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Abstract Nanoparticles of metal‐organic frameworks (nanoMOFs) possess the unusual combination of both internal and external surfaces. While internal surfaces have been the focus of fundamental and applications‐based MOF studies, the chemistry of the external surfaces remains scarcely understood. Herein we report that specific ion interactions with nanoparticles of Cu(1,2,3‐triazolate)₂(Cu(TA)₂) resemble the Hofmeister behavior of proteins and the supramolecular chemistry of synthetic macromolecules. Inspired by these anion‐selective interactions, we tested the performance of Cu(TA)₂nanoparticles as chemical field effect transistor (ChemFET) anion sensors. Rather than size‐based selectivity, the detection limits of the devices exhibit a Hofmeister trend, with the greatest sensitivity towards anions perchlorate, iodide, and nitrate. These results highlight the importance of the pore‐based supramolecular interactions, rather than localized donor‐acceptor pairs, in designing MOF‐based technologies. 

Thermally regenerative electrochemical cycles and thermogalvanic cells harness redox entropy changes (ΔSrc) to interconvert heat and electricity with applications in heat harvesting and energy storage. Their efficiencies depend on ΔSrc because it relates directly to the Seebeck coefficient, yet few approaches exist for controlling the reaction entropy. Here, we demonstrate the design principle of using highly charged molecular species as electrolytes in thermogalvanic devices. As a proof-of-concept, the highly charged Wells-Dawson ion [P2W18O62]6– exhibits a large ΔSrc (−195 J mol–1 K–1) and a Seebeck coefficient comparable to state-of-the-art electrolytes (−1.7 mV K–1), demonstrating the potential of linking the rich chemistry of polyoxometalates to thermogalvanic technologies. 

Although metal–organic framework (MOF) photocatalysts have become ubiquitous, basic aspects of their photoredox mechanisms remain elusive. 

Ti IV -containing metal–organic frameworks are known to accumulate electrons in their conduction bands, accompanied by protons, when irradiated in the presence of alcohols. The archetypal system, MIL-125, was recently shown to reach a limit of 2e − per Ti 8 octomeric node. However, the origin of this limit and the broader applicability of this unique chemistry relies not only on the presence of Ti IV , but also access to inorganic inner-sphere Lewis basic anions in the MOF nodes. Here, we study the loading of protons and electrons in MIL-125, and assess the thermodynamic limit of doping these materials. We find that the limit is determined by the reduction potential of protons: in high charging regimes the MOF exceeds the H + /H 2 potential. Generally, we offer the design principle that inorganic anions in MOF nodes can host adatomic protons, which may stabilize meta-stable low valent transition metals. This approach highlights the unique chemistry afforded by MOFs built from inorganic clusters, and provides one avenue to developing novel catalytic scaffolds for hydrogen evolution and transfer hydrogenation.