Adsorbed hydroxide is an active intermediate or spectator which can block active sites in many electrocatalytic reactions, including CO oxidation [1, 2], methanol oxidation [3], hydrogen oxidation [4], and oxygen reduction [5, 6]. Therefore, understanding the thermodynamics of hydroxide adsorption are important for designing highly active catalysts for these reactions. Experimental measurements, namely cyclic voltammograms, have shown that pH can alter the onset potential and coverage of hydroxide adsorption on Pt(111) [7]. Recent work further shows that the identity of the alkali metal cation (Li, Na, K, Cs) present in an alkaline electrolyte may also impact the thermodynamics of hydroxide adsorption [8, 9]. We use density functional theory to examine the adsorption of hydroxide onto Ir(111), Pt(111), and Au(111) in the absence (acid) and presence (alkaline) of near-surface or adsorbed alkali metal cations. The predicted hydroxide adsorption potentials compare well with experiment. On Ir(111) and Pt(111), the presence of an alkali metal cation in a high pH electrolyte weakens low coverage hydroxide adsorption and strengthens high coverage adsorption. This acts to shift the onset of hydroxide adsorption to more positive potentials, increase the adsorbed hydroxide coverage, and sharpen the experimentally measured cyclic voltammetric peak in an alkaline electrolyte, relative to an acid electrolyte. We can further capture the major differences between the alkali metal cations, including the trend in hydroxide adsorption potential on Ir(111) (Li<Na<K<Cs) and lower peak potential of hydroxide adsorption in LiOH relative to the other alkali metal cations on Pt(111). On Au(111), the coverage dependence of hydroxide adsorption is significantly different than on Ir(111) and Pt(111), and the presence of a near-surface cation may have a slight promoting effect on low coverage hydroxide adsorption. These results are important for understanding the effects of pH and alkali cation on many electrocatalytic reactions which involve adsorbed hydroxide as either a spectator species which blocks active sites or an active intermediate.

[1] J. S. Spendelow, G. Q. Lu, P. J. A. Kenis, and A. Wieckowski, "Electrooxidation of adsorbed CO on Pt(1 1 1) and Pt(1 1 1)/Ru in alkaline media and comparison with results from acidic media," Journal of Electroanalytical Chemistry, vol. 568, pp. 215-224, 2004.

[2] N. P. Lebedeva, M. T. M. Koper, J. M. Feliu, and R. A. van Santen, "Mechanism and kinetics of the electrochemical CO adlayer oxidation on Pt(111)," Journal of Electroanalytical Chemistry, vol. 524–525, pp. 242-251, 2002.

[3] S. Wasmus and A. Küver, "Methanol oxidation and direct methanol fuel cells: a selective review," Journal of Electroanalytical Chemistry, vol. 461, pp. 14-31, 1999.

[4] D. Strmcnik, M. Uchimura, C. Wang, R. Subbaraman, N. Danilovic, V. van der, et al., "Improving the hydrogen oxidation reaction rate by promotion of hydroxyl adsorption," Nat Chem, vol. 5, pp. 300-306, 2013.

[5] N. Markovic, H. Gasteiger, and P. N. Ross, "Kinetics of Oxygen Reduction on Pt(hkl) Electrodes: Implications for the Crystallite Size Effect with Supported Pt Electrocatalysts," Journal of The Electrochemical Society, vol. 144, pp. 1591-1597, 1997.

[6] H. A. Gasteiger and P. N. Ross, "Oxygen Reduction on Platinum Low-Index Single-Crystal Surfaces in Alkaline Solution: Rotating Ring DiskPt(hkl) Studies," The Journal of Physical Chemistry, vol. 100, pp. 6715-6721, 1996.

[7] G. Garcia and M. T. M. Koper, "Stripping voltammetry of carbon monoxide oxidation on stepped platinum single-crystal electrodes in alkaline solution," Physical Chemistry Chemical Physics, vol. 10, pp. 3802-3811, 2008.

[8] StrmcnikD, KodamaK, D. van der Vliet, GreeleyJ, V. R. Stamenkovic, and N. M. Marković, "The role of non-covalent interactions in electrocatalytic fuel-cell reactions on platinum," Nat Chem, vol. 1, pp. 466-472, 2009.

[9] C. Stoffelsma, P. Rodriguez, G. Garcia, N. Garcia-Araez, D. Strmcnik, N. M. Marković, et al., "Promotion of the Oxidation of Carbon Monoxide at Stepped Platinum Single-Crystal Electrodes in Alkaline Media by Lithium and Beryllium Cations," Journal of the American Chemical Society, vol. 132, pp. 16127-16133, 2010.