Nanoparticle-electrode impacts: the oxidation of copper nanoparticles has slow kinetics.

The electrochemical oxidation of copper nanoparticles in aqueous solution was studied via their electrolysis upon impacting a carbon electrode held at a suitable anodic potential. The oxidations were found to be quantitative such that complete oxidation of the particle took place allowing their sizing. Experiments were performed in 1.0 M HNO(3) and in 1.0 M HNO(3)-0.1 M KCl. In the former case a two electron oxidation to Cu(2+) was seen at a formal potential of +0.11 V (vs. SCE). In the latter case two separate one-electron oxidations at -0.01 V and +0.26 V were seen. In addition, theoretical results were derived for the analysis of impact-charge vs. potential data for reversible and irreversible charge transfer kinetics for nanoparticle oxidation. This enabled the inference that overpotential is required for the oxidations and Butler-Volmer transfer coefficients to be determined. The latter are compared with literature data seen for macroscopic copper.

[1]  R. Compton,et al.  Determining unknown concentrations of nanoparticles: the particle-impact electrochemistry of nickel and silver , 2012 .

[2]  Richard G. Compton,et al.  Electron transfer kinetics at single nanoparticles , 2012 .

[3]  A. Bard,et al.  Analysis of diffusion-controlled stochastic events of iridium oxide single nanoparticle collisions by scanning electrochemical microscopy. , 2012, Journal of the American Chemical Society.

[4]  R. Compton,et al.  Particle-impact voltammetry: The reduction of hydrogen peroxide at silver nanoparticles impacting a carbon electrode , 2012 .

[5]  M. Pumera,et al.  The inherent electrochemistry of nickel/nickel-oxide nanoparticles. , 2012, Chemistry, an Asian journal.

[6]  R. Compton,et al.  The non-destructive sizing of nanoparticles via particle–electrode collisions: Tag-redox coulometry (TRC) , 2012 .

[7]  Richard G. Compton,et al.  The electrochemical detection of tagged nanoparticles via particle-electrode collisions: nanoelectroanalysis beyond immobilisation. , 2012, Chemical communications.

[8]  R. Compton,et al.  Gold nanoparticles show electroactivity: counting and sorting nanoparticles upon impact with electrodes. , 2012, Chemical communications.

[9]  R. Compton,et al.  The aggregation of silver nanoparticles in aqueous solution investigated via anodic particle coulometry. , 2011, Chemphyschem : a European journal of chemical physics and physical chemistry.

[10]  Richard G Compton,et al.  The electrochemical detection and characterization of silver nanoparticles in aqueous solution. , 2011, Angewandte Chemie.

[11]  M. Pumera,et al.  Molybdenum metallic nanoparticle detection via differential pulse voltammetry , 2011 .

[12]  Xiaoyin Xiao,et al.  Current transients in single nanoparticle collision events. , 2008, Journal of the American Chemical Society.

[13]  Xiaoyin Xiao,et al.  Observing single nanoparticle collisions at an ultramicroelectrode by electrocatalytic amplification. , 2007, Journal of the American Chemical Society.

[14]  I. O. Wallinder,et al.  Corrosion-induced copper runoff from naturally and pre-patinated copper in a marine environment , 2006 .

[15]  M. Heyrovský,et al.  Voltammetry of Metallic Powder Suspensions on Mercury Electrodes , 2006 .

[16]  M. Muhammed,et al.  Critical evaluation of thermodynamics of complex formation of metal ions in aqueous solutions III. The system Cu(I,II) −Cl− −e at 298.15 K , 1997 .

[17]  M. Heyrovský,et al.  Polarography and voltammetry of mixed titanium(IV) oxide/iron(III) oxide colloids , 1995 .

[18]  M. Heyrovský,et al.  Polarography and voltammetry of ultrasmall colloids : introduction to a new field , 1995 .

[19]  M. Heyrovský,et al.  Polarography and Voltammetry of Aqueous Colloidal SnO2 Solutions , 1995 .

[20]  Pa Peter Bobbert,et al.  Diffusion to a slowly growing truncated sphere on a substrate , 1987 .

[21]  Z. A. El-Hadi,et al.  Mechanism of anodic dissolution of copper in aqueous acidified solutions of different anions , 1986 .

[22]  R. Winand,et al.  Determination des parametres cinetiques de l'electrodeposition du cuivre a haute densite de courant. Cas des solutions sulfuriques sans inhibiteur , 1984 .

[23]  Z. Stanković.  The effect of Cl(I)− ions on kinetics and mechanism of anodic dissolution and cathodic deposition of copper , 1984 .

[24]  J. Trainham,et al.  Potential‐Selective Deposition of Copper from Chloride Solutions Containing Iron , 1977 .

[25]  R. Compton,et al.  Making contact: charge transfer during particle–electrode collisions , 2012 .

[26]  A. Bard.  Elements of Molecular and Biomolecular Electrochemistry: An Electrochemical Approach to Electron Transfer Chemistry By Jean-Michel Savéant (Université de Paris 7, Denis Diderot). J. Wiley & Sons, Inc.: Hoboken, NJ. 2006. xviii + 486 pp. $135. ISBN 0-471-44573-8. , 2007 .