Integrated CO2 Capture and Conversion by a Robust Cu(I)-Based Metal-Organic Framework.

Metal-organic frameworks (MOFs) have shown promise in both capturing CO2 under flue gas conditions and converting it into valuable chemicals. However, the development of a single MOF capable of capturing and selectively converting CO2 has remained elusive due to a lack of a harmonious combination of selectivity, water stability, and reactivity. For example, Cu(I)-based MOFs are particularly effective for CO2 conversion, but they do not typically exhibit selective CO2 adsorption and often suffer from instability in the presence of air and moisture. Developing a Cu(I) MOF that is stable under flue gas conditions while also capturing CO2 from this mixture would likely afford a material capable of selectively capturing and converting CO2 in an integrated pathway, which would represent a significant advancement in this field. In this study, we introduce NU-2100, an ultramicroporous Cu(I) MOF, which exhibits both selectivity for CO2 adsorption and great stability even in the presence of moisture and air. Comprehensive evaluations involving exposure to air, oxygen, water, and varying temperatures reveal that NU-2100 demonstrates superior stability compared to other known Cu(I) MOFs. Utilizing adsorption isotherms and thermogravimetric analysis coupled with gas chromatography-mass spectrometry (TGA-GCMS), we establish the high selectivity of NU-2100 for CO2 over common flue gas components, including water, nitrogen, and oxygen. Additionally, under mild reaction conditions (50 °C and H2:CO2 = 3:1), NU-2100 exhibits CO2 capture and catalytic conversion to formic acid with 100% selectivity. This study marks an important step toward the design of next-generation MOFs capable of integrated carbon capture and utilization (iCCU) under industrial conditions.

Chiral Reticular Chemistry: A Tailored Approach Crafting Highly Porous and Hydrolytically Robust Metal-Organic Frameworks for Intelligent Humidity Control.

Control of humidity within confined spaces is critical for maintaining air quality and human well-being, with implications for environments ranging from international space stations and pharmacies to granaries and cultural relic preservation sites. However, existing techniques rely on energy-intensive electrically driven equipment or complex temperature and humidity control (THC) systems, resulting in imprecision and inconvenience. The development of innovative techniques and materials capable of simultaneously meeting the stringent requirements of practical applications holds the key to creating intelligent and energy-efficient humidity control devices. In this study, we introduce chiral reticular chemistry as a tailored synthetic approach, targeting a highly porous hea topological framework characterized by intrinsic interpenetrating pore architecture. This groundbreaking design successfully circumvents the traditional compromise between the pore volume and hydrolytic stability. Our metal-organic framework (MOF) exhibits an extraordinary working capacity, setting a new record at 1.35 g g-1 within the relative humidity (RH) range of 40-60%, without exhibiting hysteresis. Consequently, it emerges as a state-of-the-art candidate for intelligent humidity regulation within confined spaces. Utilizing single-crystal X-ray measurements and molecular simulations, we unequivocally elucidate the mechanism of water clustering and pore filling, underscoring the pivotal role of the linker functionality in governing the water seeding process. Our findings represent a significant advancement in the field, paving the way for the development of highly efficient humidity control technologies and offering promising solutions for diverse real-world scenarios.

Programmable Water Sorption through Linker Installation into a Zirconium Metal-Organic Framework.

Hydrolytically stable materials exhibiting a wide range of programmable water sorption behaviors are crucial for on-demand water sorption systems. While notable advancements in employing metal-organic frameworks (MOFs) as promising water adsorbents have been made, developing a robust yet easily tailorable MOF scaffold for specific operational conditions remains a challenge. To address this demand, we employed a topology-guided linker installation strategy using NU-600, which is a zirconium-based MOF (Zr-MOF) that contains three vacant crystallographically defined coordination sites. Through a judicious selection of three N-heterocyclic auxiliary linkers of specific lengths, we installed them into designated sites, giving rise to six new MOFs bearing different combinations of linkers in predetermined positions. The resulting MOFs, denoted as NU-606 to NU-611, demonstrate enhanced structural stability against capillary force-driven channel collapse during water desorption due to the increased connectivity of the Zr6 clusters in the resulting MOFs. Furthermore, incorporating these auxiliary linkers with various hydrophilic N sites enables the systematic modulation of the pore-filling pressure from about 55% relative humidity (RH) for the parent NU-600 down to below 40% RH. This topology-driven linker installation strategy offers precise control of water sorption properties for MOFs, highlighting a facile route to design MOF adsorbents for use in water sorption applications.

Precise Modulation of CO2 Sorption in Ti8Ce2-Oxo Clusters: Elucidating Lewis Acidity of the Ce Metal Sites and Structural Flexibility.

Investigating the structure-property correlation in porous materials is a fundamental and consistent focus in various scientific domains, especially within sorption research. Metal oxide clusters with capping ligands, characterized by intrinsic cavities formed through specific solid-state packing, demonstrate significant potential as versatile platforms for sorption investigations due to their precisely tunable atomic structures and inherent long-range order. This study presents a series of Ti8Ce2-oxo clusters with subtle variations in coordinated linkers and explores their sorption behavior. Notably, Ti8Ce2-BA (BA denotes benzoic acid) manifests a distinctive two-step profile during the CO2 adsorption, accompanied by a hysteresis loop. This observation marks a new instance within the metal oxide cluster field. Of intrigue, the presence of unsaturated Ce(IV) sites was found to be correlated with the stepped sorption property. Moreover, the introduction of an electrophilic fluorine atom, positioned ortho or para to the benzoic acid, facilitated precise control over gate pressure and stepped sorption quantities. Advanced in situ techniques systematically unraveled the underlying mechanism behind this unique sorption behavior. The findings elucidate that robust Lewis base-acid interactions are established between the CO2 molecules and Ce ions, consequently altering the conformation of coordinated linkers. Conversely, the F atoms primarily contribute to gate pressure variation by influencing the Lewis acidity of the Ce sites. This research advances the understanding in fabricating metal-oxo clusters with structural flexibility and provides profound insights into their host-guest interaction motifs. These insights hold substantial promise across diverse fields and offer valuable guidance for future adsorbent designs grounded in fundamental theories of structure-property relationships.

Tailoring Hydrophobicity and Pore Environment in Physisorbents for Improved Carbon Dioxide Capture under High Humidity.

CALF-20, a Zn-triazolate-based metal-organic framework (MOF), is one of the most promising adsorbent materials for CO2 capture. However, competitive adsorption of water severely limits its performance when the relative humidity (RH) exceeds 40%, limiting the potential implementation of CALF-20 in practical settings where CO2 is saturated with moisture, such as postcombustion flue gas. In this work, three newly designed MOFs related to CALF-20, denoted as NU-220, CALF-20M-w, and CALF-20M-e that feature hydrophobic methyltriazolate linkers, are presented. Inclusion of methyl groups in the linker is proposed as a strategy to improve the uptake of CO2 in the presence of water. Notably, both CALF-20M-w and CALF-20M-e retain over 20% of their initial CO2 capture efficiency at 70% RH─a threshold at which CALF-20 shows negligible CO2 uptake. Grand canonical Monte Carlo simulations reveal that the methyl group hinders water network formation in the pores of CALF-20M-w and CALF-20M-e and enhances their CO2 selectivity over N2 in the presence of a high moisture content. Moreover, calculated radial distribution functions indicate that introducing the methyl group into the triazolate linker increases the distance between water molecules and Zn coordination bonds, offering insights into the origin of the enhanced moisture stability observed for CALF-20M-w and CALF-20M-e relative to CALF-20. Overall, this straightforward design strategy has afforded more robust sorbents that can potentially meet the challenge of effectively capturing CO2 in practical industrial applications.

Metal-Organic Frameworks with a Bioinspired Porous Polymer Coating for Sieving Separation.

Polymer/metal-organic framework (MOF) composites have been widely studied for their favorable combination of polymer flexibility and MOF crystallinity. While traditional polymer-coated MOFs maximize the polymer properties at the surface, the dramatic loss of MOF porosity due to blockage by the nonporous polymeric coating remains a problem. Herein, we introduce intrinsically microporous synthetic allomelanin (AM) as a porous coating on the zirconium-based MOF (Zr-MOF) UiO-66 via an in situ surface-constrained oxidative polymerization of the AM precursor, 1,8-dihydroxynaphthalene (1,8-DHN). Transmission electron microscopy images verify the formation of well-defined nanoparticles with a core-shell morphology (AM@UiO-66), and nitrogen sorption isotherms indicate the porosity of the UiO-66 core remains constant and is not disturbed by the AM coating. Notably, such a strategy could be adapted to MOFs with larger pores, such as MOF-808 by generating porous AM polymer coatings from bulkier DHN oligomers, highlighting the versatility of this method. Finally, we showed that by tuning the AM coating thickness on UiO-66, the hierarchically porous structures of these AM@UiO-66 composites engender excellent hexane isomer separation selectivity and storage capacity.

Robust Carborane-Based Metal-Organic Frameworks for Hexane Separation.

Hexane isomers play a vital role as feedstocks and fuel additives in the petrochemical industry. However, their similar physical and chemical properties lead to significant challenges in the separation process. Traditional thermal separation techniques are energy-intensive and lead to significant carbon footprint penalties. As such, there is a growing demand for the development of less energy-intensive nonthermal separation methods. Adsorption-based separation methods, such as using solid sorbents or membranes, have emerged as promising alternatives to distillation. Here, we report the successful synthesis of two novel metal-organic frameworks (MOFs), NU-2004 and NU-2005, by incorporating a carborane-based three-dimensional (3D) linker and using aluminum and vanadium nodes, respectively. These MOFs exhibit exceptional thermal stability and structural rigidity compared to other MIL-53 analogues, which is further corroborated using synchrotron studies. Furthermore, the inclusion of the quasi-spherical 3D linker in NU-2004 demonstrates significant advancements in the separation of hexane isomers compared to other MIL MOFs containing two-dimensional (2D) and aliphatic 3D linkers.

Programmed Polarizability Engineering in a Cyclen-Based Cubic Zr(IV) Metal-Organic Framework to Boost Xe/Kr Separation.

Efficient separation of xenon (Xe) and krypton (Kr) mixtures through vacuum swing adsorption (VSA) is considered the most attractive route to reduce energy consumption, but discriminating between these two gases is difficult due to their similar properties. In this work, we report a cubic zirconium-based MOF (Zr-MOF) platform, denoted as NU-1107, capable of achieving selective separation of Xe/Kr by post-synthetically engineering framework polarizability in a programmable manner. Specifically, the tetratopic linkers in NU-1107 feature tetradentate cyclen cores that are capable of chelating a variety of transition-metal ions, affording a sequence of metal-docked cationic isostructural Zr-MOFs. NU-1107-Ag(I), which features the strongest framework polarizability among this series, achieves the best performance for a 20:80 v/v Xe/Kr mixture at 298 K and 1.0 bar with an ideal adsorbed solution theory (IAST) predicted selectivity of 13.4, placing it among the highest performing MOF materials reported to date. Notably, the Xe/Kr separation performance for NU-1107-Ag(I) is significantly better than that of the isoreticular, porphyrin-based MOF-525-Ag(II), highlighting how the cyclen core can generate relatively stronger framework polarizability through the formation of low-valent Ag(I) species and polarizable counteranions. Density functional theory (DFT) calculations corroborate these experimental results and suggest strong interactions between Xe and exposed Ag(I) sites in NU-1107-Ag(I). Finally, we validated this framework polarizability regulation approach by demonstrating the effectiveness of NU-1107-Ag(I) toward C3H6/C3H8 separation, indicating that this generalizable strategy can facilitate the bespoke synthesis of polarized porous materials for targeted separations.

Structure-Activity Relationship Insights for Organophosphonate Hydrolysis at Ti(IV) Active Sites in Metal-Organic Frameworks.

Organophosphorus nerve agents are among the most toxic chemicals known and remain threats to humans due to their continued use despite international bans. Metal-organic frameworks (MOFs) have emerged as a class of heterogeneous catalysts with tunable structures that are capable of rapidly detoxifying these chemicals via hydrolysis at Lewis acidic active sites on the metal nodes. To date, the majority of studies in this field have focused on zirconium-based MOFs (Zr-MOFs) that contain hexanuclear Zr(IV) clusters, despite the large toolbox of Lewis acidic transition metal ions that are available to construct MOFs with similar catalytic properties. In particular, very few reports have disclosed the use of a Ti-based MOF (Ti-MOF) as a catalyst for this transformation even though Ti(IV) is a stronger Lewis acid than Zr(IV). In this work, we explored five Ti-MOFs (Ti-MFU-4l, NU-1012-NDC, MIL-125, Ti-MIL-101, MIL-177(LT), and MIL-177(HT)) that each contains Ti(IV) ions in unique coordination environments, including monometallic, bimetallic, octanuclear, triangular clusters, and extended chains, as catalysts to explore how both different node structures and different linkers (e.g., azolate and carboxylate) influence the binding and subsequent hydrolysis of an organophosphorus nerve agent simulant at Ti(IV)-based active sites in basic aqueous solutions. Experimental and theoretical studies confirm that Ti-MFU-4l, which contains monometallic Ti(IV)-OH species, exhibits the best catalytic performance among this series with a half-life of roughly 2 min. This places Ti-MFU-4l as one of the best nerve agent hydrolysis catalysts of any MOF reported to date.

Air-Stable Cu(I) Metal-Organic Framework for Hydrogen Storage.

Metal-organic frameworks (MOFs) that contain open metal sites have the potential for storing hydrogen (H2) at ambient temperatures. In particular, Cu(I)-based MOFs demonstrate very high isosteric heats of adsorption for hydrogen relative to other reported MOFs with open metal sites. However, most of these Cu(I)-based MOFs are not stable in ambient conditions since the Cu(I) species display sensitivity toward moisture and can rapidly oxidize in air. As a result, researchers have focused on the synthesis of new air-stable Cu(I)-based materials for H2 storage. Here, we have developed a de novo synthetic strategy to generate a robust Cu(I)-based MOF, denoted as NU-2100, using a mixture of Cu/Zn precursors in which zinc acts as a catalyst to transform an intermediate MOF into NU-2100 without getting incorporated into the final MOF structure. NU-2100 is air-stable and displays one of the initial highest isosteric heats of adsorption (32 kJ/mol) with good hydrogen storage capability under ambient conditions (10.4 g/L, 233 K/100 bar to 296 K/5 bar). We further elucidated the H2 storage performance of NU-2100 using a combination of spectroscopic analysis and computational modeling studies. Overall, this new synthetic route may enable the design of additional stable Cu(I)-MOFs for next-generation hydrogen storage adsorbents at ambient temperatures.

A General Strategy for the Synthesis of Hierarchically Ordered Metal-Organic Frameworks with Tunable Macro-, Meso-, and Micro-Pores.

Hierarchically ordered porous materials with tailored and inter-connected macro-, meso-, and micro-pores would facilitate the heterogeneous adsorption and catalysis processes for a wide range of applications but remain a challenge for synthetic chemists. Here, a general and efficient strategy for the synthesis of inverse opal metal-organic frameworks (IO MOFs) with a tunable size of macro-, meso-, and micro-pores is reported. The strategy is based on the step-wise template formation, precursor infiltration, solvo-thermal reaction, and chemical etching. As a proof of the general applicability of this strategy, a series of inverse opal zirconium-based MOFs with intrinsic micro- and/or meso-pores, including UiO-66, MOF-808, NU-1200, NU-1000 and PCN-777, and tunable macropores (1 µm, 2 µm, 3 µm, 5 µm, and 10 µm), have been prepared with outstanding yields. These IO MOFs demonstrate significantly enhanced absorption rates and faster initial hydrolysis rates for organophosphorus (OPs) aggregates compared to those of the pristine MOFs. This work paves the way for the further development of hierarchically ordered MOFs for advanced applications.

Reticular Chemistry for Highly Porous Metal-Organic Frameworks: The Chemistry and Applications.

Current global crises related to clean energy and the environment entail the development of materials that are capable of addressing these challenges. Metal-organic frameworks (MOFs), a class of functional materials assembled from metal-containing nodes and organic ligands via coordination bonds, have been successfully developed for various applications, including catalysis, toxic chemical removal, and gas storage and separation, as a result of their highly tailorable nature and precisely engineered pore structures. In particular, the exceptionally high surface areas and porosities of MOFs are two of their most attractive characteristics and place them among the best porous materials for the storage of clean energy gases, such as hydrogen and methane. Reticular chemistry stands out as a prominent approach to the design of MOFs as this strategy allows for the rational top-down design of frameworks guided by topological nets to afford extended framework structures with precise architectural arrangements at the molecular level. Bridging the gap between reticular chemistry design strategies and highly porous MOFs can facilitate the development of next-generation high-performance materials through state-of-the-art chemical design.In this Account, we summarize our group's efforts over the past few years toward the synthesis and applications of highly porous MOFs inspired by reticular chemistry. First, we describe how we leveraged reticular chemistry to synthesize NU-1500, which is based on the 6-connected edge-transitive acs net, from the assembly of triptycene-based ligands and high-valent metal trimers. This delicate design is amenable to isoreticular expansion, and including an additional phenyl group in the rigid triptycene-based ligand of NU-1500 yields NU-1501. Importantly, NU-1501-Al exhibits both a high gravimetric Brunauer-Emmett-Teller (BET) area of 7310 m2 g-1, which is the current record after satisfying the four BET consistency criteria, and a volumetric BET area of 2060 m2 cm-3. The high porosity and surface area place NU-1501 among the most promising adsorbents for the storage of methane and hydrogen. Second, we illustrate the rational synthesis of highly porous and stable Zr-MOFs based on edge-transitive nets: (1) the successful isoreticular expansions of NU-1000 (a 4,8-connected csq net) form hierarchical mesoporous MOFs with pore sizes of up to 6.7 nm; (2) the assembly of Zr6 clusters and tetracarboxylates yields the NU-1100 series (4,12-connected ftw net) with BET areas of 4300-6500 m2 g-1; and (3) the use of hexacarboxylates in combination with Zr6 clusters results in the formation of the NU-1600 series (a 6,12-connected alb net) with BET areas of 2000-4500 m2 g-1. Third, we leveraged a reticular exploration strategy to access mesoporous uranium-based MOFs, NU-1300 (a 3,4-connected tbo net, 2100 m2 g-1) and NU-1301 (a 3-connected nun net, 4750 m2 g-1). In particular, we investigated the structurally complex NU-1301, which formed serendipitously from the combination of uranyl clusters and triangular carboxylates to afford a structure with the largest unit cell among all reported MOFs.Finally, we provide an overview of potential applications of these highly porous MOFs, including water capture, catalysis, methane storage, hydrogen storage, and the separation of organic dyes and biological macromolecules. We hope that this Account may serve as a blueprint and stimulate researchers to develop the next generation of highly porous materials for energy- and environment-related applications and beyond.

Evidence of a Uranium-Paddlewheel Node in a Catecholate-Based Metal-Organic Framework.

The interactions between uranium and non-innocent organic species are an essential component of fundamental uranium redox chemistry. However, they have seldom been explored in the context of multidimensional, porous materials. Uranium-based metal-organic frameworks (MOFs) offer a new angle to study these interactions, as these self-assembled species stabilize uranium species through immobilization by organic linkers within a crystalline framework, while potentially providing a method for adjusting metal oxidation state through coordination of non-innocent linkers. We report the synthesis of the MOF NU-1700, assembled from U4+ -paddlewheel nodes and catecholate-based linkers. We propose this highly unusual structure, which contains two U4+ ions in a paddlewheel built from four linkers-a first among uranium materials-as a result of extensive characterization via powder X-ray diffraction (PXRD), sorption, transmission electron microscopy (TEM), and thermogravimetric analysis (TGA), in addition to density functional theory (DFT) calculations.

Design Rules of Hydrogen-Bonded Organic Frameworks with High Chemical and Thermal Stabilities.

Hydrogen-bonded organic frameworks (HOFs), self-assembled from strategically pre-designed molecular tectons with complementary hydrogen-bonding patterns, are rapidly evolving into a novel and important class of porous materials. In addition to their common features shared with other functionalized porous materials constructed from modular building blocks, the intrinsically flexible and reversible H-bonding connections endow HOFs with straightforward purification procedures, high crystallinity, solution processability, and recyclability. These unique advantages of HOFs have attracted considerable attention across a broad range of fields, including gas adsorption and separation, catalysis, chemical sensing, and electrical and optical materials. However, the relatively weak H-bonding interactions within HOFs can potentially limit their stability and potential use in further applications. To that end, this Perspective highlights recent advances in the development of chemically and thermally robust HOF materials and systematically discusses relevant design rules and synthesis strategies to access highly stable HOFs.

Leveraging Chiral Zr(IV)-Based Metal-Organic Frameworks To Elucidate Catalytically Active Rh Species in Asymmetric Hydrogenation Reactions.

One of the most widely employed strategies to produce chiral molecules involves the asymmetric hydrogenation of functionalized olefins using rhodium catalysts. Despite their excellent performance, the exact identity of the active Rh species is still ambiguous as each site may plausibly feature one or two phosphorus ligands. In this work, we used a sequential postsynthetic modification approach to successfully incorporate single-site Rh species into a zirconium-based metal-organic framework comprised of chiral spinol-based ligands. These Rh species feature one phosphorus ligand per Rh, which contrasts with the molecular analogue that contains two phosphorus ligands per Rh site. Following extensive characterization of the Rh-monophosphorus material using techniques including solid-state NMR and extended X-ray absorption fine-structure (EXAFS) spectroscopy, we studied their catalytic performance in the asymmetric hydrogenations of enamides and α-dehydroamino acid esters and observed excellent yields and enantioselectivities (up to 99.9% ee). Notably, the Rh-monophosphorus catalyst is 5 times more active than the homogeneous Rh-biphosphorus control, which we attributed to the higher activity of the single-site Rh-monophosphorus species and the confined MOF cavities that can enrich reactants. In addition, we observed a unique topology-dependent behavior in which linker expansion leads to the formation of a novel Zr-MOF with a distinct 4,8-connected net that cannot be phosphorylated, presumably due to intense tensile strain and steric repulsion present within this framework. Finally, we demonstrate the utility of this single-site Rh-monophosphorus catalyst in the gram-scale synthesis of (R)-cinacalcet hydrochloride, a first-in-class drug in the therapy of secondary hyperparathyroidism and parathyroid carcinoma, with 99.1% ee.

Separation of Aromatic Hydrocarbons in Porous Materials.

Industrial-scale thermal separation processes have contributed greatly to the rise in carbon dioxide emissions. Porous materials, such as metal-organic frameworks (MOFs), can potentially reduce these emissions by achieving nonthermal chemical separations through the physical adsorption of targeted species with high selectivity. Here, we report the synthesis of the channel-based MOFs NU-2000 and NU-2001, which are constructed from three-dimensional (3D) linkers, to separate the industrially relevant xylene isomers under ambient conditions by leveraging sub-Ångstrom differences in the sizes of each isomer. While the rotation of two-dimensional (2D) linkers in MOFs often affords changes in pore apertures and pore sizes that are substantial enough to hinder separation efficiency, increasing the linker dimensionality from 2D to three-dimensional (3D) enables precise control of the MOF pore size and aperture regardless of the linker orientation, establishing this design principle as a broadly applicable strategy.

Photocatalytic Biocidal Coatings Featuring Zr6Ti4-Based Metal-Organic Frameworks.

The world is currently suffering socially, economically, and politically from the recent pandemic outbreak due to the coronavirus disease 2019 (COVID-19), and those in hospitals, schools, and elderly nursing homes face enhanced threats. Healthcare textiles, such as masks and medical staff gowns, are susceptible to contamination of various pathogenic microorganisms, including bacteria and viruses. Metal-organic frameworks (MOFs) can potentially address these challenges due to their tunable reactivity and ability to be incorporated as porous coatings on textile materials. Here, we report how incorporating titanium into the zirconium-pyrene-based MOF NU-1000, denoted as NU-1012, generates a highly reactive biocidal photocatalyst. This MOF features a rare ligand migration phenomenon, and both the Ti/Zr center and the pyrene linker act synergistically as dual active centers and widen the absorption band for this material, which results in enhanced reactive oxygen species generation upon visible light irradiation. Additionally, we found that the ligand migration process is generally applicable to other csq topology Zr-MOFs. Importantly, NU-1012 can be easily incorporated onto cotton textile cloths as a coating, and the resulting composite material demonstrates fast and potent biocidal activity against Gram-negative bacteria (Escherichia coli), Gram-positive bacteria (Staphylococcus epidermidis), and T7 bacteriophage virus with up to a 7-log(99.99999%) reduction within 1 h under simulated daylight.

Understanding Diffusional Charge Transport within a Pyrene-Based Hydrogen-Bonded Organic Framework.

Electrochemically active hydrogen-bonded organic frameworks (HOFs) offer opportunities to study charge transport in supramolecular systems where the rate of movement of charges is dependent on weak electronic coupling between individual components. Here, we used potential-step chronoamperometric measurements on electrochemically active, drop-cast HOF-102 films to estimate both redox-hopping-based apparent diffusion coefficients for charge transport and rate constants for linker-to-linker charge transfer (hole transfer) in the mesoporous two-dimensional (2D) plane created by interlinker hydrogen bonding. Also present are one-dimensional columns formed by stacking pyrene units. However, because the HOF-102 crystallites containing these columns are oriented parallel to an underlying electrode, dynamics of charge transport (hole-transport) along the column axis, in contrast to the plane, are not directly probed by the electrochemical measurements. Furthermore, we employed electrochemical impedance spectroscopy to measure the electrical conductivity of the as-deposited films biased at various potentials. We found that both the neutral/singly oxidized and the singly oxidized/doubly oxidized pyrene linker redox couples of HOF-102 can engender hopping-based film conductivity within the 2D plane of HOF-102. Consistent with the radical cation and radical dication nature of the singly and doubly oxidized linkers, respectively, HOF-102 films are electrochromic. The measured values of in-plane charge-diffusion coefficients (∼10-10 to 10-11 cm2 s-1) and electrical conductivity (∼10-6 to 10-8 S cm-1) compare favorably with those for related redox-conductive MOFs and suggest that the transport and conductivity parameters for HOF-102 are sufficiently large to support electrocatalysis by subsequently installed catalysts in films─specifically, films of micron or greater thickness, corresponding to the equivalent hundreds of monolayers of closely packed (i.e., face-to-face-packed) pyrene-derivatives, but with solution access (solvent, ion, and reactant access) still readily provided by channels oriented parallel to an underlying planar electrode.

Metal-Organic Frameworks against Toxic Chemicals.

Materials capable of the safe and efficient capture or degradation of toxic chemicals, including chemical warfare agents (CWAs) and toxic industrial chemicals (TICs), are critically important in the modern age due to continuous threats of these chemicals to human life, both directly and indirectly. Metal-organic frameworks (MOFs), atomically precise hybrid materials that are synthesized via the self-assembly of metal cations or clusters and organic linkers, offer a unique solid adsorbent design platform due to their great synthetic versatility. This review will focus on recent advancements in MOF-based adsorbent design for protection against chemical warfare agents (organophosphorus nerve agents, blistering agents, and their simulants) and toxic industrial chemicals such as H2S, NH3, SO2, CO, NO2, and NO.

Leveraging Isothermal Titration Calorimetry to Explore Structure-Property Relationships of Protein Immobilization in Metal-Organic Frameworks.

Proteins immobilized in metal-organic frameworks (MOFs) often show extraordinary stability. However, most efforts to immobilize proteins in MOFs have only been exploratory. Herein, we present the first systematic study on the thermodynamics of protein immobilization in MOFs. Using insulin as a probe, we leveraged isothermal titration calorimetry (ITC) to investigate how topology, pore size, and hydrophobicity of MOFs influence immobilization. ITC data obtained from the encapsulation of insulin in a series of Zr-MOFs reveals that MOFs provide proteins with a hydrophobic stabilizing microenvironment, making the encapsulation entropically driven. In particular, the pyrene-based NU-1000 tightly encapsulates insulin in its ideally sized mesopores and stabilizes insulin through π-π stacking interactions, resulting in the most enthalpically favored encapsulation process among this series. This study reveals critical insights into the structure-property relationships of protein immobilization.