Selective Adsorption and Thermal Evolution of Bifunctional Carboxylic Acids: Competition of O—H Dissociation and Other Reaction Products in Acrylic Acid and Propanoic Acid on Si(100)2×1Click to copy article linkArticle link copied!
Abstract
The dissociative adsorption of acrylic acid on Si(100)2×1 at room temperature has been investigated by X-ray photoelectron spectroscopy (XPS) and temperature programmed desorption (TPD), as well as density-functional theory (DFT) calculations. Three C 1s features can be attributed to the carboxyl C of bidentate acrylate (at 286.8 eV) and unidentate acrylate (at 289.3 eV), both resulting from O—H dissociation upon adsorption, and to their corresponding ethenyl C atoms (at 285.0 eV). The formation of bidentate acrylate at a low exposure is followed by that of unidentate acrylate at a higher exposure, with approximately equal populations for both adstructures at the saturation exposure. DFT calculations confirm that the bidentate acrylate adstructure gives the most stable adsorption structure configuration. The combined temperature-dependent XPS and TPD studies provide strong evidence for the formation of CO, ethylene, acetylene, and propene, with 60% of the C moiety from the adsorption configurations converted to SiC with increasing annealing temperature to 1050 K. A companion study on propanoic acid on Si(100)2×1 shows similar formation of bidentate and unidentate propanoate adsorption configurations and thermal evolution to only CO and ethylene. In both acrylic acid and propanoic acid, the respective O—H dissociation products appear to be preferred over the other reaction products, such as [O, C] bidentate formation, C—OH dissociation, C═C cycloaddition, C═O cycloaddition, and ene formation. The unreacted backbone of the acrylate adsorption configuration provides a reactive site for further functionalization by other molecules.
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