We investigated polarization dependence of the Raman modes in black phosphorus (BP) using five different excitation wavelengths. The crystallographic orientation was determined by comparing polarized optical microscopy with high-resolution transmission electron microscopy analysis. In polarized Raman spectroscopy, the B2g mode shows the same polarization dependence regardless of the excitation wavelength or the sample thickness. On the other hand, the Ag(1) and Ag(2) modes show a peculiar polarization behavior that depends on the excitation wavelength and the sample thickness. The thickness dependence can be explained by considering the anisotropic interference effect due to the birefringence and dichroism of the BP crystal, but the wavelength dependence cannot be explained. We propose a simple and fail-proof procedure to determine the orientation of a BP crystal by combining polarized Raman scattering with polarized optical microscopy.
The most efficient electrocatalyst for the hydrogen evolution reaction (HER) is a Pt‐based catalyst, but its high cost and nonperfect efficiency hinder wide‐ranging industrial/technological applications. Here, an electrocatalyst of both ruthenium (Ru) single atoms (SAs) and N‐doped‐graphitic(GN)‐shell‐covered nitrided‐Ru nanoparticles (NPs) (having a Ru‐Nx shell) embedded on melamine‐derived GN matrix {1: [Ru(SA)+Ru(NP)@RuNx@GN]/GN}, which exhibits superior HER activity in both acidic and basic media, is presented. In 0.5 m H2SO4/1 m KOH solutions, 1 shows diminutive “negative overpotentials” (−η = |η| = 10/7 mV at 10 mA cm−2, lowest ever) and high exchange current densities (4.70/1.96 mA cm−2). The remarkable HER performance is attributed to the near‐zero free energies for hydrogen adsorption/desorption on Ru(SAs) and the increased conductivity of melamine‐derived GN sheets by the presence of nitrided‐Ru(NPs). The nitridation process forming nitrided‐Ru(NPs), which are imperfectly covered by a GN shell, allows superb long‐term operation durability. The catalyst splits water into molecular oxygen and hydrogen at 1.50/1.40 V (in 0.1 m HClO4/1 m KOH), demonstrating its potential as a ready‐to‐use, highly effective energy device for industrial applications.
Fast-growth of single crystal monolayer graphene by CVD using methane and hydrogen has been achieved on "homemade" single crystal Cu/Ni(111) alloy foils over large area. Full coverage was achieved in 5 min or less for a particular range of composition (1.3 at.% to 8.6 at.% Ni), as compared to 60 min for a pure Cu(111) foil under identical growth conditions. These are the bulk atomic percentages of Ni, as a superstructure at the surface of these foils with stoichiometry CuNi (for 1.3 to 7.8 bulk at.% Ni in the Cu/Ni(111) foil) was discovered by low energy electron diffraction (LEED). Complete large area monolayer graphene films are either single crystal or close to single crystal, and include folded regions that are essentially parallel and that were likely wrinkles that "fell over" to bind to the surface; these folds are separated by large, wrinkle-free regions. The folds occur due to the buildup of interfacial compressive stress (and its release) during cooling of the foils from 1075 °C to room temperature. The fold heights measured by atomic force microscopy (AFM) and scanning tunneling microscopy (STM) prove them to all be 3 layers thick, and scanning electron microscopy (SEM) imaging shows them to be around 10 to 300 nm wide and separated by roughly 20 μm. These folds are always essentially perpendicular to the steps in this Cu/Ni(111) substrate. Joining of well-aligned graphene islands (in growths that were terminated prior to full film coverage) was investigated with high magnification SEM and aberration-corrected high-resolution transmission electron microscopy (TEM) as well as AFM, STM, and optical microscopy. These methods show that many of the "join regions" have folds, and these arise from interfacial adhesion mechanics (they are due to the buildup of compressive stress during cool-down, but these folds are different than for the continuous graphene films-they occur due to "weak links" in terms of the interface mechanics). Such Cu/Ni(111) alloy foils are promising substrates for the large-scale synthesis of single-crystal graphene film.
The process of oxidation of a copper surface coated by a layer of graphene in water-saturated air at 50 °C was studied where it was observed that oxidation started at the graphene edge and was complete after 24 h. Isotope labeling of the oxygen gas and water showed that the oxygen in the formed copper oxides originated from water and not from the oxygen in air for both Cu and graphene-coated Cu, and this has interesting potential implications for graphene as a protective coating for Cu in dry air conditions. We propose a reaction pathway where surface hydroxyl groups formed at graphene edges and defects induce the oxidation of Cu. DFT simulation shows that the binding energy between graphene and the oxidized Cu substrate is smaller than that for the bare Cu substrate, which facilitates delamination of the graphene. Using this process, dry transfer is demonstrated using poly(bisphenol A carbonate) (PC) as the support layer. The high quality of the transferred graphene is demonstrated from Raman maps, XPS, STM, TEM, and sheet resistance measurements. The copper foil substrate was reused without substantial weight loss to grow graphene (up to 3 cycles) of equal quality to the first growth after each cycle. It was found that dry transfer yielded graphene with less Cu impurities as compared to methods using etching of the Cu substrate. Using PC yielded graphene with less polymeric residue after transfer than the use of poly(methyl methacrylate) (PMMA) as the supporting layer. Hence, this dry and clean delamination technique for CVD graphene grown on copper substrates is highly advantageous for the cost-effective large-scale production of graphene, where the Cu substrate can be reused after each growth.
Low-energy density has long been the major limitation to the application of supercapacitors. Introducing topological defects and dopants in carbon-based electrodes in a supercapacitor improves the performance by maximizing the gravimetric capacitance per mass of the electrode. However, the main mechanisms governing this capacitance improvement are still unclear. We fabricated planar electrodes from CVD-derived single-layer graphene with deliberately introduced topological defects and nitrogen dopants in controlled concentrations and of known configurations, to estimate the influence of these defects on the electrical double-layer (EDL) capacitance. Our experimental study and theoretical calculations show that the increase in EDL capacitance due to either the topological defects or the nitrogen dopants has the same origin, yet these two factors improve the EDL capacitance in different ways. Our work provides a better understanding of the correlation between the atomic-scale structure and the EDL capacitance and presents a new strategy for the development of experimental and theoretical models for understanding the EDL capacitance of carbon electrodes.
Atomically smooth hexagonal boron nitride (h-BN) films are considered as a nearly ideal dielectric interface for two-dimensional (2D) heterostructure devices. Reported mono- to few-layer 2D h-BN films, however, are mostly small grain-sized, polycrystalline and randomly oriented. Here we report the growth of centimetre-sized atomically thin h-BN films composed of aligned domains on resolidified Cu. The films consist of monolayer single crystalline triangular and hexagonal domains with size of up to ∼10 μm. The domains converge to symmetrical multifaceted shapes such as "butterfly" and "6-apex-star" and exhibit ∼75% grain alignment for over millimetre distances as verified through transmission electron microscopy. Scanning electron microscopy images reveal that these domains are aligned for over centimetre distances. Defect lines are generated along the grain boundaries of mirroring h-BN domains due to the two different polarities (BN and NB) and edges with the same termination. The observed triangular domains with truncated edges and alternatively hexagonal domains are in accordance with Wulff shapes that have minimum edge energy. This work provides an extensive study on the aligned growth of h-BN single crystals over large distances and highlights the obstacles that are needed to be overcome for a 2D material with a binary configuration.
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