Electrochemical Anion Sensing Using Conductive Metal-Organic Framework Nanocrystals with Confined Pores.

Anion sensing technology is motivated by the widespread and critical roles played by anions in biological systems and the environment. Electrochemical approaches comprise a major portion of this field but so far have relied on redox-active molecules appended to electrodes that often lack the ability to produce mixtures of distinct signatures from mixtures of different anions. Here, nanocrystalline films of the conductive metal-organic framework (MOF) Cr(1,2,3-triazolate)2 are used to differentiate anions based on size, which consequently affect the reversible oxidation of the MOF. During framework oxidation, the intercalation of larger charge-balancing anions (e.g., ClO4-, PF6-, and OTf-) gives rise to redox potentials shifted anodically by hundreds of mV due to the additional work of solvent reorganization and anion desolvation. Smaller anions (e.g., BF4-) may enter partially solvated, while larger ansions (e.g., OTf-) intercalate with complete desolvation. As a proof-of-concept, we leverage this "nanoconfinement" approach to report an electrochemical ClO4- sensor in aqueous media that is recyclable, reusable, and sensitive to sub-100-nM concentrations. Taken together, these results exemplify an unusual combination of distinct external versus internal surface chemistry in MOF nanocrystals and the interfacial chemistry they enable as a novel supramolecular approach for redox voltammetric anion sensing.

Ligand-Mediated Hydrogenic Defects in Two-Dimensional Electrically Conductive Metal-Organic Frameworks.

Compared to dense analogues, high-surface-area metals offer several key advantages in electrocatalysis and energy storage. Of the porous manifolds, metal-organic frameworks (MOFs) boast the highest known surface area of any material class, and a subset of known frameworks also conduct electricity. The premier conductive scaffolds, Ni3(HITP)2 and Ni3(HIB)2, are both predicted to be metallic, but experiments have yet to measure bulk metallicity. In this paper, we explore the thermodynamics of hydrogen vacancies and interstitials and demonstrate that interstitial hydrogen is a plausible and prevalent defect in the conductive MOF family. The existence of this defect is predicted to render both Ni3(HITP)2 and Ni3(HIB)2 as bulk semiconductors, not metals, and emphasizes that hydrogenic defects play a critical role in determining the bulk properties of conductive MOFs.

Giant Redox Entropy in the Intercalation vs Surface Chemistry of Nanocrystal Frameworks with Confined Pores.

Redox intercalation involves coupled ion-electron motion within host materials, finding extensive application in energy storage, electrocatalysis, sensing, and optoelectronics. Monodisperse MOF nanocrystals, compared to their bulk phases, exhibit accelerated mass transport kinetics that promote redox intercalation inside nanoconfined pores. However, nanosizing MOFs significantly increases their external surface-to-volume ratios, making the intercalation redox chemistry into MOF nanocrystals difficult to understand due to the challenge of differentiating redox sites at the exterior of MOF particles from the internal nanoconfined pores. Here, we report that Fe(1,2,3-triazolate)2 possesses an intercalation-based redox process shifted ca. 1.2 V from redox at the particle surface. Such distinct chemical environments do not appear in idealized MOF crystal structures but become magnified in MOF nanoparticles. Quartz crystal microbalance and time-of-flight secondary ion mass spectrometry combined with electrochemical studies identify the existence of a distinct and highly reversible Fe2+/Fe3+ redox event occurring within the MOF interior. Systematic manipulation of experimental parameters (e.g., film thickness, electrolyte species, solvent, and reaction temperature) reveals that this feature arises from the nanoconfined (4.54 Å) pores gating the entry of charge-compensating anions. Due to the requirement for full desolvation and reorganization of electrolyte outside the MOF particle, the anion-coupled oxidation of internal Fe2+ sites involves a giant redox entropy change (i.e., 164 J K-1 mol-1). Taken together, this study establishes a microscopic picture of ion-intercalation redox chemistry in nanoconfined environments and demonstrates the synthetic possibility of tuning electrode potentials by over a volt, with profound implications for energy capture and storage technologies.

Identification of a metastable uranium metal-organic framework isomer through non-equilibrium synthesis.

Since the structure of supramolecular isomers determines their performance, rational synthesis of a specific isomer hinges on understanding the energetic relationships between isomeric possibilities. To this end, we have systematically interrogated a pair of uranium-based metal-organic framework topological isomers both synthetically and through density functional theory (DFT) energetic calculations. Although synthetic and energetic data initially appeared to mismatch, we assigned this phenomenon to the appearance of a metastable isomer, driven by levers defined by Le Châtelier's principle. Identifying the relationship between structure and energetics in this study reveals how non-equilibrium synthetic conditions can be used as a strategy to target metastable MOFs. Additionally, this study demonstrates how defined MOF design rules may enable access to products within the energetic phase space which are more complex than conventional binary (e.g., kinetic vs. thermodynamic) products.

Comparative study of crystallization process in metallic melts using ab initio molecular dynamics simulations.

The crystallization process of liquid metals is studied using ab initio molecular dynamics simulations. The evolution of short-range order during quenching in Pb and Zn liquids is compared with body-centered cubic (bcc) Nb and V, and hexagonal closed-packed (hcp) Mg. We found that the fraction and type of the short-range order depends on the system under consideration, in which the icosahedral symmetry seems to dominate in the body-centered cubic metals. Although the local atomic structures in stable liquids are similar, liquid hcp-like Zn, bcc-like Nb and V can be deeply supercooled far below its melting point before crystallization while the supercooled temperature range in liquid Pb is limited. Further investigations into the nucleation process reveal the process of polymorph selection. In the body-centered cubic systems, the polymorph selection occurs in the supercooled state before the nucleation is initiated, while in the closed-packed systems it starts at the time of onset of crystallization. Atoms with bcc-like lattices in all studied supercooled liquids are always detected before the polymorph selection. It is also found that the bond orientational ordering is strongly correlated with the crystallization process in supercooled Zn and Pb liquids.