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Formation of HCO+ by protonation of carbon monoxide in zeolites

13 February 2023, Version 2
Working Paper
This content is a preprint and has not undergone peer review at the time of posting.

Abstract

We show both experimentally and theoretically that CO can be activated (protonated) by Bronsted acid sites to form the super-electrophilic HCO+ cation in H-zeolites such as mordenite. This mode of activation of carbon monoxide is novel for solid materials and has not been observed before. This reactivity stems from the confining environment of zeolitic micropores. HCO+ is a catalytically active super-electrophile showing catalytic reactivity in C-H and C-O bond activation, leading, for example, to methanol carbonylation to acetic acid.

Keywords

carbon monoxide protonation
zeolite
methanol and dimethyl ether carbonylation
carbon monoxide CO chemistry in zeolites

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Version History

Feb 13, 2023 Version 2

Version Notes

We have added extensive DFT theoretical calculations and experimental data, further corroborating and strengthening our conclusions.

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The content is available under CC BY NC ND 4.0 [opens in a new tab]

DOI

10.26434/chemrxiv-2021-lpb2g-v2
D O I: 10.26434/chemrxiv-2021-lpb2g-v2 [opens in a new tab]

Funding

The research described in paper is part of the Quickstarter Initiative at Pacific Northwest National Laboratory. It was conducted under the Laboratory Directed Research and Development Program at PNNL, a multiprogram national laboratory operated by Battelle for the U.S. Department of Energy (DOE) under Contract DE-AC05-76RL01830. The research described in this paper was performed in the Environmental Molecular Sciences Laboratory (EMSL), a national scientific user facility sponsored by the DOE's Office of Biological and Environmental Research. This work was supported by US Department of Energy, Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Biosciences, and Geosciences. HAA acknowledges the support by Bulgarian National Science Fund (project КП-06-Н59/5). GNV acknowledges the support of the project EXTREME, funded by the Bulgarian Ministry of Education and Science, D01-76/30.03.2021 through the programme “European Scientific Networks”.

Author’s competing interest statement

The author(s) have declared they have no conflict of interest with regard to this content

Ethics

The author(s) have declared ethics committee/IRB approval is not relevant to this content

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