ABSTRACT
We report a catalyst family of high-entropy alloy (HEA) atomic layers having three elements from iron-group metals (IGMs) and two elements from platinum-group metals (PGMs). Ten distinct quinary compositions of IGM-PGM-HEA with precisely controlled square atomic arrangements are used to explore their impact on hydrogen evolution reaction (HER) and hydrogen oxidation reaction (HOR). The PtRuFeCoNi atomic layers perform enhanced catalytic activity and durability toward HER and HOR when benchmarked against the other IGM-PGM-HEA and commercial Pt/C catalysts. Operando synchrotron x-ray absorption spectroscopy and density functional theory simulations confirm the cocktail effect arising from the multielement composition. This effect optimizes hydrogen-adsorption free energy and contributes to the remarkable catalytic activity observed in PtRuFeCoNi. In situ electron microscopy captures the phase transformation of metastable PtRuFeCoNi during the annealing process. They transform from random atomic mixing (25°C), to ordered L10 (300°C) and L12 (400°C) intermetallic, and finally phase-separated states (500°C).
ABSTRACT
High-entropy alloy (HEA) nanocrystals have attracted extensive attention in catalysis. However, there are no effective strategies for synthesizing them in a controllable and predictable manner. With quinary HEA nanocrystals made of platinum-group metals as an example, we demonstrate that their structures with spatial compositions can be predicted by quantitatively knowing the reduction kinetics of metal precursors and entropy of mixing in the nanocrystals under dropwise addition of the mixing five-metal precursor solution. The time to reach a steady state for each precursor plays a pivotal role in determining the structures of HEA nanocrystals with homogeneous alloy and core-shell features. Compared to the commercial platinum/carbon and phase-separated counterparts, the dendritic HEA nanocrystals with a defect-rich surface show substantial enhancement in catalytic activity and durability toward both hydrogen evolution and oxidation. This quantitative study will lead to a paradigm shift in the design of HEA nanocrystals, pushing away from the trial-and-error approach.
ABSTRACT
In this study, the high-density SiC/SiO2 core-shell nanowires were synthesized on the nickel coated SiO2 (100 nm)/Si substrate by chemical vapor deposition (CVD) method with ferrocene precursor at temperature 1000 °C compared to previous studies (1300-1600 °C). The present work provides an efficient strategy for the production of SiC/SiO2 nanowires with uniform morphology and good optical properties, where the Ni layer plays important roles for this fabrication at low temperature which reduces the decomposition temperature of hydrocarbon gases and improves the growth quality of SiC nanowires. The as-synthesized SiC/SiO2 nanowires consist of single crystal 3C structures as well as 3C structures with defects along [111] direction. In the photoluminescence (PL) spectrum, the SiC/SiO2 core-shell nanowires revealed an obvious blueshift. The blueshift is due to the formation of nanoscale silicon carbide polytypism caused by the stacking faults in 3C-SiC and the nanoscale polytypism also caused the transition from indirect to direct bandgap which explains why the stacking faults percentage in SiC confirmed from X-ray diffraction (XRD) is 19%, but ultimately makes the strongest emission intensity. Finally, the PL characteristics are further improved by changing the diameter of the SiC nanowire and etching and an approximate model followed by the vapor-liquid-solid (VLS) mechanism was proposed to explain the possible growth mechanism of the SiC/SiO2 nanowires.
ABSTRACT
Nanoelectronics of two-dimensional (2D) materials and related applications are hindered with critical contact issues with the semiconducting monolayers. To solve these issues, a fundamental challenge is selective and controllable fabrication of p-type or ambipolar transistors with a low Schottky barrier. Most p-type transistors are demonstrated with tungsten selenides (WSe2) but a high growth temperature is required. Here, we utilize seeding promoter and low pressure CVD process to enhance sequential WSe2 growth with a reduced growth temperature of 800 °C for reduced compositional fluctuations and high hetero-interface quality. Growth behavior of the sequential WSe2 growth at the edge of patterned graphene is discussed. With optimized growth conditions, high-quality interface of the laterally stitched WSe2-graphene is achieved and characterized with transmission electron microscopy (TEM). Device fabrication and electronic performances of the laterally stitched WSe2-graphene are presented.
ABSTRACT
The multilayer 1T-TaSe2 is successfully synthesized by annealing a Se-implanted Ta thin film on the SiO2/Si substrate. Material analyses confirm the 1T (octahedral) structure and the quasi-2D nature of the prepared TaSe2. Temperature-dependent resistivity reveals that the multilayer 1T-TaSe2 obtained by our method undergoes a commensurate charge-density wave (CCDW) transition at around 500 K. This synthesis process has been applied to synthesize MoSe2 and HfSe2 and expanded for synthesis of one more transition-metal dichalcogenide (TMD) material. In addition, the main issue of the process, that is, the excess metal capping on the TMD layers, is solved by the reduction of thickness of the as-deposited metal thin film in this work.