Infrared spectroscopic and voltammetric study of adsorbed CO on stepped surfaces of copper monocrystalline electrodes

Abstract

Voltammetric and infrared (IR) spectroscopic measurements were carried out to study adsorbed CO on two series of copper single crystal electrodes n(1 1 1)–(1 1 1) and n(1 1 1)–(1 0 0) in 0.1 M KH 2PO 4 + 0.1 M K 2HPO 4 at 0 °C. Reversible voltammetric waves were observed below −0.55 V versus SHE for adsorption of CO which displaces preadsorbed phosphate anions. The electric charge of the redox waves is proportional to the step atom density for both single crystal series. This fact indicates that phosphate anions are specifically adsorbed on the step sites below −0.55 V versus SHE. Voltammetric measurements indicated that (1 1 1) terrace of Cu is covered with adsorbed CO below −0.5 V versus SHE. Nevertheless, no IR absorption band of adsorbed CO is detected from (1 1 1) terrace. Presence of adsorbed CO on (1 1 1) terrace is presumed which is not visible by the potential difference spectroscopy used in the present work. IR spectroscopic measurements showed that CO is reversibly adsorbed with an on-top manner on copper single crystal electrodes of n(1 1 1)–(1 1 1) and n(1 1 1)–(1 0 0) with approximately same wavenumber of C O stretching vibration of 2070 cm −1. The IR band intensity is proportional to the step atom density. Thus CO is adsorbed on (1 1 1) or (1 0 0) steps on the single crystal surfaces. An analysis of the IR band intensity suggested that one CO molecule is adsorbed on every two or more Cu step atom of the monocrystalline surface. The spectroscopic data were compared with those reported for u h v system. The C O stretching wavenumber of adsorbed CO in the electrode–electrolyte system is 30–40 cm −1 lower than those in u h v system.