H5PV2Mo10O40 Polyoxometalate Encapsulated in NU-1000 Metal-Organic Framework for Aerobic Oxidation of a Mustard Gas Simulant

Cassandra T. Buru; Megan C. Wasson; Omar K. Farha

doi:10.1021/acsanm.9b02176

H₅PV₂Mo₁₀O₄₀ Polyoxometalate Encapsulated in NU-1000 Metal-Organic Framework for Aerobic Oxidation of a Mustard Gas Simulant

Cassandra T. Buru, Megan C. Wasson, Omar K. Farha^*

^*Corresponding author for this work

Chemistry

Research output: Contribution to journal › Article › peer-review

85 Scopus citations

Abstract

The immobilization of H₅PV₂Mo₁₀O₄₀ polyoxometalates (POMs) in the in the mesoporous channel-type metal-organic framework (MOF), NU-1000, via simple impregnation method is reported here. Characterization of the composite PV₂Mo₁₀@NU-1000 activated by supercritical CO₂ revealed that the POMs occupy the mesopore. Upon heating as low as 40 °C in the absence of bulk solvent, the POMs migrate to the micropore. However, the presence of solvent, such as cyclohexane, impedes this transformation. The material was active for the aerobic oxidation of the mustard gas simulant, 2-chloroethyl ethyl sulfide (CEES), in cyclohexane using isobutyraldehyde a sacrificial reductant and O₂ as the oxidant. The activity of the POM allowed for efficient oxidation of CEES in the dark and in air. Immobilization of the POM in the MOF was found to improve the initial turnover frequency compared to the POM itself. Further, the POM catalyst was found to be unstable under the chosen reaction conditions and no activity was found upon washing and reusing the POM. As a composite PV₂Mo₁₀@NU-1000, the POMs retained their catalytic activity and allowed for recycling of the catalytic material.

Original language	English (US)
Pages (from-to)	658-664
Number of pages	7
Journal	ACS Applied Nano Materials
Volume	3
Issue number	1
DOIs	https://doi.org/10.1021/acsanm.9b02176
State	Published - Jan 24 2020

Funding

O.K.F. gratefully acknowledges support from HDTRA1-18-1-0003. Metal analysis was performed at the Northwestern University Quantitative Bioelement Imaging Center. This work made use of the EPIC facility 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-1720139) at the Materials Research Center; the International Institute for Nanotechnology (IIN); the Keck Foundation; and the State of Illinois, through the IIN. This work made use of the IMSERC at Northwestern University, which has received support from the NSF (CHE-1048773 and DMR-0521267); Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource (NSF ECCS-1542205); the State of Illinois and International Institute for Nanotechnology (IIN). M.C.W. is supported by the NSF Graduate Research Fellowship under grant DGE-1842165.

Keywords

aerobic oxidation
catalysis
chemical warfare agent detoxification
metal-organic frameworks
polyoxometalates

ASJC Scopus subject areas

General Materials Science

Access to Document

10.1021/acsanm.9b02176

Cite this

@article{e149ba84e43742d0af7f42cf304a84ee,

title = "H5PV2Mo10O40 Polyoxometalate Encapsulated in NU-1000 Metal-Organic Framework for Aerobic Oxidation of a Mustard Gas Simulant",

abstract = "The immobilization of H5PV2Mo10O40 polyoxometalates (POMs) in the in the mesoporous channel-type metal-organic framework (MOF), NU-1000, via simple impregnation method is reported here. Characterization of the composite PV2Mo10@NU-1000 activated by supercritical CO2 revealed that the POMs occupy the mesopore. Upon heating as low as 40 °C in the absence of bulk solvent, the POMs migrate to the micropore. However, the presence of solvent, such as cyclohexane, impedes this transformation. The material was active for the aerobic oxidation of the mustard gas simulant, 2-chloroethyl ethyl sulfide (CEES), in cyclohexane using isobutyraldehyde a sacrificial reductant and O2 as the oxidant. The activity of the POM allowed for efficient oxidation of CEES in the dark and in air. Immobilization of the POM in the MOF was found to improve the initial turnover frequency compared to the POM itself. Further, the POM catalyst was found to be unstable under the chosen reaction conditions and no activity was found upon washing and reusing the POM. As a composite PV2Mo10@NU-1000, the POMs retained their catalytic activity and allowed for recycling of the catalytic material.",

keywords = "aerobic oxidation, catalysis, chemical warfare agent detoxification, metal-organic frameworks, polyoxometalates",

author = "Buru, {Cassandra T.} and Wasson, {Megan C.} and Farha, {Omar K.}",

note = "Funding Information: O.K.F. gratefully acknowledges support from HDTRA1-18-1-0003. Metal analysis was performed at the Northwestern University Quantitative Bioelement Imaging Center. This work made use of the EPIC facility of Northwestern University{\textquoteright}s NUANCE Center, which has received support from the Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource (NSF ECCS-1542205); the MRSEC program (NSF DMR-1720139) at the Materials Research Center; the International Institute for Nanotechnology (IIN); the Keck Foundation; and the State of Illinois, through the IIN. This work made use of the IMSERC at Northwestern University, which has received support from the NSF (CHE-1048773 and DMR-0521267); Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource (NSF ECCS-1542205); the State of Illinois and International Institute for Nanotechnology (IIN). M.C.W. is supported by the NSF Graduate Research Fellowship under grant DGE-1842165. Publisher Copyright: Copyright {\textcopyright} 2019 American Chemical Society.",

year = "2020",

month = jan,

day = "24",

doi = "10.1021/acsanm.9b02176",

language = "English (US)",

volume = "3",

pages = "658--664",

journal = "ACS Applied Nano Materials",

issn = "2574-0970",

publisher = "American Chemical Society",

number = "1",

}

TY - JOUR

T1 - H5PV2Mo10O40 Polyoxometalate Encapsulated in NU-1000 Metal-Organic Framework for Aerobic Oxidation of a Mustard Gas Simulant

AU - Buru, Cassandra T.

AU - Wasson, Megan C.

AU - Farha, Omar K.

N1 - Funding Information: O.K.F. gratefully acknowledges support from HDTRA1-18-1-0003. Metal analysis was performed at the Northwestern University Quantitative Bioelement Imaging Center. This work made use of the EPIC facility 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-1720139) at the Materials Research Center; the International Institute for Nanotechnology (IIN); the Keck Foundation; and the State of Illinois, through the IIN. This work made use of the IMSERC at Northwestern University, which has received support from the NSF (CHE-1048773 and DMR-0521267); Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource (NSF ECCS-1542205); the State of Illinois and International Institute for Nanotechnology (IIN). M.C.W. is supported by the NSF Graduate Research Fellowship under grant DGE-1842165. Publisher Copyright: Copyright © 2019 American Chemical Society.

PY - 2020/1/24

Y1 - 2020/1/24

N2 - The immobilization of H5PV2Mo10O40 polyoxometalates (POMs) in the in the mesoporous channel-type metal-organic framework (MOF), NU-1000, via simple impregnation method is reported here. Characterization of the composite PV2Mo10@NU-1000 activated by supercritical CO2 revealed that the POMs occupy the mesopore. Upon heating as low as 40 °C in the absence of bulk solvent, the POMs migrate to the micropore. However, the presence of solvent, such as cyclohexane, impedes this transformation. The material was active for the aerobic oxidation of the mustard gas simulant, 2-chloroethyl ethyl sulfide (CEES), in cyclohexane using isobutyraldehyde a sacrificial reductant and O2 as the oxidant. The activity of the POM allowed for efficient oxidation of CEES in the dark and in air. Immobilization of the POM in the MOF was found to improve the initial turnover frequency compared to the POM itself. Further, the POM catalyst was found to be unstable under the chosen reaction conditions and no activity was found upon washing and reusing the POM. As a composite PV2Mo10@NU-1000, the POMs retained their catalytic activity and allowed for recycling of the catalytic material.

AB - The immobilization of H5PV2Mo10O40 polyoxometalates (POMs) in the in the mesoporous channel-type metal-organic framework (MOF), NU-1000, via simple impregnation method is reported here. Characterization of the composite PV2Mo10@NU-1000 activated by supercritical CO2 revealed that the POMs occupy the mesopore. Upon heating as low as 40 °C in the absence of bulk solvent, the POMs migrate to the micropore. However, the presence of solvent, such as cyclohexane, impedes this transformation. The material was active for the aerobic oxidation of the mustard gas simulant, 2-chloroethyl ethyl sulfide (CEES), in cyclohexane using isobutyraldehyde a sacrificial reductant and O2 as the oxidant. The activity of the POM allowed for efficient oxidation of CEES in the dark and in air. Immobilization of the POM in the MOF was found to improve the initial turnover frequency compared to the POM itself. Further, the POM catalyst was found to be unstable under the chosen reaction conditions and no activity was found upon washing and reusing the POM. As a composite PV2Mo10@NU-1000, the POMs retained their catalytic activity and allowed for recycling of the catalytic material.

KW - aerobic oxidation

KW - catalysis

KW - chemical warfare agent detoxification

KW - metal-organic frameworks

KW - polyoxometalates

UR - http://www.scopus.com/inward/record.url?scp=85077430050&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=85077430050&partnerID=8YFLogxK

U2 - 10.1021/acsanm.9b02176

DO - 10.1021/acsanm.9b02176

M3 - Article

AN - SCOPUS:85077430050

SN - 2574-0970

VL - 3

SP - 658

EP - 664

JO - ACS Applied Nano Materials

JF - ACS Applied Nano Materials

IS - 1

ER -