Controlling the morphology of Pt nanostructures can provide a great opportunity to improve their catalytic properties and increase their activity on a mass basis. We synthesized Pd-Pt bimetallic nanodendrites consisting of a dense array of Pt branches on a Pd core by reducing K2PtCl4 with L-ascorbic acid in the presence of uniform Pd nanocrystal seeds in an aqueous solution. The Pt branches supported on faceted Pd nanocrystals exhibited relatively large surface areas and particularly active facets toward the oxygen reduction reaction (ORR), the rate-determining step in a proton-exchange membrane fuel cell. The Pd-Pt nanodendrites were two and a half times more active on the basis of equivalent Pt mass for the ORR than the state-of-the-art Pt/C catalyst and five times more active than the first-generation supportless Pt-black catalyst.
We examined the effects of the thickness of the Pt shell, lattice mismatch, and particle size on specific and mass activities from the changes in effective surface area and activity for oxygen reduction induced by stepwise Pt-monolayer depositions on Pd and Pd(3)Co nanoparticles. The core-shell structure was characterized at the atomic level using Z-contrast scanning transmission electron microscopy coupled with element-sensitive electron energy loss spectroscopy. The enhancements in specific activity are largely attributed to the compressive strain effect based on the density functional theory calculations using a nanoparticle model, revealing the effect of nanosize-induced surface contraction on facet-dependent oxygen binding energy. The results suggest that moderately compressed (111) facets are most conducive to oxygen reduction reaction on small nanoparticles and indicate the importance of concerted structure and component optimization for enhancing core-shell nanocatalysts' activity and durability.
MoS presents a promising low-cost catalyst for the hydrogen evolution reaction (HER), but the understanding about its active sites has remained limited. Here we present an unambiguous study of the catalytic activities of all possible reaction sites of MoS, including edge sites, sulfur vacancies, and grain boundaries. We demonstrate that, in addition to the well-known catalytically active edge sites, sulfur vacancies provide another major active site for the HER, while the catalytic activity of grain boundaries is much weaker. The intrinsic turnover frequencies (Tafel slopes) of the edge sites, sulfur vacancies, and grain boundaries are estimated to be 7.5 s (65-75 mV/dec), 3.2 s (65-85 mV/dec), and 0.1 s (120-160 mV/dec), respectively. We also demonstrate that the catalytic activity of sulfur vacancies strongly depends on the density of the vacancies and the local crystalline structure in proximity to the vacancies. Unlike edge sites, whose catalytic activity linearly depends on the length, sulfur vacancies show optimal catalytic activities when the vacancy density is in the range of 7-10%, and the number of sulfur vacancies in high crystalline quality MoS is higher than that in low crystalline quality MoS, which may be related with the proximity of different local crystalline structures to the vacancies.
Materials that undergo a conversion reaction with lithium (e.g., metal fluorides MF(2): M = Fe, Cu, ...) often accommodate more than one Li atom per transition-metal cation, and are promising candidates for high-capacity cathodes for lithium ion batteries. However, little is known about the mechanisms involved in the conversion process, the origins of the large polarization during electrochemical cycling, and why some materials are reversible (e.g., FeF(2)) while others are not (e.g., CuF(2)). In this study, we investigated the conversion reaction of binary metal fluorides, FeF(2) and CuF(2), using a series of local and bulk probes to better understand the mechanisms underlying their contrasting electrochemical behavior. X-ray pair-distribution-function and magnetization measurements were used to determine changes in short-range ordering, particle size and microstructure, while high-resolution transmission electron microscopy (TEM) and electron energy-loss spectroscopy (EELS) were used to measure the atomic-level structure of individual particles and map the phase distribution in the initial and fully lithiated electrodes. Both FeF(2) and CuF(2) react with lithium via a direct conversion process with no intercalation step, but there are differences in the conversion process and final phase distribution. During the reaction of Li(+) with FeF(2), small metallic iron nanoparticles (<5 nm in diameter) nucleate in close proximity to the converted LiF phase, as a result of the low diffusivity of iron. The iron nanoparticles are interconnected and form a bicontinuous network, which provides a pathway for local electron transport through the insulating LiF phase. In addition, the massive interface formed between nanoscale solid phases provides a pathway for ionic transport during the conversion process. These results offer the first experimental evidence explaining the origins of the high lithium reversibility in FeF(2). In contrast to FeF(2), no continuous Cu network was observed in the lithiated CuF(2); rather, the converted Cu segregates to large particles (5-12 nm in diameter) during the first discharge, which may be partially responsible for the lack of reversibility in the CuF(2) electrode.
In this Letter we show that superconducting Fe(1.01)Se undergoes a structural transition at 90 K from a tetragonal to an orthorhombic phase but that nonsuperconducting Fe(1.03)Se does not. High resolution electron microscopy at low temperatures further reveals an unexpected additional modulation of the crystal structure of the superconducting phase that involves displacements of the Fe atoms, and that the nonsuperconducting composition shows a different, complex nanometer-scale structural modulation. Finally, we show that magnetism is not the driving force for the phase transition in the superconducting phase.
This article provides an overview of recent developments regarding synthesis of Pd nanocrystals with well‐controlled shapes in aqueous solutions. In a solution‐phase synthesis, the final shape taken by a nanocrystal is determined by the twin structures of seeds and the growth rates of different crystallographic facets. Here, the maneuvering of these factors in an aqueous system to achieve shape control for Pd nanocrystals is discussed. L‐ascorbic acid, citric acid, and poly(vinyl pyrrolidone) are tested for manipulating the reduction kinetics, with citric acid and Br– ions used as capping agents to selectively promote the formation of {111} and {100} facets, respectively. The distribution of single‐crystal versus multiple‐twinned seeds can be further manipulated by employing or blocking oxidative etching. The shapes obtained for the Pd nanocrystals include truncated octahedron, icosahedron, octahedron, decahedron, hexagonal and triangular plates, rectangular bar, and cube. The ability to control the shape of Pd nanocrystals provides a great opportunity to systematically investigate their catalytic, electrical, and plasmonic properties.
Lattice oxygen can play an intriguing role in electrochemical processes, not only maintaining structural stability, but also influencing electron and ion transport properties in high-capacity oxide cathode materials for Li-ion batteries. Here, we report the design of a gas–solid interface reaction to achieve delicate control of oxygen activity through uniformly creating oxygen vacancies without affecting structural integrity of Li-rich layered oxides. Theoretical calculations and experimental characterizations demonstrate that oxygen vacancies provide a favourable ionic diffusion environment in the bulk and significantly suppress gas release from the surface. The target material is achievable in delivering a discharge capacity as high as 301 mAh g−1 with initial Coulombic efficiency of 93.2%. After 100 cycles, a reversible capacity of 300 mAh g−1 still remains without any obvious decay in voltage. This study sheds light on the comprehensive design and control of oxygen activity in transition-metal-oxide systems for next-generation Li-ion batteries.
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