The growth of ultrathin copper films by surface limited redox replacement is discussed and experimentally illustrated. Cyclic voltammetry, in situ scanning tunneling microscopy (STM), and X-ray diffraction are employed to monitor the two-dimensional growth and characterize the structure of up to 100 monolayers (ML) of Cu on Ag (111) and Au(111) substrates. The growth is carried out by multiple redox replacement of a layer of underpotentially deposited (upd) Pb used as a sacrificial metal. Open-circuit potential monitoring during the replacement reaction is used to control the completion of each deposition event. Anodic film stripping is performed to determine the film thickness and calculate the yield of the employed deposition strategy. The excellent surface quality of an epitaxially grown Cu film is manifested by a distinct Pb upd voltammetry and ascertained by in situ STM showing uniform surface morphology maintained during the entire growth process. High-resolution STM imaging of Pb upd layer deposited on as-grown Cu films reveals a structure identical to Pb on Cu(111). X-ray photoelectron spectroscopy analysis shows no traces of Pb into accordingly deposited Cu films.

The development of a new method for epitaxial growth of metals in solution by galvanic displacement of layers predeposited by underpotential deposition ͑UPD͒ is discussed and experimentally illustrated. Cyclic voltammetry and scanning tunneling microscopy are employed to carry out and monitor a "quasi-perfect," two-dimensional growth of up to 35 monolayers of Ag on Au͑111͒ by repetitive galvanic displacement of underpotentially deposited Tl and Pb monolayers. A complementary kinetic study of Pb and Tl UPD layer stability at open-circuit potential identifies the oxygen reduction reaction and hydrogen evolution reaction as key oxidative competitors of Ag in the proposed displacement protocol. Analysis of the morphology evolution during the growth of Ag by displacement Pb and Tl UPD layers suggests the one-to-one exchange scenario ͑Ag-Tl͒ as more efficient for longer maintenance of a layer-by-layer silver deposition. The excellent quality of layers deposited by monolayer-restricted galvanic displacement is manifested by a steady UPD voltammetry and ascertained by an overall flat and uniform surface morphology maintained during the entire growth process. An X-ray photoelectron spectroscopy analysis finds no traces of Pb and Tl in the Ag deposit.

Anisotropic Mg nanowires have been successfully prepared by electrocrystallization of Grignard's reagents thought to proceed via a modified faces, steps, and kinks (FSK) mechanism. Mg nanoparticles with roughly hexagonal shapes have also been obtained via chemical reduction of the same Grignard's reagents.

Corrosion of base metals represents a tremendous problem that has spurred a global search for cost-effective and environmentally friendly alternatives to current corrosion-inhibiting technologies. In this work, we report a novel sustainable hybrid Mg/poly­(ether imide) (PEI) nanocomposite coating that provides corrosion protection to low-alloy steels at relatively low coating thicknesses and with reduced weight as compared to conventional metallic coatings. The coatings are constituted using Mg nanoplatelets dispersed within a polyamic acid matrix that is subsequently imidized on the steel substrate to form PEI. The coatings function through a combination of sacrificial cathodic protection (afforded by the preferential oxidation of the Mg nanoplatelets), anodic passivation through precipitation of corrosion products, and the inhibitive action of the PEI polymeric matrix. The use of nanostructured Mg allows for reduced coating thicknesses and a smoother surface finish, whereas the PEI matrix provides excellent adhesion to the metal surface. Based on potentiodynamic testing and prolonged exposure to saline environments, the novel coating materials significantly outperform galvanized Zn and Zn-rich primer coatings of comparable thickness.