A DFT Study of CO(2) Hydrogenation on Faujasite‐Supported Ir(4) Clusters: on the Role of Water for Selectivity Control

Reaction mechanisms for the catalytic hydrogenation of CO(2) by faujasite‐supported Ir(4) clusters were studied by periodic DFT calculations. The reaction can proceed through two alternative paths. The thermodynamically favoured path results in the reduction of CO(2) to CO, whereas the other, kineti...

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Autores principales: Szyja, Bartłomiej M., Smykowski, Daniel, Szczygieł, Jerzy, Hensen, Emiel J. M., Pidko, Evgeny A.
Formato: Online Artículo Texto
Lenguaje:English
Publicado: John Wiley and Sons Inc. 2016
Materias:
Full Papers
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC5094556/
https://www.ncbi.nlm.nih.gov/pubmed/27840663
http://dx.doi.org/10.1002/cctc.201600644
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author Szyja, Bartłomiej M.
Smykowski, Daniel
Szczygieł, Jerzy
Hensen, Emiel J. M.
Pidko, Evgeny A.
author_facet Szyja, Bartłomiej M.
Smykowski, Daniel
Szczygieł, Jerzy
Hensen, Emiel J. M.
Pidko, Evgeny A.
author_sort Szyja, Bartłomiej M.
collection PubMed
description Reaction mechanisms for the catalytic hydrogenation of CO(2) by faujasite‐supported Ir(4) clusters were studied by periodic DFT calculations. The reaction can proceed through two alternative paths. The thermodynamically favoured path results in the reduction of CO(2) to CO, whereas the other, kinetically preferred channel involves CO(2) hydrogenation to formic acid under water‐free conditions. Both paths are promoted by catalytic amounts of water confined inside the zeolite micropores with a stronger promotion effect for the reduction path. Co‐adsorbed water facilitates the cooperation between the zeolite Brønsted acid sites and Ir(4) cluster by opening low‐energy reaction channels for CO(2) conversion.
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spelling pubmed-50945562016-11-09 A DFT Study of CO(2) Hydrogenation on Faujasite‐Supported Ir(4) Clusters: on the Role of Water for Selectivity Control Szyja, Bartłomiej M. Smykowski, Daniel Szczygieł, Jerzy Hensen, Emiel J. M. Pidko, Evgeny A. ChemCatChem Full Papers Reaction mechanisms for the catalytic hydrogenation of CO(2) by faujasite‐supported Ir(4) clusters were studied by periodic DFT calculations. The reaction can proceed through two alternative paths. The thermodynamically favoured path results in the reduction of CO(2) to CO, whereas the other, kinetically preferred channel involves CO(2) hydrogenation to formic acid under water‐free conditions. Both paths are promoted by catalytic amounts of water confined inside the zeolite micropores with a stronger promotion effect for the reduction path. Co‐adsorbed water facilitates the cooperation between the zeolite Brønsted acid sites and Ir(4) cluster by opening low‐energy reaction channels for CO(2) conversion. John Wiley and Sons Inc. 2016-06-23 2016-08-08 /pmc/articles/PMC5094556/ /pubmed/27840663 http://dx.doi.org/10.1002/cctc.201600644 Text en © 2016 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA. This is an open access article under the terms of the Creative Commons Attribution (http://creativecommons.org/licenses/by/4.0/) License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited.
spellingShingle Full Papers
Szyja, Bartłomiej M.
Smykowski, Daniel
Szczygieł, Jerzy
Hensen, Emiel J. M.
Pidko, Evgeny A.
A DFT Study of CO(2) Hydrogenation on Faujasite‐Supported Ir(4) Clusters: on the Role of Water for Selectivity Control
title A DFT Study of CO(2) Hydrogenation on Faujasite‐Supported Ir(4) Clusters: on the Role of Water for Selectivity Control
title_full A DFT Study of CO(2) Hydrogenation on Faujasite‐Supported Ir(4) Clusters: on the Role of Water for Selectivity Control
title_fullStr A DFT Study of CO(2) Hydrogenation on Faujasite‐Supported Ir(4) Clusters: on the Role of Water for Selectivity Control
title_full_unstemmed A DFT Study of CO(2) Hydrogenation on Faujasite‐Supported Ir(4) Clusters: on the Role of Water for Selectivity Control
title_short A DFT Study of CO(2) Hydrogenation on Faujasite‐Supported Ir(4) Clusters: on the Role of Water for Selectivity Control
title_sort dft study of co(2) hydrogenation on faujasite‐supported ir(4) clusters: on the role of water for selectivity control
topic Full Papers
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC5094556/
https://www.ncbi.nlm.nih.gov/pubmed/27840663
http://dx.doi.org/10.1002/cctc.201600644
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