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Enantiospecific Adsorption of (R)-3-Methylcyclohexanone on Naturally Chiral Surfaces Vicinal to Cu(110)

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Abstract

(R)-3-methylcyclohexanone (R-3MCHO) has been shown to adsorb enantiospecifically on naturally chiral Cu surfaces vicinal to the Cu(110) plane. Adsorption of R-3MCHO on seven Cu single crystal surfaces vicinal to (110) was studied using temperature programmed desorption. These surfaces include Cu(110), Cu(771), Cu(430), Cu(13,9,1)R&S and Cu(651)R&S. The Cu(13,9,1)R&S and Cu(651)R&S surfaces are naturally chiral surfaces with terrace-step-kink structures. Enantioselective adsorption of R-3MCHO takes place on the chiral kink sites of these surfaces. Three R-3MCHO desorption features were resolved in the TPD spectra on Cu(13,9,1)R&S and Cu(651)R&S surfaces. Based upon comparisons between these and other Cu single crystal surfaces, they were assigned to desorption of R-3MCHO from flat terrace, close-packed step and kink sites. The desorption of R-3MCHO from the row and trough structure of the Cu(110) surface resembled desorption from a step structure rather than from a flat Cu(111) terrace. R-3MCHO desorbs enantiospecifically from the Cu(13,9,1)R&S and Cu(651)R&S surfaces. The peaks associated with R-3MCHO desorbing from the R- and S-chiral kink sites on Cu(13,9,1)R&S differed in temperature by 2.4 ± 0.8 K. This corresponds to an enantiospecific difference in the desorption energies of 0.7 ± 0.2 kJ/mol, with a preference for R-3MCHO adsorption at the R-kinks. In contrast, R-3MCHO has a desorption energy from the S-kinks on the Cu(651)S surface that is 0.7 ± 0.2 kJ/mol higher than from the R-kinks on the Cu(651)R surface.

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Acknowledgment

The authors would like to acknowledge support from the US DOE through grant number DE-FG02-03ER15472.

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Authors and Affiliations

  1. Department of Chemical Engineering, Carnegie Mellon University, Pittsburgh, PA, 15213, USA

    Ye Huang & Andrew J. Gellman

  2. National Energy Technology Laboratory, U.S. Department of Energy, P.O. Box 10940, Pittsburgh, PA, 15236, USA

    Andrew J. Gellman

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  1. Ye Huang
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  2. Andrew J. Gellman
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Correspondence to Andrew J. Gellman.

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Huang, Y., Gellman, A.J. Enantiospecific Adsorption of (R)-3-Methylcyclohexanone on Naturally Chiral Surfaces Vicinal to Cu(110). Top Catal 54, 1403–1413 (2011). https://doi.org/10.1007/s11244-011-9756-0

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  • DOI: https://doi.org/10.1007/s11244-011-9756-0

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