Solute interaction-driven and solvent interaction-driven liquid-liquid phase separation induced by molecular size difference.

We conducted molecular dynamics (MD) simulations in a binary Lennard-Jones system as a model system for molecular solutions and investigated the mechanism of liquid-liquid phase separation (LLPS), which has recently been recognized as a fundamental step in crystallization and organelle formation. Our simulation results showed that LLPS behavior varied drastically with the size ratio of solute to solvent molecules. Interestingly, increasing the size ratio can either facilitate or inhibit LLPS, depending on the combination of interaction strengths. We demonstrated that the unique behavior observed in MD simulation could be reasonably explained by the free energy barrier height calculated using our thermodynamic model based on the classical nucleation theory. Our model proved that the molecular size determines the change in number of interaction pairs through LLPS. Varying the size ratio changes the net number of solute-solvent and solvent-solvent interaction pairs that are either broken or newly generated per solute-solute pair generation, thereby inducing a complicated trend in LLPS depending on the interaction parameters. As smaller molecules have more interaction pairs per unit volume, their contribution is more dominant in the promotion of LLPS. Consequently, as the size ratio of the solute to the solvent increased, the LLPS mode changed from solute-related interaction-driven to solvent-related interaction-driven.

Generalised analytical method unravels framework-dependent kinetics of adsorption-induced structural transition in flexible metal-organic frameworks.

Flexible metal-organic frameworks (MOFs) exhibiting adsorption-induced structural transition can revolutionise adsorption separation processes, including CO2 separation, which has become increasingly important in recent years. However, the kinetics of this structural transition remains poorly understood despite being crucial to process design. Here, the CO2-induced gate opening of ELM-11 ([Cu(BF4)2(4,4'-bipyridine)2]n) is investigated by time-resolved in situ X-ray powder diffraction, and a theoretical kinetic model of this process is developed to gain atomistic insight into the transition dynamics. The thus-developed model consists of the differential pressure from the gate opening (indicating the ease of structural transition) and reaction model terms (indicating the transition propagation within the crystal). The reaction model of ELM-11 is an autocatalytic reaction with two pathways for CO2 penetration of the framework. Moreover, gas adsorption analyses of two other flexible MOFs with different flexibilities indicate that the kinetics of the adsorption-induced structural transition is highly dependent on framework structure.

Fast Gas-Adsorption Kinetics in Supraparticle-Based MOF Packings with Hierarchical Porosity.

Metal-organic frameworks (MOFs) are microporous adsorbents for high-throughput gas separation. Such materials exhibit distinct adsorption characteristics owing to the flexibility of the crystal framework in a nanoparticle, which can be different from its bulk crystal. However, for practical applications, such particles need to be compacted into macroscopic pellets, creating mass-transport limitations. In this work, this problem is addressed by forming materials with structural hierarchy, using a supraparticle-based approach. Spherical supraparticles composed of nanosized MOF particles are fabricated by emulsion templating and they are used as the structural component forming a macroscopic material. Zeolitic imidazolate framework-8 (ZIF-8) particles are used as a model system and the gas-adsorption kinetics of the hierarchical material are compared with conventional pellets without structural hierarchy. It is demonstrated that a pellet packed with supraparticles exhibits a 30 times faster adsorption rate compared to an unstructured ZIF-8 powder pellet. These results underline the importance of controlling structural hierarchy to maximize the performance of existing materials. In the hierarchical MOFs, large macropores between the supraparticles, smaller macropores between individual ZIF-8 primary particles, and micropores inherent to the ZIF-8 framework collude to combine large surface area, defined adsorption sites, and efficient mass transport to enhance performance.

Crossover Sorption of C2 H2 /CO2 and C2 H6 /C2 H4 in Soft Porous Coordination Networks.

Porous sorbents are materials that are used for various applications, including storage and separation. Typically, the uptake of a single gas by a sorbent decreases with temperature, but the relative affinity for two similar gases does not change. However, in this study, we report a rare example of "crossover sorption," in which the uptake capacity and apparent affinity for two similar gases reverse at different temperatures. We synthesized two soft porous coordination polymers (PCPs), [Zn2 (L1)(L2)2 ]n (PCP-1) and [Zn2 (L1)(L3)2 ]n (PCP-2) (L1= 1,4-bis(4-pyridyl)benzene, L2=5-methyl-1,3-di(4-carboxyphenyl)benzene, and L3=5-methoxy-1,3-di(4-carboxyphenyl)benzene). These PCPs exhibits structural changes upon gas sorption and show the crossover sorption for both C2 H2 /CO2 and C2 H6 /C2 H4 , in which the apparent affinity reverse with temperature. We used in situ gas-loading single-crystal X-ray diffraction (SCXRD) analysis to reveal the guest inclusion structures of PCP-1 for C2 H2 , CO2 , C2 H6 , and C2 H4 gases at various temperatures. Interestingly, we observed three-step single-crystal to single-crystal (sc-sc) transformations with the different loading phases under these gases, providing insight into guest binding positions, nature of host-guest or guest-guest interactions, and their phase transformations upon exposure to these gases. Combining with theoretical investigation, we have fully elucidated the crossover sorption in the flexible coordination networks, which involves a reversal of apparent affinity and uptake of similar gases at different temperatures. We discovered that this behaviour can be explained by the delicate balance between guest binding and host-guest and guest-guest interactions.

Theoretical isotherm equation for adsorption-induced structural transition on flexible metal-organic frameworks.

Flexible metal-organic frameworks (MOFs) exhibit an adsorption-induced structural transition known as "gate opening" or "breathing," resulting in an S-shaped adsorption isotherm. This unique feature of flexible MOFs offers significant advantages, such as a large working capacity, high selectivity, and intrinsic thermal management capability, positioning them as crucial candidates for revolutionizing adsorption separation processes. Therefore, the interest in the industrial applications of flexible MOFs is increasing, and the adsorption engineering for flexible MOFs is becoming important. However, despite the establishment of the theoretical background for adsorption-induced structural transitions, no theoretical equation is available to describe S-shaped adsorption isotherms of flexible MOFs. Researchers rely on various empirical equations for process simulations that can lead to unreliable outcomes or may overlook insights into improving material performance owing to parameters without physical meaning. In this study, we derive a theoretical equation based on statistical mechanics that could be a standard for the structural transition type adsorption isotherms, as the Langmuir equation represents type I isotherms. The versatility of the derived equation is shown through four examples of flexible MOFs that exhibit gate opening and breathing. The consistency of the formula with existing theories, including the osmotic free energy analysis and intrinsic thermal management capabilities, is also discussed. The developed theoretical equation may lead to more reliable and insightful outcomes in adsorption separation processes, further advancing the direction of industrial applications of flexible MOFs.

Validating the Mechanism Underlying the Slacking of the Gate-Opening Behavior in Flexible Metal-Organic Frameworks Arising from the Application of External Force.

Flexible metal-organic frameworks (MOFs) are innovative adsorbents expected to revolutionize conventional separation systems as they exhibit stepwise adsorption arising from structural transitions, commonly known as "gate opening." However, because MOFs are typically obtained in powder form, they require shaping for industrial applications. In our previous study, we reported that the stepwise uptake observed in the CO2 gate opening of ELM-11 ([Cu(BF4)2(4,4'-bipyridine)2]) became less distinct when molded with polymer binders and found that this slacking phenomenon could be caused by the polymer binder inhibiting the structural change of the ELM-11 particles. In this study, we aimed to fully validate and generalize the mechanism behind the slacking of gate adsorption from both theoretical and experimental perspectives. First, we conducted grand canonical molecular dynamics simulations for a simplified MOF model to directly calculate free energy profiles of the particle to validate the slacking theory without any assumptions. The results confirmed the fundamental assumption made in our previous study that the deformation of the flexible motifs within the MOF particles occurs sequentially, which is a key factor contributing to the slacking phenomenon. The second part of the study focused on the relationship between the volume expansion ratio of MOFs and the degree of slacking. The relationship predicted by the theory was experimentally validated by comparing ELM-11, which exhibits 30% volume expansion, to another MOF with a mutually interpenetrating jungle-gym structure, which exhibits 10% volume expansion. These findings strengthened and generalized the understanding of the mechanism underlying the slacking of gate adsorption induced upon the application of external force, which could guide the fabrication of molded MOFs while maintaining a high adsorption efficiency for various industrial applications.

Slacking of Gate Adsorption Behavior on Metal-Organic Frameworks under an External Force.

As flexible metal-organic frameworks (MOFs) and their gate adsorption behaviors are increasingly expected to be used in gas storage and separation systems, evaluating their performance by considering their usage patterns in actual processes is becoming increasingly important. Herein, we show that the shaping of the elastic layer-structured MOF-11 (ELM-11; [Cu(BF4)2(4,4'-bipyridine)2]) into pellet forms using polymer binders smears its stepwise uptake associated with the CO2 gate adsorption. This is a critical problem because the superior adsorption properties of flexible MOFs are highly dependent on the sharpness of the step. Free energy analysis by molecular simulations revealed that the slacking of the gate adsorption is natural from a thermodynamic point of view. In other words, the external force exerted by the polymer binders, which prevents the expansion of MOF particles upon the gate opening, changes the free energy landscape of the system. This causes the flexible motifs within the MOF particles to undergo a structural transition at slightly different pressures from each other. The force profile dependence of the slacking phenomenon on both adsorption and desorption isotherms was also investigated. It was revealed that controlling the force profile applied to MOF particles is important to mold MOF pellets that satisfy the robustness and sharpness of the gate adsorption. Finally, we examined the coating of pellets to verify the relationship between the force profile and the degree of slacking and discussed possible strategies to improve the sharpness of the gate adsorption on MOF pellets considering the revealed mechanism.

High-throughput gas separation by flexible metal-organic frameworks with fast gating and thermal management capabilities.

Establishing new energy-saving systems for gas separation using porous materials is indispensable for ensuring a sustainable future. Herein, we show that ELM-11 ([Cu(BF4)2(4,4'-bipyridine)2]n), a member of flexible metal-organic frameworks (MOFs), exhibits rapid responsiveness to a gas feed and an 'intrinsic thermal management' capability originating from a structural deformation upon gas adsorption (gate-opening). These two characteristics are suitable for developing a pressure vacuum swing adsorption (PVSA) system with rapid operations. A combined experimental and theoretical study reveals that ELM-11 enables the high-throughput separation of CO2 from a CO2/CH4 gas mixture through adiabatic operations, which are extreme conditions in rapid pressure vacuum swing adsorption. We also propose an operational solution to the 'slipping-off' problem, which is that the flexible MOFs cannot adsorb target molecules when the partial pressure of the target gas decreases below the gate-opening pressure. Furthermore, the superiority of our proposed system over conventional systems is demonstrated.

Fast continuous measurement of synchrotron powder diffraction synchronized with controlling gas and vapour pressures at beamline BL02B2 of SPring-8.

A gas- and vapour-pressure control system synchronized with the continuous data acquisition of millisecond high-resolution powder diffraction measurements was developed to study structural change processes in gas storage and reaction materials such as metal organic framework compounds, zeolite and layered double hydroxide. The apparatus, which can be set up on beamline BL02B2 at SPring-8, mainly comprises a pressure control system of gases and vapour, a gas cell for a capillary sample, and six one-dimensional solid-state (MYTHEN) detectors. The pressure control system can be remotely controlled via developed software connected to a diffraction measurement system and can be operated in the closed gas and vapour line system. By using the temperature-control system on the sample, high-resolution powder diffraction data can be obtained under gas and vapour pressures ranging from 1 Pa to 130 kPa in temperatures ranging from 30 to 1473 K. This system enables one to perform automatic and high-throughput in situ X-ray powder diffraction experiments even at extremely low pressures. Furthermore, this developed system is useful for studying crystal structures during the adsorption/desorption processes, as acquired by millisecond and continuous powder diffraction measurements. The acquisition of diffraction data can be synchronized with the control of the pressure with a high frame rate of up to 100 Hz. In situ and time-resolved powder diffraction measurements are demonstrated for nanoporous Cu coordination polymer in various gas and vapour atmospheres.

Central metal dependent modulation of induced-fit gas uptake in molecular porphyrin solids.

The induced-fit accommodation of a variety of gaseous molecules including non-polar molecules has been demonstrated in porphyrin-based supramolecular architectures for the first time. Moreover, the gas uptake behaviour can be modulated by changing the central cation of porphyrin.

Intrinsic Thermal Management Capabilities of Flexible Metal-Organic Frameworks for Carbon Dioxide Separation and Capture.

We show that flexible metal-organic frameworks (MOFs) exhibiting "gate openings/closings" for CO2 can intrinsically suppress the exothermic heat released by adsorption and the endothermic heat gained by desorption, both of which reduce the working capacity of CO2 in a separation process under near-adiabatic conditions. We use the elastic layer-structured metal-organic framework-11 (ELM-11) [Cu(4,4'-bipyridine)2(BF4)2], which exhibits a two-step gate-adsorption isotherm, as a model system for flexible MOFs, and perform free energy analyses with the aid of grand canonical Monte Carlo simulations for ELM-11 structures that were determined by the Rietveld method using in situ synchrotron X-ray powder diffraction data. We demonstrate that the thermal management capabilities of ELM-11 showing the two-step gating for CO2 at lower and higher pressures are nearly identical and quite effective (41% and 44% at 298 K, respectively). Moreover, we show that ELM-11 has an extremely high CO2 selectivity for both CO2/N2 and CO2/CH4 mixtures at 298 K that, in addition to the intrinsic thermal management capability, is a crucial factor for application to carbon capture and storage (CCS). The multigate closing pressures of ELM-11 are not necessarily matched to the operating pressures used in CCS; however, our findings, and perspectives based on free energy analyses regarding modification of the host framework structure to tune the gating pressure, suggest that flexible MOFs exhibiting multigate openings/closings are promising materials for further development into systems with intrinsic thermal management mechanisms for CCS applications.

Understanding gate adsorption behaviour of CO2 on elastic layer-structured metal-organic framework-11.

We demonstrate that CO2 gate adsorption behaviour of elastic layer-structured metal-organic framework-11 (ELM-11: [Cu(BF4)2(4,4'-bipyridine)2]), which is a family of soft porous crystals (SPCs), can be described by a thermodynamic model by free energy analysis with the aid of an adsorption experiment and a molecular simulation. The structures of ELM-11 (closed structure) at 273 K after its evacuation and CO2-encapsulated ELM-11 (open structure) at 195-298 K were determined by the Rietveld analysis using in situ synchrotron X-ray powder diffraction data. We then performed grand canonical Monte Carlo (GCMC) simulations for CO2 adsorption on the open host framework structures of ELM-11 from the Rietveld analysis. The temperature dependence of the Helmholtz free energy change of host ΔF(host) from the closed structure to the open structure was obtained by the free energy analysis using the GCMC data. We show that there is a linear correlation between ΔF(host) and temperature, and thus, the internal energy and entropy changes of host, ΔU(host) and ΔS(host), respectively, can be obtained. The obtained ΔU(host) value is in good agreement with that obtained from the quantum chemical calculations using the closed and open host framework structures, which demonstrates that the thermodynamic model for gate adsorption is highly appropriate. Moreover, our result suggests that the gate adsorption pressure depends on not only the guest-host interaction and the internal energy change of host, but also the entropy change of host, which should be one of the key factors for the tailored synthesis of SPCs.