Title

Water Deficient Environment Accelerates Proton Exchange: Acetone-Water Reaction Catalyzed by Calix 4 hydroquinone Nanotubes

Authors

Authors

M. Zakharov; A. E. Masunov;A. Dreuw

Abbreviated Journal Title

J. Phys. Chem. C

Keywords

ORGANIC NANOTUBES; ELECTRONIC-STRUCTURE; WAVE-FUNCTIONS; BASIS-SETS; GAS-PHASE; HYDROGEN; ENERGIES; ENOL; NMR; Chemistry, Physical; Nanoscience & Nanotechnology; Materials Science, ; Multidisciplinary

Abstract

Calix[4]hydroquinone nanotubes possess the unique property to catalyze proton exchange between water and acetone. Since concerted proton transfer mechanisms could be excluded previously, stepwise proton transfer via ionic intermediates created by predissociation of CHQ OH groups is studied using state-of-the-art quantum chemical methodology. In fact, the presence of charged species, protonated acetone or deprotonated hydroquinone, leads to a substantial decrease of the proton transfer energy barrier and to calculated reaction rates that provide an explanation for the experimentally observed proton exchange. Furthermore, our quantum chemical investigation demonstrates that the catalytic activity of CHQ aggregates is not based on a reduction of the energy barrier connected with proton transfer but on the desolvation of acetone and prevention of solvent water cluster formation.

Journal Title

Journal of Physical Chemistry C

Volume

113

Issue/Number

24

Publication Date

1-1-2009

Document Type

Article

Language

English

First Page

10395

Last Page

10401

WOS Identifier

WOS:000266930400016

ISSN

1932-7447

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