Electrochemical and FTIRS characterisation of NO adlayers on cyanide-modified Pt(111) electrodes: the mechanism of nitric oxide electroreduction on Pt.
We report here a study, using cyclic voltammetry and FTIRS, of NO irreversibly adsorbed on a cyanide-modified Pt(111) electrode. NO adlayers were formed by immersion of the cyanide-modified Pt(111) electrode in an acidic solution of KNO(2). The behaviour of NO adsorbed on the cyanide-modified electrode is very similar to that of NO on the clean Pt(111) surface, suggesting that adsorbed cyanide (saturation coverage theta(CN) = 0.5) behaves simply as a third body, blocking some of the surface sites but leaving the free Pt sites unaffected. Comparison of the voltammetric profile for NO electroreduction on Pt(111) and on cyanide-modified Pt(111) electrodes has allowed us: (i) to confirm that the reduction of three-fold hollow NO and atop NO on Pt(111) electrodes occurs in two distinct reduction peaks, as previously proposed by Rosca et al. (Langmuir, 2005, 21, 1448); (ii) to suggest that the reduction of irreversibly adsorbed NO layers on Pt electrodes can proceed through two possible paths, one involving an EE mechanism in which the rate-determining step (rds) is an Eley-Rideal reaction, with a direct proton transfer from the solution to adsorbed NO, and the other involving an EC mechanism in which the rds is a Langmuir-Hinshelwood reaction of adsorbed NO with adsorbed H. The availability of adsorbed hydrogen determines which path is followed by the reaction; (iii) to identify the smallest atomic ensemble for the reduction of NO on Pt as being composed of two adjacent Pt atoms.
Cuesta
Angel
A
Instituto de Química Física "Rocasolano", CSIC, C. Serrano, 119, E-28006, Madrid, Spain. a.cuesta@iqfr.csic.es
Escudero
María
M
D000327:Adsorption; D004563:Electrochemistry; D004566:Electrodes; D006859:Hydrogen / Q000737:chemistry; D008956:Models, Chemical; D009569:Nitric Oxide / Q000737:chemistry*; D010084:Oxidation-Reduction; D010984:Platinum / Q000737:chemistry*; D011190:Potassium Cyanide / Q000737:chemistry*; D017550:Spectroscopy, Fourier Transform Infrared
D009569:Nitric Oxide; D010984:Platinum; D006859:Hydrogen; D011190:Potassium Cyanide