The corrosion behavior of nanometer-scale solids is important in applications ranging from sensing to catalysis. Here we present a general thermodynamic analysis of this for the case of elemental metals and use the analysis to demonstrate the construction of a particle-size-dependent potential?pH diagram for the case of platinum. We discuss the data set required for the construction of such diagrams in general and describe how some parameters are accessible via experiment while others can only be reliably determined from first-principles-based electronic structure calculations. In the case of Pt, our analysis predicts that particles of diameter less than ?4 nm dissolve via the direct electrochemical dissolution pathway, Pt ? Pt2+ + 2e?, while larger particles form an oxide. As an extension of previously published work by our group, electrochemical scanning tunneling microscopy is used to examine the stability of individual Pt-black particles with diameters ranging from 1 to 10 nm. Our experimental results confirm the thermodynamic predictions, suggesting that our analysis provides a general framework for the assessment of the electrochemical stability of nanoscale elemental metals.
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