 °C to create alloyed nanoparticles containing 10.9, 20.2, and 28.5% Pd (w/w). Monometallic Pd nanoparticles sintered during calcination at 300 °C, but no sintering was observed for AuPd nanoparticles. Diffuse reflectance infrared Fourier transform (DRIFT) spectra of adsorbed CO suggests that Au donates d electron density to Pd in the core–shell and alloy structures and confirms the presence of Au and Pd atoms on the surface of the nanoparticles after calcination and reduction. The properties of the AuPd alloy catalysts were tested in the vapor-phase conversion of α-limonene to p-cymene. AuPd nanoparticles containing 20% or more Pd per particle produced p-cymene yields greater than 80%, equivalent to conventional Pd catalysts prepared ...

Mesoporous delafossite CuCrO2 and spinel CuCr2O4: synthesis and catalysis

Abstract: Delafossite CuCrO2 and spinel CuCr2O4 with mesoporous structures have been successfully synthesized using nanocasting methods based on a KIT-6 template. The functional activity of the mesoporous materials was evaluated in applications as heterogeneous catalysts. The activity for photocatalytic hydrogen production of the delafossite structures with different morphologies was characterized and the oxidation state changes associated with photocorrosion of Cu+ investigated using electron energy loss spectroscopy (EELS). Mg2+ doping was found to facilitate the casting of ordered structures for CuCrO2 and improves the photocorrosion resistance of delafossite structures. The mesoporous spinel CuCr2O4 nanostructures were found to be active for low temperature CO oxidation.

Three-dimensional structural analysis of MgO-supported osmium clusters by electron microscopy with single-atom sensitivity.

Abstract: Size, shape, nuclearity: Aberration-corrected scanning transmission electron microscopy was used to determine the 3D structures of MgO-supported Os3, Os4, Os5, and Os10 clusters, which have structures nearly matching those of osmium carbonyl compounds with known crystal structures. The samples are among the best-defined supported catalysts.

Quantifying stoichiometry-induced variations in structure and energy of a SrTiO3 symmetric Σ13 {510}/ grain boundary

Abstract: Grain boundaries (GBs) in complex oxides such as perovskites have been shown to readily accommodate nonstoichiometry changing the electrostatic potential at the boundary plane and effectively controlling material properties such as capacitance, magnetoresistance and superconductivity. Understanding and quantifying exactly how variations in atomic scale nonstoichiometry at the boundary plane extend to the practical mesoscale operating length of the system is therefore critical for improving the overall properties. Bicrystals of SrTiO3 were fabricated to provide the model GB model structures that are analysed in this paper. We show that statistical analysis of aberration-corrected scanning transmission electron microscope images acquired from a large area of GB is an effective routine to understanding the variation in boundary structure that occurs to accommodate nonstoichiometry. In the case of the SrTiO3 22.6° ∑13 (510)/[100] GB analysed here, the symmetric atomic structures observed from a micron-long GB...

Sidewall morphology-dependent formation of multiple twins in Si nanowires.

Abstract: Precise placement of twin boundaries and stacking faults promises new opportunities to fundamentally manipulate the optical, electrical, and thermal properties of semiconductor nanowires. Here we report on the appearance of consecutive twin boundaries in Si nanowires and show that sidewall morphology governs their spacing. Detailed electron microscopy analysis reveals that thin {111} sidewall facets, which elongate following the first twin boundary (TB1), are responsible for deforming the triple-phase line and favoring the formation of the second twin boundary (TB2). While multiple, geometrically correlated defect planes are known in group III–V nanowires, our findings show that this behavior is also possible in group IV materials.

Templated one-step catalytic fabrication of uniform diameter MgxBy nanostructures

Abstract: Direct fabrication of MgxBy nanostructures is achieved by employing Ni–Mg incorporated MCM-41 in the Hybrid Physical–Chemical Vapor Deposition (HPCVD) reaction. Different reaction conditions are tested to optimize the fabrication process. TEM analysis shows the fabrication of MgxBy nanostructures starting at a reaction temperature of 600 °C, and the yield of the nanostructures increases with the reaction temperature. The as-synthesized MgxBy nanostructures have the diameters in the range of 3–5 nm, which do not increase with the reaction temperature. EELS analysis of the template removed nanostructures confirms the existence of B and Mg with minimal contamination of Si and O. NEXAFS and Raman spectroscopy analyses suggested a concentric layered structure for our as-synthesized MgxBy nanotube/nanowire, which is in good agreement with the theoretical calculations. Ni K-edge XAS indicates that the formation of MgNi alloy particles is important for the Vapor–Liquid–Solid (VLS) growth of MgxBy nanostructures with fine diameters, and the presence of Mg vapor not just Mg in the catalyst is crucial for the formation of Ni–Mg clusters. Physical templating by MCM-41 might also help to confine the diameter of the nanostructures. DC magnetization measurements indicate possible superconductive behaviors in the as-synthesized sample.

Room-Temperature Multiferroic Hexagonal LuFeO3

Abstract: We observed the coexistence of ferroelectricity and weak ferromagnetism at room temperature in the hexagonal phase of LuFeO3 stabilized by epitaxial thin film growth. While the ferroelectricity in hexagonal LuFeO3 can be understood as arising from its polar structure, the observation of weak ferromagnetism at room temperature is remarkable considering the frustrated triangular spin structure. An explanation of the room temperature weak ferromagnetism is proposed in terms of a subtle lattice distortion revealed by the structural characterization. The combination of ferroelectricity and weak ferromagnetism in epitaxial films at room temperature offers great potential for the application of this novel multiferroic material in next generation devices.

Novel Closed-Cell Gas-Reaction Holder Allows Characterization of Behavior of Bimetallic Nanoparticles at Elevated Temperatures and Gas Pressures

Abstract: Extended abstract of a paper presented at Microscopy and Microanalysis 2013 in Indianapolis, Indiana, USA, August 4 – August 8, 2013.