We study the effects of a planar interface and confinement on a generic catalytically activated ring-closing polymerization reaction near an unstructured catalyst. For this, we employ a coarse-grained polymer model using grand-canonical molecular dynamics simulations with a Monte Carlo reaction scheme. Inspired by recent experiments in the group of M. Buchmeiser that demonstrated an increase in ring-closing selectivity under confinement, we show that both the interface effects, i.e., placing the catalyst near a planar wall, and the confinement effects, i.e., locating the catalyst within a pore, lead to an increase of selectivity. We furthermore demonstrate that curvature effects for cylindrical mesopores (2 nm < d < 12.3 nm) influence the distribution of the chain ends, leading to a further increase in selectivity. This leads us to speculate that specially corrugated surfaces might also help to enhance catalytically activated polymerization processes.
%0 Journal Article
%1 Tischler_2023
%A Tischler, Ingo
%A Schlaich, Alexander
%A Holm, Christian
%D 2023
%I American Chemical Society (ACS)
%J ACS Omega
%K EXC2075 PN3 PN3-3 selected
%N 1
%P 598–606
%R 10.1021/acsomega.3c06195
%T Disentanglement of Surface and Confinement Effects for Diene Metathesis in Mesoporous Confinement
%U http://dx.doi.org/10.1021/acsomega.3c06195
%V 9
%X We study the effects of a planar interface and confinement on a generic catalytically activated ring-closing polymerization reaction near an unstructured catalyst. For this, we employ a coarse-grained polymer model using grand-canonical molecular dynamics simulations with a Monte Carlo reaction scheme. Inspired by recent experiments in the group of M. Buchmeiser that demonstrated an increase in ring-closing selectivity under confinement, we show that both the interface effects, i.e., placing the catalyst near a planar wall, and the confinement effects, i.e., locating the catalyst within a pore, lead to an increase of selectivity. We furthermore demonstrate that curvature effects for cylindrical mesopores (2 nm < d < 12.3 nm) influence the distribution of the chain ends, leading to a further increase in selectivity. This leads us to speculate that specially corrugated surfaces might also help to enhance catalytically activated polymerization processes.
@article{Tischler_2023,
abstract = {We study the effects of a planar interface and confinement on a generic catalytically activated ring-closing polymerization reaction near an unstructured catalyst. For this, we employ a coarse-grained polymer model using grand-canonical molecular dynamics simulations with a Monte Carlo reaction scheme. Inspired by recent experiments in the group of M. Buchmeiser that demonstrated an increase in ring-closing selectivity under confinement, we show that both the interface effects, i.e., placing the catalyst near a planar wall, and the confinement effects, i.e., locating the catalyst within a pore, lead to an increase of selectivity. We furthermore demonstrate that curvature effects for cylindrical mesopores (2 nm < d < 12.3 nm) influence the distribution of the chain ends, leading to a further increase in selectivity. This leads us to speculate that specially corrugated surfaces might also help to enhance catalytically activated polymerization processes.},
added-at = {2024-06-18T14:47:29.000+0200},
author = {Tischler, Ingo and Schlaich, Alexander and Holm, Christian},
biburl = {https://puma.ub.uni-stuttgart.de/bibtex/2f965023517814d651514617573e08ce5/testusersimtech},
doi = {10.1021/acsomega.3c06195},
interhash = {2c9d833f89279fbcb2c472ff16efdfb8},
intrahash = {f965023517814d651514617573e08ce5},
issn = {2470-1343},
journal = {ACS Omega},
keywords = {EXC2075 PN3 PN3-3 selected},
month = {12},
number = 1,
pages = {598–606},
publisher = {American Chemical Society (ACS)},
timestamp = {2024-06-18T14:47:29.000+0200},
title = {Disentanglement of Surface and Confinement Effects for Diene Metathesis in Mesoporous Confinement},
url = {http://dx.doi.org/10.1021/acsomega.3c06195},
volume = 9,
year = 2023
}
