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Optimizing the use of expensive precious metals is critical to developing sustainable and low-cost processes for heterogeneous catalysis or electrochemistry. Here, we report a synthesis method that yields core-shell Cu-Ru, Cu-Rh, and Cu-Ir nanoparticles with the platinum-group metals segregated on the surface. The synthesis of Cu-Ru, Cu-Rh, and Cu-Ir particles allows maximization of the surface area of these metals and improves catalytic performance. Furthermore, the Cu core can be selectively etched to obtain nanoshells of the platinum-group metal components, leading to a further increase in the active surface area. Characterization of the samples was performed with X-ray absorption spectroscopy, X-ray powder diffraction, and ex situ and in situ transmission electron microscopy. CO oxidation was used as a reference reaction: the three core-shell particles and derivatives exhibited promising catalyst performance and stability after redox cycling. These results suggest that this synthesis approach may optimize the use of platinum-group metals in catalytic applications.

Rapid developments of DNA-based assembly methods provide versatile capabilities in organizing nanoparticles (NPs) in three-dimensional (3D) organized nanomaterials, which is important for optics, catalysis, mechanics, and beyond. However, the use of these nanomaterials is often limited by the narrow range of conditions in which DNA lattices are stable. We demonstrate here an approach to creating an inorganic, silica-based replica of 3D periodic DNA-NP structures with different lattice symmetries. The created ordered nanomaterials, through the precise 3D mineralization, maintain the spatial topology of connections between NPs by DNA struts and exhibit a controllable degree of the porosity. The formed silicated DNA-NP lattices exhibit excellent resiliency. They are stable when exposed to extreme temperatures (>1000°C), pressures (8 GPa), and harsh radiation conditions and can be processed by the conventional nanolithography methods. The presented approach allows the use of a DNA assembly strategy to create organized nanomaterials for a broad range of operational conditions., (Copyright © 2021 The Authors, some rights reserved; exclusive licensee American Association for the Advancement of Science. No claim to original U.S. Government Works. Distributed under a Creative Commons Attribution NonCommercial License 4.0 (CC BY-NC).)

We demonstrate extension of electron-beam lithography using conventional resists and pattern transfer processes to single-digit nanometer dimensions by employing an aberration-corrected scanning transmission electron microscope as the exposure tool. Here, we present results of single-digit nanometer patterning of two widely used electron-beam resists: poly (methyl methacrylate) and hydrogen silsesquioxane. The method achieves sub-5 nanometer features in poly (methyl methacrylate) and sub-10 nanometer resolution in hydrogen silsesquioxane. High-fidelity transfer of these patterns into target materials of choice can be performed using metal lift-off, plasma etch, and resist infiltration with organometallics.

We report a morphotropic phase transformation in vanadium dioxide (VO2) nanobeams annealed in a high-pressure hydrogen gas, which leads to the stabilization of metallic phases. Structural analyses show that the annealed VO2 nanobeams are hexagonal-close-packed structures with roughened surfaces at room temperature, unlike as-grown VO2 nanobeams with the monoclinic structure and with clean surfaces. Quantitative chemical examination reveals that the hydrogen significantly reduces oxygen in the nanobeams with characteristic nonlinear reduction kinetics which depend on the annealing time. Surprisingly, the work function and the electrical resistance of the reduced nanobeams follow a similar trend to the compositional variation due mainly to the oxygen-deficiency-related defects formed at the roughened surfaces. The electronic transport characteristics indicate that the reduced nanobeams are metallic over a large range of temperatures (room temperature to 383 K). Our results demonstrate the interplay between oxygen deficiency and structural/electronic phase transitions, with implications for engineering electronic properties in vanadium oxide systems.

Well-defined surface, such as surface of a single crystal, is being used to provide precise interpretation of catalytic processes, while the nanoparticulate model catalyst more closely represents the real catalysts that are used in industrial processes. Nanocrystal superlattice, which combines the chemical and physical properties of different materials in a single crystalline structure, is an ideal model catalyst, that bridge between conventional models and real catalysts. We identify the active sites for carbon monoxide (CO) oxidation on Au-FeO(x) catalysts by using Au-FeO(x) binary superlattices correlating the activity to the number density of catalytic contacts between Au and FeO(x). Moreover, using nanocrystal superlattices, we propose a general strategy of keeping active metals spatially confined to enhance the stability of metal catalysts. With a great range of nanocrystal superlattice structures and compositions, we establish that nanocrystal superlattices are useful model materials through which to explore, understand, and improve catalytic processes bridging the gap between traditional single crystal and supported catalyst studies.

We use real-time observations of the growth of copper-catalyzed silicon nanowires to determine the nanowire growth mechanism directly and to quantify the growth kinetics of individual wires. Nanowires were grown in a transmission electron microscope using chemical vapor deposition on a copper-coated Si substrate. We show that the initial reaction is the formation of a silicide, eta'-Cu(3)Si, and that this solid silicide remains on the wire tips during growth so that growth is by the vapor-solid-solid mechanism. Individual wire directions and growth rates are related to the details of orientation relation and catalyst shape, leading to a rich morphology compared to vapor-liquid-solid grown nanowires. Furthermore, growth occurs by ledge propagation at the silicide/silicon interface, and the ledge propagation kinetics suggest that the solubility of precursor atoms in the catalyst is small, which is relevant to the fabrication of abrupt heterojunctions in nanowires.