Abstract
Adsorption of gaseous HClO{sub 4} on Ag(110) was studied under ultrahigh vacuum to investigate the surface chemistry of electrolytes. Surface reactions and adsorbate structure were studied over the temperature range of 100-900 K and coverage range of zero to several multilayers with thermal desorption spectroscopy (TDS), low-energy electron diffraction (LEED), and electron-stimulated desorption ion angular distribution (ESDIAD). HClO{sub 4} adsorbed molecularly at 100 K with a sticking coefficient of {approx} 10{sup {minus}1} or less. The sticking coefficient increased to unity with increasing coverage due to hydrogen-bonding interactions with concurrently adsorbed H{sub 2}O. Once adsorbed, HClO{sub 4} deprotonated below 150 K to produce adsorbed perchlorate (ClO{sub 4}). Saturation coverage of ClO{sub 4} was 0.5 monolayer for which a c(2{times}2) LEED pattern was observed. Adsorbed perchlorate decomposed above 450 K to give adsorbed chlorine and gaseous oxygen in a Cl:O atomic ratio of 1:4.
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