This activity presents a comparison study between nanocubes (NC) and nano-octahedra (NO) as well as (100) and (111) thin films of Pt 4 Cu, all used as.

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This activity presents a comparison study between nanocubes (NC) and nano-octahedra (NO) as well as (100) and (111) thin films of Pt 4 Cu, all used as catalysts for formic acid oxidation. This work introduces for the first time (i) a novel synthetic method for Pt 4 Cu NO and (ii) the use of surface limited redox replacement (SLRR) of Pb underpotentially deposited (UPD) layer for epitaxial growth of thin alloy films. The NP catalysts exhibit superior durability when compared to their thin film counterparts, but feature nearly five-fold lower activity. Overall, the Pt 4 Cu (100) catalysts outperform the (111) ones in terms of durability but feature equal to lower activity. Development and Application of a New Method for Epitaxial Growth of Metals, Alloys and Multilayers by Surface Limited Redox Replacement Nikolay Dimitrov, SUNY at Binghamton, DMR Homo- and Hetero-epitaxial Deposition of Au by SLRR of Pb UPD Layer in One-Cell Configuration Catalytic Performance Comparison of Shape-Dependent Nanocrystals and Oriented Ultra Thin Films of Pt 4 Cu Alloy in the Formic Acid Oxidation Process This work reports on homo and hetero-epitaxial Au deposition realized by surface limited redox replacement (SLRR) of Pb underpotentially deposited (UPD) layer by [AuCl 4 ] - ions. An over-stoichiometric amount of deposited Au hinted at by EQCM kinetic experiments and validated by separate pulse experiments has been attributed to reduction a pre-adsorbed layer of [AuCl 4 ] - ions. After as little as one replacement event on Pt (111) the deposit displays a Pb UPD CV curve alike to the one on a bare Au (111) face. High quality epitaxial Au has been grown for up to 40 SLRR events as evidenced by CV and ex-situ STM. However, growth of thicker films yields a significant surface roughness evolution. Pt 4 Cu (111) Pt 4 Cu (100) Pt 4 Cu (110)

Dissemination: A large portion of the reported activities supported by this grant, was presented as oral talks by Nikolay Dimitrov and Dr. Natasa Vasiljevic at the 222 th PRiME Meeting of ECS in October 2012 in Honolulu, HI. Matt Fayette, (SUNY Potsdam), Lori Bromberg (SUNY Fredonia), and Corey Mitchell (Lycoming College) presented talks in their Alma Mater institutions. Four related papers were published in Electrocatalysis, Electrochimica Acta, and ACS Catalysis. Professional Development  Martha Kamundi graduated with Ph.D. in May of 2013 and is currently looking for future challenges.  Matt Fayette defended his Ph.D. dissertation in June of 2013 and is currently a postdoc at Cornel University.  Lori Bromberg defended her M.S. thesis in July of 2013  During the 2013 summer first recipient of all new “Mike Starzak” Award, Ryan Rooney, worked with our group. Ongoing Collaborations  Results on the durability of Pt-coated catalysts for formic acid oxidation have been published in collaboration with Dr. Natasa Vasiljevic from University of Bristol, UK.  Work on the catalytic activity of Pt 4 Cu(hkl) alloy nanoparticles and thin films with Dr. Fang’s group has been finalized and published in Electrocatalysis.  Glass interposers development work has expanded in collaboration with Dr. Borgesen’s group at Binghamton thus helping the PI to attract industrial funding. Dr. Natasa Vasiljevic Department of Physics, University of Bristol, UK Ryan Rooney, a junior student pursuing chemistry major joined in September of 2012 the PI’s group and was research trained during the academic year. He also received the all new “Mike Starzak Award ” and worked all summer with the PI’s group. Dr. Peter Borgesen (i) Epitaxial Growth of Au on Pt (111) and Pt (poly) by Surface Limited Redox Replacement of Pb UPD Layer. (ii) Highly-Active Pt Coated NPG Catalyst for HCOOH Oxidation: Synthesis, SLRR Coating, Activity and Durability. DEPARTMENT OF SYSTEMS SCIENCE AND INDUSTRIAL ENGINEERING Nikolay Dimitrov - Invited Talks at PRiME 2012: Lori Bromberg, a graduate student in the PI’s group, defended her M.S. dissertation in July of She is currently appointed full time by IBM at Endicott, NY. She also intends to continue part-time with the PI’s group for a Ph.D. degree Matt Fayette, a graduate student in the PI’s group, defended his Ph.D. dissertation in June 2013 and accepted right after that an offer for postdoctoral position at Cornell University starting in mid-July. Martha Kamundi, a graduate student in the PI’s group, defended her Ph.D. dissertation in May of 2013 and received her Ph.D. degree from SUNY Binghamton. She is currently exploring different employment opportunities. Development and Application of a New Method for Epitaxial Growth of Metals, Alloys and Multilayers by Surface Limited Redox Replacement Nikolay Dimitrov, SUNY at Binghamton, DMR