A remarkable shape-catalytic effect of confinement on the rotational isomerization of small hydrocarbons

The Journal of Chemical Physics
Erik E SantisoKeith E Gubbins

Abstract

As part of an effort to understand the effect of confinement by porous carbons on chemical reactions, we have carried out density functional theory calculations on the rotational isomerization of three four-membered hydrocarbons: n-butane, 1-butene, and 1,3-butadiene. Our results show that the interactions with the carbon walls cause a dramatic change on the potential energy surface for pore sizes comparable to the molecular dimensions. The porous material enhances or hinders reactions depending on how similar is the shape of the transition state to the shape of the confining material. The structure of the stable states and their equilibrium distributions are also drastically modified by confinement. Our results are consistent with a doubly exponential behavior of the reaction rates as a function of pore size, illustrating how the shape of a catalytic support can dramatically change the efficiency of a catalyst.

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Citations

Oct 28, 2015·The Journal of Physical Chemistry. B·Takehiko TsukaharaTakehiko Kitamori
Jul 9, 2016·Journal of Chemical Theory and Computation·Pietro GiacintoMatteo Calvaresi
Dec 3, 2008·Chemical Communications : Chem Comm·Xiulian Pan, Xinhe Bao
Dec 15, 2017·Journal of Computational Chemistry·Roland TóbiásGyula Tasi
Dec 1, 2010·Physical Chemistry Chemical Physics : PCCP·Keith E GubbinsJeremy C Palmer
May 28, 2021·Scientific Reports·Pranay AsaiMilind Deo
Dec 15, 2017·The Journal of Physical Chemistry. B·Deepti SrivastavaKeith E Gubbins

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