Dynamic two-dimensional covalent organic frameworks.

Porous covalent organic frameworks (COFs) enable the realization of functional materials with molecular precision. Past research has typically focused on generating rigid frameworks where structural and optoelectronic properties are static. Here we report dynamic two-dimensional (2D) COFs that can open and close their pores upon uptake or removal of guests while retaining their crystalline long-range order. Constructing dynamic, yet crystalline and robust frameworks requires a well-controlled degree of flexibility. We have achieved this through a 'wine rack' design where rigid π-stacked columns of perylene diimides are interconnected by non-stacked, flexible bridges. The resulting COFs show stepwise phase transformations between their respective contracted-pore and open-pore conformations with up to 40% increase in unit-cell volume. This variable geometry provides a handle for introducing stimuli-responsive optoelectronic properties. We illustrate this by demonstrating switchable optical absorption and emission characteristics, which approximate 'null-aggregates' with monomer-like behaviour in the contracted COFs. This work provides a design strategy for dynamic 2D COFs that are potentially useful for realizing stimuli-responsive materials.

Real-Time Multiscale Imaging of Heterogeneous Multistage Reactions: Insights into Nanoscale TiO2 Synthesis.

Hydrothermal methods are widely used to synthesize functional inorganic materials. The interplay between the reactive species, solution chemistry, and the nanoscale product makes it challenging to control the reaction pathway to achieve a uniform product. Here, we resolve the heterogeneity that arises during hydrothermal synthesis across different length scales. We combine spatially resolved in situ X-ray pair distribution function (PDF) and small-angle X-ray scattering analysis, which are sensitive to structure on the atomic and nanoscale, with a novel time-lapse optical imaging strategy that reveals heterogeneity and phase separations across the entire reaction. For TiO2 synthesis via hydrothermal hydrolysis of TiCl4, we identify multiple cycles of TiO2 formation and separation that contribute to nonuniformity in the polymorphic product. The PDF data show that the characteristics of TiO2 formed during each formation-separation cycle differ, contributing to the ongoing challenge of precisely identifying reaction controls. The imaging strategy pioneered here provides an efficient in situ means to systematically compare how the reaction evolves under different chemical conditions, thereby advancing our understanding of functional inorganic material synthesis.

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.

In Situ Single-crystal X-ray Diffraction Studies of Physisorption and Chemisorption of SO2 within a Metal-Organic Framework and Its Competitive Adsorption with Water.

Living on an increasingly polluted planet, the removal of toxic pollutants such as sulfur dioxide (SO2) from the troposphere and power station flue gas is becoming more and more important. The CPO-27/MOF-74 family of metal-organic frameworks (MOFs) with their high densities of open metal sites is well suited for the selective adsorption of gases that, like SO2, bind well to metals and have been extensively researched both practically and through computer simulations. However, until now, focus has centered upon the binding of SO2 to the open metal sites in this MOF (called chemisorption, where the adsorbent-adsorbate interaction is through a chemical bond). The possibility of physisorption (where the adsorbent-adsorbate interaction is only through weak intermolecular forces) has not been identified experimentally. This work presents an in situ single-crystal X-ray diffraction (scXRD) study that identifies discrete adsorption sites within Ni-MOF-74/Ni-CPO-27, where SO2 is both chemisorbed and physisorbed while also probing competitive adsorption of SO2 of these sites when water is present. Further features of this site have been confirmed by variable SO2 pressure scXRD studies, DFT calculations, and IR studies.

Probing Structural Transformations and Degradation Mechanisms by Direct Observation in SIFSIX-3-Ni for Direct Air Capture.

Despite global efforts to reduce carbon dioxide (CO2) emissions, continued industrialization threatens to exacerbate climate change. This work investigates methods to capture CO2, with a focus on the SIFSIX-3-Ni metal-organic framework (MOF) as a direct air capture (DAC) sorbent. SIFSIX-3-Ni exhibits promising CO2 adsorption properties but suffers from degradation processes under accelerated aging, which are akin to column regeneration conditions. Herein, we have grown the largest SIFSIX-3-Ni single crystals to date, facilitating single crystal X-ray diffraction analyses that enabled direct observation of the H2O and CO2 dynamics through adsorption and desorption. In addition, a novel space group (I4/mcm) for the SIFSIX-3-Ni is identified, which provided insights into structural transitions within the framework and elucidated water's role in degrading CO2 uptake performance as the material ages. In situ X-ray scattering methods revealed long-range and local structural transformations associated with CO2 adsorption in the framework pores as well as a temperature-dependent desorption mechanism. Pair distribution function analysis revealed a partial decomposition to form nonporous single-layer nanosheets of edge-sharing nickel oxide octahedra upon aging. The formation of these nanosheets is irreversible and reduces the amount of active material for the CO2 sorption. These findings provide crucial insights for the development of efficient and stable DAC sorbents, effectively reducing greenhouse gases, and suggest avenues for enhancing MOF stability under practical DAC conditions.

Resolving Fast Relative Kinetics in Inorganic Solid-State Synthesis.

Solid-state syntheses are generally regarded as being slow, limited by transport, and, as such, are often only stopped to check the products after many hours at high temperature. Here, using a custom-designed reactor to rapidly initiate solid-state syntheses, we are able to capture the earliest stages of a reaction using in situ X-ray scattering. For the reaction of TiO2 and Li2CO3 to form spinel lithium titanate (Li4Ti5O12)─an anode material for fast-charging applications─we capture two distinct kinetic regimes, including fast initial kinetics in the first seconds-minutes of the reaction that account for significant product formation. We use an Avrami model to compare the reaction at high temperatures (700-750 °C), which results in the rapid formation of Li4Ti5O12 within minutes, and lower temperatures (482 °C), consistent with conditions that might be chosen based on "Tamman's rule", a common heuristic. Our analysis reveals characteristic Avrami slopes (i.e., dimensionalities) for each step in the chemical transformation. We anticipate that the fast initial reaction kinetics found here are likely to be common in the synthesis of other materials used in battery electrodes, solid-state electrolytes, ion-conductive membranes, etc. where ion transport is a prerequisite for functionality.

Mixed Metal-Organic Framework Mixed-Matrix Membranes: Insights into Simultaneous Moisture-Triggered and Catalytic Delivery of Nitric Oxide using Cryo-scanning Electron Microscopy.

The fundamental chemical and structural diversity of metal-organic frameworks (MOFs) is vast, but there is a lack of industrial adoption of these extremely versatile compounds. To bridge the gap between basic research and industry, MOF powders must be formulated into more application-relevant shapes and/or composites. Successful incorporation of varying ratios of two different MOFs, CPO-27-Ni and CuBTTri, in a thin polymer film represents an important step toward the development of mixed MOF mixed-matrix membranes. To gain insight into the distribution of the two different MOFs in the polymer, we report their investigation by Cryo-scanning electron microscopy (Cryo-SEM) tomography, which minimizes surface charging and electron beam-induced damage. Because the MOFs are based on two different metal ions, Ni and Cu, the elemental maps of the MOF composite cross sections clearly identify the size and location of each MOF in the reconstructed 3D model. The tomography run was about six times faster than conventional focused ion beam (FIB)-SEM and the first insights to image segmentation combined with machine learning could be achieved. To verify that the MOF composites combined the benefits of rapid moisture-triggered release of nitric oxide (NO) from CPO-27-Ni with the continuous catalytic generation of NO from CuBTTri, we characterized their ability to deliver NO individually and simultaneously. These MOF composites show great promise to achieve optimal dual NO delivery in real-world medical applications.

Impedance-Based Detection of NO2 Using Ni-MOF-74: Influence of Competitive Gas Adsorption.

Chemically robust, low-power sensors are needed for the direct electrical detection of toxic gases. Metal-organic frameworks (MOFs) offer exceptional chemical and structural tunability to meet this challenge, though further understanding is needed regarding how coadsorbed gases influence or interfere with the electrical response. To probe the influence of competitive gases on trace NO2 detection in a simulated flue gas stream, a combined structure-property study integrating synchrotron powder diffraction and pair distribution function analyses was undertaken, to elucidate how structural changes associated with gas binding inside Ni-MOF-74 pores correlate with the electrical response from Ni-MOF-74-based sensors. Data were evaluated for 16 gas combinations of N2, NO2, SO2, CO2, and H2O at 50 °C. Fourier difference maps from a rigid-body Rietveld analysis showed that additional electron density localized around the Ni-MOF-74 lattice correlated with large decreases in Ni-MOF-74 film resistance of up to a factor of 6 × 103, observed only when NO2 was present. These changes in resistance were significantly amplified by the presence of competing gases, except for CO2. Without NO2, H2O rapidly (<120 s) produced small (1-3×) decreases in resistance, though this effect could be differentiated from the slower adsorption of NO2 by the evaluation of the MOF's capacitance. Furthermore, samples exposed to H2O displayed a significant shift in lattice parameters toward a larger lattice and more diffuse charge density in the MOF pore. Evaluating the Ni-MOF-74 impedance in real time, NO2 adsorption was associated with two electrically distinct processes, the faster of which was inhibited by competitive adsorption of CO2. Together, this work points to the unique interaction of NO2 and other specific gases (e.g., H2O, SO2) with the MOF's surface, leading to orders of magnitude decrease in MOF resistance and enhanced NO2 detection. Understanding and leveraging these coadsorbed gases will further improve the gas detection properties of MOF materials.

Unveiling Unexpected Modulator-CO2 Dynamics within a Zirconium Metal-Organic Framework.

Carbon capture, storage, and utilization (CCSU) represents an opportunity to mitigate carbon emissions that drive global anthropogenic climate change. Promising materials for CCSU through gas adsorption have been developed by leveraging the porosity, stability, and tunability of extended crystalline coordination polymers called metal-organic frameworks (MOFs). While the development of these frameworks has yielded highly effective CO2 sorbents, an in-depth understanding of the properties of MOF pores that lead to the most efficient uptake during sorption would benefit the rational design of more efficient CCSU materials. Though previous investigations of gas-pore interactions often assumed that the internal pore environment was static, discovery of more dynamic behavior represents an opportunity for precise sorbent engineering. Herein, we report a multifaceted in situ analysis following the adsorption of CO2 in MOF-808 variants with different capping agents (formate, acetate, and trifluoroacetate: FA, AA, and TFA, respectively). In situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) analysis paired with multivariate analysis tools and in situ powder X-ray diffraction revealed unexpected CO2 interactions at the node associated with dynamic behavior of node-capping modulators in the pores of MOF-808, which had previously been assumed to be static. MOF-808-TFA displays two binding modes, resulting in higher binding affinity for CO2. Computational analyses further support these dynamic observations. The beneficial role of these structural dynamics could play an essential role in building a deeper understanding of CO2 binding in MOFs.

In situ single-crystal synchrotron X-ray diffraction studies of biologically active gases in metal-organic frameworks.

Metal-organic frameworks (MOFs) are well known for their ability to adsorb various gases. The use of MOFs for the storage and release of biologically active gases, particularly nitric oxide (NO) and carbon monoxide (CO), has been a subject of interest. To elucidate the binding mechanisms and geometry of these gases, an in situ single crystal X-ray diffraction (scXRD) study using synchrotron radiation at Diamond Light Source has been performed on a set of MOFs that display promising gas adsorption properties. NO and CO, were introduced into activated Ni-CPO-27 and the related Co-4,6-dihydroxyisophthalate (Co-4,6-dhip). Both MOFs show strong binding affinity towards CO and NO, however CO suffers more from competitive co-adsorption of water. Additionally, we show that morphology can play an important role in the ease of dehydration for these two systems.

Surface-Functionalized Metal-Organic Frameworks for Binding Coronavirus Proteins.

Since the outbreak of SARS-CoV-2, a multitude of strategies have been explored for the means of protection and shielding against virus particles: filtration equipment (PPE) has been widely used in daily life. In this work, we explore another approach in the form of deactivating coronavirus particles through selective binding onto the surface of metal-organic frameworks (MOFs) to further the fight against the transmission of respiratory viruses. MOFs are attractive materials in this regard, as their rich pore and surface chemistry can easily be modified on demand. The surfaces of three MOFs, UiO-66(Zr), UiO-66-NH2(Zr), and UiO-66-NO2(Zr), have been functionalized with repurposed antiviral agents, namely, folic acid, nystatin, and tenofovir, to enable specific interactions with the external spike protein of the SARS virus. Protein binding studies revealed that this surface modification significantly improved the binding affinity toward glycosylated and non-glycosylated proteins for all three MOFs. Additionally, the pores for the surface-functionalized MOFs can adsorb water, making them suitable for locally dehydrating microbial aerosols. Our findings highlight the immense potential of MOFs in deactivating respiratory coronaviruses to be better equipped to fight future pandemics.

Relative Kinetics of Solid-State Reactions: The Role of Architecture in Controlling Reactivity.

Countless inorganic materials are prepared via high temperature solid-state reaction of mixtures of reagents powders. Understanding and controlling the phenomena that limit these solid-state reactions is crucial to designing reactions for new materials synthesis. Here, focusing on topotactic ion-exchange between NaFeO2 and LiBr as a model reaction, we manipulate the mesoscale reaction architecture and transport pathways by changing the packing and interfacial contact between reagent particles. Through analysis of in situ synchrotron X-ray diffraction data, we identify multiple kinetic regimes that reflect transport limitations on different length scales: a fast kinetic regime in the first minutes of the reaction and a slow kinetic regime that follows. The fast kinetic regime dominates the observed reaction progress and depends on the reagent packing; this challenges the view that solid-state reactions are necessarily slow. Using a phase-field model, we simulated the reaction process and showed that particles without direct contact to the other reactant phases experience large reduction in the reaction rate, even when transport hindrance at particle-particle contacts is not considered.

Controlled Synthesis of Large Single Crystals of Metal-Organic Framework CPO-27-Ni Prepared by a Modulation Approach: In situ Single-Crystal X-ray Diffraction Studies.

The size of single crystals of the metal-organic framework CPO-27-Ni was incrementally increased through a series of modulated syntheses. A novel linker modulated synthesis using 2,5-dihydroxyterephthalic acid and the isomeric ligand 4,6-dihydroxyisophthalic acid yielded large single crystals of CPO-27-Ni (∼70 µm). All materials were shown to have high crystallinity and phase purity through powder X-ray diffraction, electron microscopy methods, thermogravimetry, and compositional analysis. For the first time single-crystal structure analyses were carried out on CPO-27-Ni. High BET surface areas and nitric oxide (NO) release efficiencies were recorded for all materials. Large single crystals of CPO-27-Ni showed a prolonged NO release and proved suitable for in situ single-crystal diffraction experiments to follow the NO adsorption. An efficient activation protocol was developed, leading to a dehydrated structure after just 4 h, which subsequently was NO-loaded, leading to a first NO loaded single-crystal structural model of CPO-27-Ni.

In situ flow pair distribution function analysis to probe the assembly-disassembly-organisation-reassembly (ADOR) mechanism of zeolite IPC-2 synthesis.

The assembly-disassembly-organisation-reassembly (ADOR) process is an important tool to access zeolite structures that are otherwise unfeasible via hydrothermal methods. In situ flow pair distribution function (PDF) analysis has been used to probe the mechanism of the disassembly and organisation steps, with the disassembly a rapid step that is often difficult to capture. Zeolite UTL was hydrolysed by 6 M hydrochloric acid, with PDF measurements used to monitor framework alterations as the reaction proceeded. The resulting disassembly mechanism shows an initial rapid removal of germanium from the germanium-rich double 4 rings (d4r), followed by silicon rearrangement and gradual silanol condensation to form IPC-2P.

Multifaceted Study of the Interactions between CPO-27-Ni and Polyurethane and Their Impact on Nitric Oxide Release Performance.

A multifaceted study involving focused ion beam scanning electron microscopy techniques, mechanical analysis, water adsorption measurements, and molecular simulations is employed to rationalize the nitric oxide release performance of polyurethane films containing 5, 10, 20, and 40 wt % of the metal-organic framework (MOF) CPO-27-Ni. The polymer and the MOF are first demonstrated to exhibit excellent compatibility. This is reflected in the even distribution and encapsulation of large wt % MOF loadings throughout the full thickness of the films and by the rather minimal influence of the MOF on the mechanical properties of the polymer at low wt %. The NO release efficiency of the MOF is attenuated by the polymer and found to depend on wt % of MOF loading. The formation of a fully connected network of MOF agglomerates within the films at higher wt % is proposed to contribute to a more complex guest transport in these formulations, resulting in a reduction of NO release efficiency and film ductility. An optimum MOF loading of 10 wt % is identified for maximizing NO release without adversely impacting the polymer properties. Bactericidal efficacy of released NO from the films is demonstrated against Pseudomonas aeruginosa, with a >8 log10 reduction in cell density observed after a contact period of 24 h.

Low temperature synthesis study of metal-organic framework CPO-27: investigating metal, solvent and base effects down to -78 °C.

CPO-27-M (M = Co, Mg, Ni, Zn) metal-organic frameworks have been successfully synthesized at temperatures down to -78 °C in a range of solvent systems and their crystallinity and morphology analyzed by powder X-ray diffraction and scanning electron microscopy. CPO-27-Mg and -Zn could be synthesized at lower temperatures using MeOH-NaOH as the solvent with CPO-27-Zn showing the most crystalline material at -78 °C. CPO-27-Zn afforded the most crystalline samples of all studies in MeOH-TEA. However, in MeOH a non-porous monomeric [Zn(H2dhtp)(H2O)2] complex was formed when no base was present. In THF with base (NaOH, TEA) the reaction produced crystalline MOFs in a controlled and stable manner at low temperatures, whilst the reagents were insoluble in THF at low temperature when no base was present. SEM was used to analyze the morphologies of the products.