Presence versus Proximity: The Role of Pendant Amines in the Catalytic Hydrolysis of a Nerve Agent Simulant

Timur Islamoglu; Manuel A. Ortuño; Emmanuel Proussaloglou; Ashlee J. Howarth; Nicolaas A. Vermeulen; Ahmet Atilgan; Abdullah M. Asiri; Christopher J. Cramer; Omar K. Farha

doi:10.1002/anie.201712645

Presence versus Proximity: The Role of Pendant Amines in the Catalytic Hydrolysis of a Nerve Agent Simulant

Timur Islamoglu, Manuel A. Ortuño, Emmanuel Proussaloglou, Ashlee J. Howarth, Nicolaas A. Vermeulen, Ahmet Atilgan, Abdullah M. Asiri, Christopher J. Cramer, Omar K. Farha

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127 Scopus citations

Abstract

Amino-functionalized zirconium-based metal-organic frameworks (MOFs) have shown unprecedented catalytic activity compared to non-functionalized analogues for hydrolysis of organophosphonate-based toxic chemicals. Importantly, the effect of the amino group on the catalytic activity is significantly higher in the case of UiO-66-NH₂, where the amino groups reside near the node, compared to UiO-67-m-NH₂, where they are directed away from the node. Herein, we show that the proximity of the amino group is crucial for fast catalytic activity towards hydrolysis of organophosphonate-based nerve agents. The generality of the observed amine-proximity-dictated catalytic activity has been tested on two different MOF systems which have different topology. DFT calculations reveal that amino groups on all the MOFs studied are not acting as Brønsted bases; instead they control the microsolvation environment at the Zr₆-node active site and therefore increase the overall catalytic rates.

Original language	English (US)
Pages (from-to)	1949-1953
Number of pages	5
Journal	Angewandte Chemie - International Edition
Volume	57
Issue number	7
DOIs	https://doi.org/10.1002/anie.201712645
State	Published - Feb 12 2018

Bibliographical note

Funding Information:
O.K.F. gratefully acknowledges support from the Defense Threat Reduction Agency (HDTRA1-18-1-0003) for the catalysis study and Army Research Office-STTR (W911SR-17-C-0007) for the linkers and the MOFs syntheses. C.J.C. acknowledge the US DOE, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences and Biosciences (Award DE-FG02-12ER16362) as well as the Minnesota Supercomputing Institute (MSI) at the University of Minnesota for providing resources that contributed to the theoretical modelling results reported within this paper. This work made use of the EPIC, Keck-II, and/or SPID facilities of Northwestern University≫s NUANCE Center, which has received support from the Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource (NSF ECCS-1542205); the MRSEC program (NSF DMR-1121262) at the Materials Research Center; the International Institute for Nanotechnology (IIN); the Keck Foundation; and the State of Illinois, through the IIN.

Publisher Copyright:
© 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Keywords

amino groups
heterogeneous catalysis
hydrolysis
metal–organic frameworks
nerve agents

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title = "Presence versus Proximity: The Role of Pendant Amines in the Catalytic Hydrolysis of a Nerve Agent Simulant",

abstract = "Amino-functionalized zirconium-based metal-organic frameworks (MOFs) have shown unprecedented catalytic activity compared to non-functionalized analogues for hydrolysis of organophosphonate-based toxic chemicals. Importantly, the effect of the amino group on the catalytic activity is significantly higher in the case of UiO-66-NH2, where the amino groups reside near the node, compared to UiO-67-m-NH2, where they are directed away from the node. Herein, we show that the proximity of the amino group is crucial for fast catalytic activity towards hydrolysis of organophosphonate-based nerve agents. The generality of the observed amine-proximity-dictated catalytic activity has been tested on two different MOF systems which have different topology. DFT calculations reveal that amino groups on all the MOFs studied are not acting as Br{\o}nsted bases; instead they control the microsolvation environment at the Zr6-node active site and therefore increase the overall catalytic rates.",

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note = "Funding Information: O.K.F. gratefully acknowledges support from the Defense Threat Reduction Agency (HDTRA1-18-1-0003) for the catalysis study and Army Research Office-STTR (W911SR-17-C-0007) for the linkers and the MOFs syntheses. C.J.C. acknowledge the US DOE, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences and Biosciences (Award DE-FG02-12ER16362) as well as the Minnesota Supercomputing Institute (MSI) at the University of Minnesota for providing resources that contributed to the theoretical modelling results reported within this paper. This work made use of the EPIC, Keck-II, and/or SPID facilities of Northwestern University≫s NUANCE Center, which has received support from the Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource (NSF ECCS-1542205); the MRSEC program (NSF DMR-1121262) at the Materials Research Center; the International Institute for Nanotechnology (IIN); the Keck Foundation; and the State of Illinois, through the IIN. Publisher Copyright: {\textcopyright} 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim",

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AU - Asiri, Abdullah M.

AU - Cramer, Christopher J.

AU - Farha, Omar K.

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Presence versus Proximity: The Role of Pendant Amines in the Catalytic Hydrolysis of a Nerve Agent Simulant

Abstract

Bibliographical note

Keywords

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NMGC: Nanoporous Materials Genome: Methods and Software to Optimize Gas Storage, Separations, and Catalysis (Phase 2)

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Presence versus Proximity: The Role of Pendant Amines in the Catalytic Hydrolysis of a Nerve Agent Simulant

Abstract

Bibliographical note

Keywords

Access

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Other files and links

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Projects

NMGC: Nanoporous Materials Genome: Methods and Software to Optimize Gas Storage, Separations, and Catalysis (Phase 2)

Cite this