We introduce a simple and inexpensive procedure for epitaxial lift-off of wafer-size flexible and transparent foils of single-crystal gold using silicon as a template. Lateral electrochemical undergrowth of a sacrificial SiO layer was achieved by photoelectrochemically oxidizing silicon under light irradiation. A 28-nanometer-thick gold foil with a sheet resistance of 7 ohms per square showed only a 4% increase in resistance after 4000 bending cycles. A flexible organic light-emitting diode based on tris(bipyridyl)ruthenium(II) that was spin-coated on a foil exploited the transmittance and flexibility of the gold foil. Cuprous oxide as an inorganic semiconductor that was epitaxially electrodeposited onto the gold foils exhibited a diode quality factor of 1.6 (where = 1.0 for an ideal diode), compared with a value of 3.1 for a polycrystalline deposit. Zinc oxide nanowires electrodeposited epitaxially on a gold foil also showed flexibility, with the nanowires intact up to 500 bending cycles.
Epitaxial films through spin coating A simple way to coat a surface with a uniform film is by spin coating. The substrate is spun at high speed, and a droplet of solution containing the coating is added at the center, spreads out, and evaporates. This method is used to make polycrystalline inorganic coatings and amorphous films, such as polymers used in lithography. Kelso et al. performed spin coating with single-crystal substrates, carefully controlling the thickness of the spreading solution on the basis of its viscosity and the rotation rate. In this way, they achieved epitaxial growth—in which the crystallites are oriented by the substrate—for perovskites, zinc oxide, and sodium chloride. Science , this issue p. 166
Designing high-efficiency electrocatalysts for water oxidation has become an increasingly important concept in the catalysis community due to its implications in clean energy generation and storage. In this respect transition-metal-doped mixed-metal selenides incorporating earth-abundant elements such as Ni and Fe have attracted attention due to their unexpectedly high electrocatalytic activity toward the oxygen evolution reaction (OER) with low overpotential in alkaline medium. In this article, quaternary mixed-metal selenide compositions incorporating Ni-Fe-Co were investigated through combinatorial electrodeposition by exploring the ternary phase diagram of Ni-Fe-Co systems. The OER electrocatalytic activity of the resultant quaternary and ternary mixed-metal selenide compositions was measured in order to systematically investigate the trend of catalytic activity as a function of catalyst composition. Accordingly, the composition(s) exhibiting the best catalytic efficiency for the quaternary Fe-Co-Ni mixed-metal selenide was identified. It was observed that the quaternary selenide outperformed the binary as well as the ternary metal selenides in this Ni-Fe-Co phase space. The elemental composition and relative abundance of the elements in the catalyst film was ascertained from energy dispersive spectroscopy (EDS) and X-ray photoelectron spectroscopy (XPS). Mapping of the OER catalytic activity as a function of catalyst composition indicated that catalytic efficiency was more pronounced in the Fe-rich region with moderate amounts of Ni and trace amounts of Co doping, and the best performance was exhibited by (Ni0.25Fe0.68Co0.07)3Se4, which showed an overpotential of 230 mV (vs RHE) at 10 mA cm–2 with stability exceeding 8 h for continuous oxygen generation. It was also observed that typically the quaternary metal selenide composition was close to AB2Se4, which shows a spinel structure type. Electrochemical measurements along with density functional theory (DFT) calculations were performed to correlate the enhancement of catalytic activity toward the Fe-rich region with composition. First-principles DFT calculations were used to estimate the hydroxyl adsorption energy (E ads) on the surface of the mixed-metal selenides with varying compositions. This adsorption energy could be directly correlated to the onset of OER activity, and the results matched very well with the experimentally observed trend with respect to onset overpotential. The knowledge of the trend of catalytic activity as a function of composition will be very important for catalyst design through targeted material synthesis. This work represents an example of a systematic phase exploration for quaternary metal selenides and provides a strong foundation which can be expanded to study other mixed-metal selenide combinations.
Surfaces of achiral materials exhibit two-dimensional chirality if they lack mirror symmetry. An example is the (643) surface of face-centered-cubic metals such as Au. The (643) and (6̅4̅3̅) surfaces are non-superimposable mirror images of each other. Chiral surfaces offer the possibility of serving as heterogeneous catalysts for chiral synthesis or providing a platform for chiral separation or crystallization. Here, we show the symmetry requirements for surface chirality, and we demonstrate that chiral surfaces can be produced by electrochemically depositing epitaxial films of Au onto commercially available Si(643) wafers. Au(643) is deposited onto one side of the wafer, and its enantiomer Au(6̅4̅3̅) is deposited on the other side of the wafer. In addition to the (643) orientation, the (8 14 17) orientation of Au is produced on the Si(643) wafers. The (8 14 17) orientation has a similar kinked surface to the (643) surface, but it has staggered kinks. Other metal films including Pt, Ni, Cu, and Ag that are electrodeposited onto the Au films exhibit strong in-plane and out-of-plane order. Hence, the method provides a pathway for producing chiral surfaces of a wide range of materials, and it obviates the need to work with expensive single crystals. The Ag/Au/Si(643) surface showed a preference for the electrochemical oxidation of d-glucose, whereas the Ag/Au/Si(6̅4̅3̅) surface showed preference for the oxidation of l-glucose.
An eco-friendly method was developed for the synthesis of 2-benzimidazoles over an Fe3O4@SiO2@(NH4)6Mo7O24 magnetic core–shell nanocomposite using hydrogen peroxide.
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