Hydrogen and Deuterium Exchange on Pt(111) and Its Poisoning by Carbon Monoxide Studied by Surface Sensitive High-Pressure Techniques

摘要

Catalytic hydrogen/deuterium exchange on a platinum (111) single crystal and its poisoning with carbon monoxide was studied using scanning tunneling microscopy (STM),X-ray photoelectron spectroscopy (XPS),sum frequency generation vibrational spectroscopy (SFG),and mass spectrometry under reaction conditions at pressures in the mTorr to atmospheric range.At 298 K and in the presence of 200 mTorr of hydrogen and 20 mTorr of deuterium the surface is catalytically active,producing HD with activation energy of approx 5.3 kcal/mol.Addition of 5 mTorr of CO stops the reaction completely.In situ STM images reveal an ordered surface structure of chemisorbed CO.At 353 K the addition of 5 mTorr of CO slows the reaction by 3 orders of magnitude,but HD production continues with an activation energy of 17.4 kcal/mol.Changes in coverage and adsorption site of CO were followed by XPS and SFG up to a temperature of 480 K.From these data,a CO dominated,mobile and catalytically active surface model is proposed.