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

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

doi:10.1021/acsami.4c05016

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

Journal Article · Sun Jun 02 00:00:00 EDT 2024 · ACS Applied Materials and Interfaces

DOI:https://doi.org/10.1021/acsami.4c05016· OSTI ID:2467583

^[1]; ^[2]; Reischauer, Susanne ^[2]; ^[2]; ^[2]; ^[2]

Northwestern University, Evanston, IL (United States); University of Chicago
Northwestern University, Evanston, IL (United States)

Polyoxometalates (POMs) are discrete anionic clusters whose rich redox properties, strong Brønsted acidity, and high availability of active sites poise them as potent catalysts for oxidation reactions. Here, 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, K_a) of POM binding. Six different 8-connected hexanuclear Zr-MOFs were investigated to determine the impact of MOF topology (csq, scu, the) on POM encapsulation thermodynamics.

View Accepted Manuscript (DOE)

Research Organization:: University of Chicago, IL (United States)

Sponsoring Organization:: National Science Foundation Graduate Research Fellowship (NSF GRFP); USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0023383

OSTI ID:: 2467583

Journal Information:: ACS Applied Materials and Interfaces, Journal Name: ACS Applied Materials and Interfaces Journal Issue: 23 Vol. 16; ISSN 1944-8244

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
encapsulation
granular materials
isothermal titration calorimetry
mathematical methods
metal organic frameworks
metal−organic framework
polyoxometalate
thermodynamics

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

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References (45)

Figures / Tables (6)

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