Hydrogen and deuterium exchange on Pt(111) and its poisoning by carbon monoxide studied by surface sensitive high-pressure techniques.

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 approximately 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.