Electrochemical dissolution of surface alloys in acids: Thermodynamic trends from first-principles calculations

Abstract A simple procedure is introduced to use periodic Density Functional Theory calculations to estimate trends in the thermodynamics of surface alloy dissolution in acidic media. With this approach, the dissolution potentials for solute metal atoms embedded in the surface layer of various host metals (referenced to the dissolution potential of the solute in its pure, metallic form) are calculated. Periodic trends in the calculated potentials are found to be related to trends in surface segregation energies of the various solute/host pairs. The effects of water splitting and concomitant hydroxyl adsorption on the dissolution potentials are also considered; these effects do not change the potentials for highly oxophilic solutes embedded in less active hosts, but they do decrease the dissolution potential for more inert solutes on oxophilic hosts. Finally, the dissolution of Pt “skin” layers from Pt 3 X (X = Fe, Co, and Ni) bulk alloys is analyzed; the Pt skins are found to be stabilized compared to pure Pt.

[1]  J. Nørskov,et al.  Hydrogen evolution over bimetallic systems: understanding the trends. , 2006, Chemphyschem : a European journal of chemical physics and physical chemistry.

[2]  Hiroyuki Uchida,et al.  Enhancement of the Electroreduction of Oxygen on Pt Alloys with Fe, Ni, and Co , 1999 .

[3]  Philip N. Ross,et al.  Improved Oxygen Reduction Activity on Pt3Ni(111) via Increased Surface Site Availability , 2007, Science.

[4]  G. Kresse,et al.  Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set , 1996 .

[5]  Philip N. Ross,et al.  Surface segregation effects in electrocatalysis: Kinetics of oxygen reduction reaction on polycrystalline Pt3Ni alloy surfaces , 2002 .

[6]  Manos Mavrikakis,et al.  Adsorption and dissociation of O2 on Pt-Co and Pt-Fe alloys. , 2004, Journal of the American Chemical Society.

[7]  I. Fried,et al.  Voltammetric studies of alkali metal reduction on platinum electrodes , 1971 .

[8]  H. Gerischer,et al.  Underpotential deposition of metals and work function differences , 1974 .

[9]  D. Vanderbilt,et al.  Soft self-consistent pseudopotentials in a generalized eigenvalue formalism. , 1990, Physical review. B, Condensed matter.

[10]  L. Bengtsson,et al.  Dipole correction for surface supercell calculations , 1999 .

[11]  Clausen,et al.  Design of a surface alloy catalyst for steam reforming , 1998, Science.

[12]  N. Marković,et al.  Effect of surface composition on electronic structure, stability, and electrocatalytic properties of Pt-transition metal alloys: Pt-skin versus Pt-skeleton surfaces. , 2006, Journal of the American Chemical Society.

[13]  L. Blum,et al.  Phase transitions at electrode interfaces , 1996 .

[14]  J. Nørskov,et al.  Computational high-throughput screening of electrocatalytic materials for hydrogen evolution , 2006, Nature materials.

[15]  D. Kolb Electrochemical Surface Science , 2001 .

[16]  D. Kolb,et al.  Tuning reaction rates by lateral strain in a palladium monolayer. , 2005, Angewandte Chemie.

[17]  G. Georg,et al.  Amino acid-derived enaminones: a study in ring formation providing valuable asymmetric synthons. , 2006, Journal of the American Chemical Society.

[18]  Guichang Wang,et al.  Kinetic mechanism of methanol decomposition on Ni(111) surface: a theoretical study. , 2005, The journal of physical chemistry. B.

[19]  O. J. Murphy,et al.  Electrochemistry in transition : from the 20th to the 21st century , 1992 .

[20]  Andrei V. Ruban,et al.  Surface segregation energies in transition-metal alloys , 1999 .

[21]  Manos Mavrikakis,et al.  Electronic structure and catalysis on metal surfaces. , 2002, Annual review of physical chemistry.

[22]  S. Trasatti Development of the Work Function Approach to the Underpotential Deposition of Metals. Application to the Hydrogen Evolution Reaction* , 1975 .

[23]  H. Jónsson,et al.  Origin of the Overpotential for Oxygen Reduction at a Fuel-Cell Cathode. , 2004, The journal of physical chemistry. B.

[24]  Manos Mavrikakis,et al.  Why Au and Cu Are More Selective Than Pt for Preferential Oxidation of CO at Low Temperature , 2004 .

[25]  Jens K Nørskov,et al.  Changing the activity of electrocatalysts for oxygen reduction by tuning the surface electronic structure. , 2006, Angewandte Chemie.

[26]  A. Karma,et al.  Evolution of nanoporosity in dealloying , 2001, Nature.

[27]  Junliang Zhang,et al.  Mixed-metal pt monolayer electrocatalysts for enhanced oxygen reduction kinetics. , 2005, Journal of the American Chemical Society.

[28]  J. Ziegler,et al.  Nanoscale decoration of electrode surfaces with an STM , 2000 .

[29]  J. Nørskov,et al.  Improved adsorption energetics within density-functional theory using revised Perdew-Burke-Ernzerhof functionals , 1999 .

[30]  E. Leiva Recent developments in the theory of metal upd , 1996 .

[31]  M. Sangaranarayanan,et al.  Underpotential deposition of metals – Progress and prospects in modelling , 2005 .

[32]  J. Nørskov,et al.  A general scheme for the estimation of oxygen binding energies on binary transition metal surface alloys , 2005 .

[33]  Junliang Zhang,et al.  Controlling the catalytic activity of platinum-monolayer electrocatalysts for oxygen reduction with different substrates. , 2005, Angewandte Chemie.

[34]  R. C. Weast CRC Handbook of Chemistry and Physics , 1973 .