Role of Metal-Organic Framework Topology on Thermodynamics of Polyoxometalate Encapsulation

Kira M. Fahy; Fanrui Sha; Susanne Reischauer; Seryeong Lee; Tzu Yi Tai; Omar K. Farha

doi:10.1021/acsami.4c05016

Role of Metal-Organic Framework Topology on Thermodynamics of Polyoxometalate Encapsulation

Kira M. Fahy, Fanrui Sha, Susanne Reischauer, Seryeong Lee, Tzu Yi Tai, Omar K. Farha^*

^*Corresponding author for this work

Chemistry

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

1 Scopus citations

Abstract

Polyoxometalates (POMs) are discrete anionic clusters whose rich redox properties, strong Bro̷nsted acidity, and high availability of active sites make them potent catalysts for oxidation reactions. Metal-organic frameworks (MOFs) have emerged as tunable, porous platforms to immobilize POMs, thus increasing their solution stability and catalytic activity. While POM@MOF composite materials have been widely used for a variety of applications, little is known about the thermodynamics of the encapsulation process. Here, we utilize an up-and-coming technique in the field of heterogeneous materials, isothermal titration calorimetry (ITC), to obtain full thermodynamic profiles (ΔH, ΔS, ΔG, and K_a) of POM binding. Six different 8-connected hexanuclear Zr-MOFs were investigated to determine the impact of MOF topology (csq, scu, and the) on POM encapsulation thermodynamics.

Original language	English (US)
Pages (from-to)	30296-30305
Number of pages	10
Journal	ACS Applied Materials and Interfaces
Volume	16
Issue number	23
DOIs	https://doi.org/10.1021/acsami.4c05016
State	Published - Jun 12 2024

Funding

O.K.F. gratefully acknowledges support from the Defense Threat Reduction Agency (HDTRA1-19-1-0007) and the Catalyst Design for Decarbonization Center, an Energy Frontier Research Center, which is funded by the US Department of Energy (DOE), Office of Science, Basic Energy Sciences (BES) DE-SC0023383. This work made use of the IMSERC X-RAY facility at Northwestern University, which has received support from the Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource (NSF ECCS-2025633), and Northwestern University. This work also made use of the EPIC facility of Northwestern University\u2019s NU Center, which has received support from the SHyNE Resource (NSF ECCS-2025633), the IIN, and Northwestern\u2019s MRSEC program (NSF DMR-1720139). F.S. gratefully acknowledges support from the Ryan Fellowship and the International Institute for Nanotechnology at Northwestern University. K.M.F. is supported by the National Science Foundation Graduate Research Fellowship (NSF GRFP) under Grant No. DGE-1842165. The authors thank Dr. Florencia Son and Dr. Timothy Goetjen for their contributions in helping synthesize materials and collect preliminary data.

Keywords

isothermal titration calorimetry
metal−organic framework
polyoxometalate

ASJC Scopus subject areas

General Materials Science

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10.1021/acsami.4c05016

Cite this

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title = "Role of Metal-Organic Framework Topology on Thermodynamics of Polyoxometalate Encapsulation",

abstract = "Polyoxometalates (POMs) are discrete anionic clusters whose rich redox properties, strong Bro̷nsted acidity, and high availability of active sites make them potent catalysts for oxidation reactions. Metal-organic frameworks (MOFs) have emerged as tunable, porous platforms to immobilize POMs, thus increasing their solution stability and catalytic activity. While POM@MOF composite materials have been widely used for a variety of applications, little is known about the thermodynamics of the encapsulation process. Here, we utilize an up-and-coming technique in the field of heterogeneous materials, isothermal titration calorimetry (ITC), to obtain full thermodynamic profiles (ΔH, ΔS, ΔG, and Ka) of POM binding. Six different 8-connected hexanuclear Zr-MOFs were investigated to determine the impact of MOF topology (csq, scu, and the) on POM encapsulation thermodynamics.",

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AU - Fahy, Kira M.

AU - Sha, Fanrui

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AU - Lee, Seryeong

AU - Tai, Tzu Yi

AU - Farha, Omar K.

PY - 2024/6/12

Y1 - 2024/6/12

N2 - Polyoxometalates (POMs) are discrete anionic clusters whose rich redox properties, strong Bro̷nsted acidity, and high availability of active sites make them potent catalysts for oxidation reactions. Metal-organic frameworks (MOFs) have emerged as tunable, porous platforms to immobilize POMs, thus increasing their solution stability and catalytic activity. While POM@MOF composite materials have been widely used for a variety of applications, little is known about the thermodynamics of the encapsulation process. Here, we utilize an up-and-coming technique in the field of heterogeneous materials, isothermal titration calorimetry (ITC), to obtain full thermodynamic profiles (ΔH, ΔS, ΔG, and Ka) of POM binding. Six different 8-connected hexanuclear Zr-MOFs were investigated to determine the impact of MOF topology (csq, scu, and the) on POM encapsulation thermodynamics.

AB - Polyoxometalates (POMs) are discrete anionic clusters whose rich redox properties, strong Bro̷nsted acidity, and high availability of active sites make them potent catalysts for oxidation reactions. Metal-organic frameworks (MOFs) have emerged as tunable, porous platforms to immobilize POMs, thus increasing their solution stability and catalytic activity. While POM@MOF composite materials have been widely used for a variety of applications, little is known about the thermodynamics of the encapsulation process. Here, we utilize an up-and-coming technique in the field of heterogeneous materials, isothermal titration calorimetry (ITC), to obtain full thermodynamic profiles (ΔH, ΔS, ΔG, and Ka) of POM binding. Six different 8-connected hexanuclear Zr-MOFs were investigated to determine the impact of MOF topology (csq, scu, and the) on POM encapsulation thermodynamics.

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Role of Metal-Organic Framework Topology on Thermodynamics of Polyoxometalate Encapsulation

Abstract

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Keywords

ASJC Scopus subject areas

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