Epitaxial Metal Electrodeposition Controlled by Graphene Layer Thickness.

Control over material structure and morphology during electrodeposition is necessary for material synthesis and energy applications. One approach to guide crystallite formation is to take advantage of epitaxy on a current collector to facilitate crystallographic control. Single-layer graphene on metal foils can promote "remote epitaxy" during Cu and Zn electrodeposition, resulting in growth of metal that is crystallographically aligned to the substrate beneath graphene. However, the substrate-graphene-deposit interactions that allow for epitaxial electrodeposition are not well understood. Here, we investigate how different graphene layer thicknesses (monolayer, bilayer, trilayer, and graphite) influence the electrodeposition of Zn and Cu. Scanning transmission electron microscopy and electron backscatter diffraction are leveraged to understand metal morphology and structure, demonstrating that remote epitaxy occurs on mono- and bilayer graphene but not trilayer or thicker. Density functional theory (DFT) simulations reveal the spatial electronic interactions through thin graphene that promote remote epitaxy. This work advances our understanding of electrochemical remote epitaxy and provides strategies for improving control over electrodeposition.

Tuning the Electronic Properties of Prussian Blue Analogues for Efficient Water Oxidation Electrocatalysis: Experimental and Computational Studies.

Although several Prussian Blue analogues (PBAs) have been investigated as water oxidation catalysts, the field lacks a comprehensive study that focuses on the design of the ideal PBA for this purpose. Here, members of a series of PBAs with different cyanide precursors have been investigated to study the effect of hexacyanometal groups on their electrocatalytic water oxidation activities. Cyclic voltammetric, chronoamperometric, and chronopotentiometric measurements have revealed a close relationship between the electron density of electroactive cobalt sites and electrocatalytic activity, which has also been confirmed by infrared and XPS studies. Furthermore, pH-dependent cyclic voltammetry and computational studies have been performed to gain insight into the catalytic mechanism and electronic structure of cyanide-based systems to identify possible intermediates and to assign the rate-determining step of the target process.

Molten Salt Assisted Self-Assembly: Synthesis of Mesoporous LiCoO2 and LiMn2 O4 Thin Films and Investigation of Electrocatalytic Water Oxidation Performance of Lithium Cobaltate.

Mesoporous thin films of transition metal lithiates (TML) belong to an important group of materials for the advancement of electrochemical systems. This study demonstrates a simple one pot method to synthesize the first examples of mesoporous LiCoO2 and LiMn2 O4 thin films. Molten salt assisted self-assembly can be used to establish an easy route to produce mesoporous TML thin films. The salts (LiNO3 and [Co(H2 O)6 ](NO3 )2 or [Mn(H2 O)4 ](NO3 )2 ) and two surfactants (10-lauryl ether and cethyltrimethylammonium bromide (CTAB) or cethyltrimethylammonium nitrate (CTAN)) form stable liquid crystalline mesophases. The charged surfactant is needed for the assembly of the necessary amount of salt in the hydrophilic domains of the mesophase, which produces stable metal lithiate pore-walls upon calcination. The films have a large pore size with a high surface area that can be increased up to 82 m2 g-1 . The method described can be adopted to synthesize other metal oxides and metal lithiates. The mesoporous thin films of LiCoO2 show promising performance as water oxidation catalysts under pH 7 and 14 conditions. The electrodes, prepared using CTAN as the cosurfactant, display the lowest overpotentials in the literature among other LiCoO2 systems, as low as 376 mV at 10 mA cm-2 and 282 mV at 1 mA cm-2 .