Abstract
The adsorption and decomposition of ethanol and deuterated analogues at Ni(100) surfaces were studied in the range 100 – 400 K using Fourier-transform infrared reflection-absorption spectroscopy (FT-IRAS) and thermodesorption spectroscopy (TDS). Ethanol was found to coexist as a chemisorbed and hydrogen bridge bonded species in the monolayer at 100 K, the O-H bond of chemisorbed ethanol oriented parallel to the surface. When heated to 140 K some ethanol desorbs, the remaining adsorbate layer completely converts to the chemisorbed state. At 160 K conversion to the ethoxy-species starts, as deduced from a frequency shift of a combined C-C stretching and COH bending mode of ethanol and intensity variations of methyl bending modes. Up to 260 K ethanol and ethoxy species coexist. Decomposition starts at 260 K, with the rate limiting step being the abstraction of hydrogen from the α-carbon atom. The decomposition products give rise to recombinative hydrogen and methane desorption peaks at 200 K and a molecular CO desorption peak at 420 K.
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