New Electrochemical Approach for Synthesis of Nanoporous Silver

Cu-Ag alloy films were electrodeposited on Au substrates to serve as precursor alloys for synthesizing finely-structured nanoporous Ag (NPS) structures. Two innovative approaches, surface limited redox replacement (SLRR) and defect mediated growth (DMG) along with overpotential deposition (OPD), were comparatively utilized to fabricate Cu-Ag alloy films. The electrolyte for these novel approaches contained Pb2+ ions to serve either as a sacrificial metal to be replaced by the co-depositing Cu and Ag (in SLRR) or as mediating metal to facilitate the 2D growth of both alloy constituents (in DMG). The resulting alloy films from both approaches displayed superior uniformity and miscibility compared to the OPD alloy, as evidenced by electrochemical scanning electron microscopy (SEM) and X-ray diffraction characterization routines. In a subsequent step, NPS structures were generated through the de-alloying of as-deposited Cu-Ag alloys, as illustrated by SEM imaging that revealed ligament and pore sizes with a thickness in the ballpark of 40 nm. Also, surface area measurements done by a Pb underpotential deposition assay suggested a surface enhancement ratio nearly five times higher than that of flat Ag. Furthermore, various de-alloying potentials were assessed to determine the optimal de-alloying potential for the best outcome of the de-alloying process. Highlights Two new, kinetically mediated approaches were applied to electrodeposit CuAg alloys. Nanoporous Ag (NPS) was synthesized by dealloying of as-deposited CuAg alloys. The optimal dealloying potential range was identified by anodic polarization work. Overpotential growth of CuAg alloy was used as reference throughout the NPS synthesis. The interconnected-porosity NPS structures were studied by SEM and Pb UPD methods.