271735 Autocatalytic Decomposition Mechanism of Aspartic Acid On Cu(110) Surfaces

Thursday, November 1, 2012: 2:30 PM
317 (Convention Center )
Bharat S. Mhatre, Department of Chemical Engineering, Carnegie Mellon University, Pittsburgh, PA and Andrew J. Gellman, Chemical Engineering, Carnegie Mellon University, Pittsburgh, PA

Surface explosions are surface reaction mechanisms wherein an autocatalytic increase in the reaction rate results in the reaction proceeding to completion over a very narrow temperature range during heating. While several substrate-adsorbate systems exhibiting decomposition via surface explosion mechanism have been identified, a detailed understanding of the mechanism remains unclear.  We have successfully identified aspartic acid as a suitable probe for studying surface explosion mechanism on Cu(110) surface. Because a wide range of isotopically labeled varieties of aspartic acid are commercially available, we have been able to conduct a detailed investigation of its autocatalytic reaction mechanism. Using specifically labeled aspartic acid molecules, we have identified the reaction products and identified the origins of atoms in the decomposing aspartic acid molecules. The explosive nature of the reaction mechanism has enabled us to study its kinetics using isothermal methods by heating the Cu(110) surface to a constant temperature and then monitoring the product desorption as a function of time. We observe a significant lag time during which nucleation of the reaction is occurring without observable desorption of products.  Once the reaction begins, it the proceeds to completion over a relatively short time period. Our preliminary studies on chiral Cu(643)R&S surfaces indicate that aspartic acid exhibits enantiospecific surface decomposition kinetics. The ultimate objective of this work is to be able to identify the mechanism and in particular, the steps in the mechanism which are responsible for the enantiospecificity.

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See more of this Session: Fundamentals of Surface Reactivity I
See more of this Group/Topical: Catalysis and Reaction Engineering Division