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Steering CO(2) hydrogenation toward C–C coupling to hydrocarbons using porous organic polymer/metal interfaces

The conversion of CO(2) into fuels and chemicals is an attractive option for mitigating CO(2) emissions. Controlling the selectivity of this process is beneficial to produce desirable liquid fuels, but C–C coupling is a limiting step in the reaction that requires high pressures. Here, we propose a s...

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Autores principales: Zhou, Chengshuang, Asundi, Arun S., Goodman, Emmett D., Hong, Jiyun, Werghi, Baraa, Hoffman, Adam S., Nathan, Sindhu S., Bent, Stacey F., Bare, Simon R., Cargnello, Matteo
Formato: Online Artículo Texto
Lenguaje:English
Publicado: National Academy of Sciences 2022
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8851537/
https://www.ncbi.nlm.nih.gov/pubmed/35135880
http://dx.doi.org/10.1073/pnas.2114768119
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author Zhou, Chengshuang
Asundi, Arun S.
Goodman, Emmett D.
Hong, Jiyun
Werghi, Baraa
Hoffman, Adam S.
Nathan, Sindhu S.
Bent, Stacey F.
Bare, Simon R.
Cargnello, Matteo
author_facet Zhou, Chengshuang
Asundi, Arun S.
Goodman, Emmett D.
Hong, Jiyun
Werghi, Baraa
Hoffman, Adam S.
Nathan, Sindhu S.
Bent, Stacey F.
Bare, Simon R.
Cargnello, Matteo
author_sort Zhou, Chengshuang
collection PubMed
description The conversion of CO(2) into fuels and chemicals is an attractive option for mitigating CO(2) emissions. Controlling the selectivity of this process is beneficial to produce desirable liquid fuels, but C–C coupling is a limiting step in the reaction that requires high pressures. Here, we propose a strategy to favor C–C coupling on a supported Ru/TiO(2) catalyst by encapsulating it within the polymer layers of an imine-based porous organic polymer that controls its selectivity. Such polymer confinement modifies the CO(2) hydrogenation behavior of the Ru surface, significantly enhancing the C(2+) production turnover frequency by 10-fold. We demonstrate that the polymer layers affect the adsorption of reactants and intermediates while being stable under the demanding reaction conditions. Our findings highlight the promising opportunity of using polymer/metal interfaces for the rational engineering of active sites and as a general tool for controlling selective transformations in supported catalyst systems.
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spelling pubmed-88515372022-08-08 Steering CO(2) hydrogenation toward C–C coupling to hydrocarbons using porous organic polymer/metal interfaces Zhou, Chengshuang Asundi, Arun S. Goodman, Emmett D. Hong, Jiyun Werghi, Baraa Hoffman, Adam S. Nathan, Sindhu S. Bent, Stacey F. Bare, Simon R. Cargnello, Matteo Proc Natl Acad Sci U S A Physical Sciences The conversion of CO(2) into fuels and chemicals is an attractive option for mitigating CO(2) emissions. Controlling the selectivity of this process is beneficial to produce desirable liquid fuels, but C–C coupling is a limiting step in the reaction that requires high pressures. Here, we propose a strategy to favor C–C coupling on a supported Ru/TiO(2) catalyst by encapsulating it within the polymer layers of an imine-based porous organic polymer that controls its selectivity. Such polymer confinement modifies the CO(2) hydrogenation behavior of the Ru surface, significantly enhancing the C(2+) production turnover frequency by 10-fold. We demonstrate that the polymer layers affect the adsorption of reactants and intermediates while being stable under the demanding reaction conditions. Our findings highlight the promising opportunity of using polymer/metal interfaces for the rational engineering of active sites and as a general tool for controlling selective transformations in supported catalyst systems. National Academy of Sciences 2022-02-08 2022-02-15 /pmc/articles/PMC8851537/ /pubmed/35135880 http://dx.doi.org/10.1073/pnas.2114768119 Text en Copyright © 2022 the Author(s). Published by PNAS. https://creativecommons.org/licenses/by-nc-nd/4.0/This article is distributed under Creative Commons Attribution-NonCommercial-NoDerivatives License 4.0 (CC BY-NC-ND) (https://creativecommons.org/licenses/by-nc-nd/4.0/) .
spellingShingle Physical Sciences
Zhou, Chengshuang
Asundi, Arun S.
Goodman, Emmett D.
Hong, Jiyun
Werghi, Baraa
Hoffman, Adam S.
Nathan, Sindhu S.
Bent, Stacey F.
Bare, Simon R.
Cargnello, Matteo
Steering CO(2) hydrogenation toward C–C coupling to hydrocarbons using porous organic polymer/metal interfaces
title Steering CO(2) hydrogenation toward C–C coupling to hydrocarbons using porous organic polymer/metal interfaces
title_full Steering CO(2) hydrogenation toward C–C coupling to hydrocarbons using porous organic polymer/metal interfaces
title_fullStr Steering CO(2) hydrogenation toward C–C coupling to hydrocarbons using porous organic polymer/metal interfaces
title_full_unstemmed Steering CO(2) hydrogenation toward C–C coupling to hydrocarbons using porous organic polymer/metal interfaces
title_short Steering CO(2) hydrogenation toward C–C coupling to hydrocarbons using porous organic polymer/metal interfaces
title_sort steering co(2) hydrogenation toward c–c coupling to hydrocarbons using porous organic polymer/metal interfaces
topic Physical Sciences
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8851537/
https://www.ncbi.nlm.nih.gov/pubmed/35135880
http://dx.doi.org/10.1073/pnas.2114768119
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