Role of Metal-Organic Framework Topology on Thermodynamics of Polyoxometalate Encapsulation.
ACS applied materials & interfaces(2024)
摘要
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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