The Relationship Between Adsorption Structure and Surface Reactivity: Thiols and Alcohols to Rh Surfaces

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This grant is in the general field of analytical and surface chemistry and in the subfield of surface chemical and kinetic studies of molecular transformations at single crystal surfaces. Professor Cynthia Friend of Harvard University will study the adsorption kinetics of alcohol and thiol molecules at rhodium single crystal surfaces. The understanding of this chemistry will advance the study of poisoning on catalyst surfaces. The study of oxidation and sulfidation of surfaces from organometallic surface chemistry allows understanding of these surfaces for adhesion and corrosion protection. Thiolate and alkoxide intermediate adsorption structure and kinetics will be studied using synchrotron radiation, photoemission and vibrational spectroscopies, in concert with temperature programmed desorption. The effects of coverage induced changes in adsorbate structure and desorption kinetics will be followed. The importance of the oxygen and sulfur heteroatom in C-O (S) linkages, vis a vis the Rh-O (S) bond strength will be investigated. Kinetically important intermediates will be investigated. Taken together, these studies will impact broadly on active metal surface chemistry applied to complex organic molecular adsorbates.