Investigating the effect of metal nuclearity on activity for ethylene hydrogenation by metal-organic
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Wang, Qining↗
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Understanding the Mechanism of High Capacitance in Nickel Hexaaminobenzene-Based Conductive Metal-Organic Frameworks in Aqueous Electrolytes
Recently, intrinsically conductive metal-organic frameworks (MOFs) have demonstrated promising performance in fast-charging energy storage applications and may outperform some current electrode materials (e.g., porous carbons) for supercapacitors in terms of both gravimetric and volumetric capacitance. In this report, we examine the mechanism of high capacitance in a nickel hexaaminobenzene-based MOF (NiHAB). Using a combination of in situ Raman and X-Ray absorption spectroscopies, as well as detailed electrochemical studies in a series of aqueous electrolytes, we demonstrate in this work that the charge storage mechanism is in fact a pH-dependent surface pseudocapacitance, and, unlike typical inorganic systems, where transition metals change oxidation state during charge/discharge cycles, NiHAB redox activity is ligand-centered.
25 ENERGY STORAGE↗
Revisiting Competitive Adsorption of Small Molecules in the Metal–Organic Framework Ni-MOF-74
To precisely evaluate the potential of metal-organic frameworks (MOFs) for gas separation and purification applications, it is crucial to understand how various molecules competitively adsorb inside MOFs. In this paper, we combine in situ infrared spectroscopy with ab initio calculations to investigate the mechanisms associated with co-adsorption of a number of small molecules including CO, NO, and CO 2 inside the prototypical framework Ni-MOF-74. Surprisingly, we find that the displacement of CO bound inside Ni-MOF-74 (binding energy of 53 kJ/mol) is readily driven by CO 2 exposure, even though CO 2 has a noticeably weaker binding energy of only 41 kJ/mol; meanwhile, the significantly more strongly binding NO molecule (90 kJ/mol) is not able to easily displace bound CO inside Ni-MOF74. These results show that single-phase binding energies of a molecule inside the MOF cannot completely describe their interaction with the MOF in the presence of other guest molecules. Here, we unveil a number of crucial factors such as the kinetic barrier, partial pressure, secondary binding sites, and guest-host/lateral interactions that control the co-adsorption process and combined with the binding energy are better descriptors of the behavior and adsorption of gas mixtures inside MOFs.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Binding of uranyl cations to a Zr-based metal-organic framework by density functional theory
Zr-based metal–organic frameworks (Zr-MOFs) have been widely used as ion adsorbents for the removal or extraction of toxic and/or radionuclide species from aqueous solutions. However, the mechanisms by which uranyl cations (UO 2 2+ ) interact with Zr-MOFs have not been established. In this work, the nature of the bonding of uranyl cations with a Zr-MOF was determined using density functional theory for nineteen structurally distinct candidate complexes. Further, the results showed that in all cases the binding energy was of the order of 1.5 eV, but depended on the specific bonding site. The most stable structure involved coordination of the uranyl cation and two structurally distinct oxygens in the Zr-MOF metal node. It was also found that higher degree of deprotonation in Zr-MOF correlated with higher binding energy between the Zr-MOF and uranyl cations. These insights can aid in the design of Zr-MOFs with optimized features for efficient capture of uranyl cations.
36 MATERIALS SCIENCE↗
Atomically Dispersed Copper Sites in a Metal–Organic Framework for Reduction of Nitrogen Dioxide
Metal-organic framework (MOF) materials provide an excellent platform to fabricate single-atom catalysts due to their structural diversity, intrinsic porosity, and designable functionality. However, the unambiguous identification of atomically dispersed metal sites and the elucidation of their role in catalysis are challenging due to limited methods of characterization and lack of direct structural information. Here, we report a comprehensive investigation of the structure and the role of atomically dispersed copper sites in UiO-66 for the catalytic reduction of NO 2 at ambient temperature. The atomic dispersion of copper sites on UiO-66 is confirmed by high-angle annular dark-field scanning transmission electron microscopy, electron paramagnetic resonance spectroscopy, and inelastic neutron scattering, and their location is identified by neutron powder diffraction and solid-state nuclear magnetic resonance spectroscopy. The Cu/UiO-66 catalyst exhibits superior catalytic performance for the reduction of NO 2 at 25 °C without the use of reductants. A selectivity of 88% for the formation of N2 at a 97% conversion of NO 2 with a lifetime of >50 h and an unprecedented turnover frequency of 6.1 h-1 is achieved under nonthermal plasma activation. In situ and operando infrared, solid-state NMR, and EPR spectroscopy reveal the critical role of copper sites in the adsorption and activation of NO 2 molecules, with the formation of {Cu(I)···NO} and {Cu···NO 2 } adducts promoting the conversion of NO 2 to N 2 . This study will inspire the further design and study of new efficient single-atom catalysts for NO 2 abatement via detailed unravelling of their role in catalysis.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Fiber Composites of Metal–Organic Frameworks
The high chemical and structural diversity of metal–organic frameworks (MOFs), which are porous crystalline materials, has attracted significant academic and industrial interest. However, the poor processability of MOF powders limits their full potential in practical applications. Toward this end, MOF-based composite materials increase the framework robustness and subsequent utility. Among these hybrid materials, MOF composites prepared on commercially available textile fibers offer the high flexibility needed for important applications—such as heterogeneous catalysis, chemical sensing, pollutant removal, and drug release—while maintaining the functional properties of MOFs. The ability to further tailor these composites’ shapes for incorporation into industrial equipment increases their potential in applications such as adsorption devices and protective gears. In this Review, we summarize recently reported MOF/fiber fabrication methods and applications. In conclusion, our discussion on the advancements and remaining issues of these production methods segues into several highlighted applications of MOF/fiber composites, especially within adsorption devices and protective gears.
36 MATERIALS SCIENCE↗
Comparing Classical and Machine Learning Force Fields for Modeling Deformation of Metal–Organic Frameworks Relevant for Direct Air Capture
Deformation of metal–organic frameworks (MOFs) induced by adsorbate molecules can affect adsorption properties such as capacity and selectivity, but most computational studies of MOFs assume framework rigidity to simplify calculations. Although flexible force fields (FFs) for MOFs have been parametrized for specific materials, the generality of FFs for reliably modeling adsorbate-induced deformation to accuracy nearing that of density functional theory (DFT) has not been established. This work confirms using DFT calculations that adsorbate-induced deformation can affect CO 2 and H 2 O adsorption energies in a considerable fraction of MOFs promising for direct air capture (DAC). We then benchmark the efficacy of several general-purpose FFs in describing adsorbate-induced deformation for DAC against DFT. Our results show that current classical FFs are insufficient for describing MOF deformation, especially in cases of interest for DAC where strong interactions exist between adsorbed molecules and MOF frameworks. Some emerging machine learning force fields (MLFFs) we tested, particularly CHGNet, MACE-MP-0, and Equiformer V2, appear to be more promising than the classical FF for emulating the deformation behavior described by DFT. The best performing FF (CHGNet), however, fails to achieve the accuracy required for practical predictions with a mean absolute adsorption energy error of 0.124 eV.
adsorption↗
Role of Metal–Organic Framework Topology on Thermodynamics of Polyoxometalate Encapsulation
Polyoxometalates (POMs) are discrete anionic clusters whose rich redox properties, strong Brønsted acidity, and high availability of active sites poise them as potent catalysts for oxidation reactions. Here, metal–organic frameworks (MOFs) have emerged as tunable, porous platforms to immobilize POMs, thus increasing their solution stability and catalytic activity. While POM@MOF composite materials have been widely used for a variety of applications, little is known about the thermodynamics of the encapsulation process. Here, we utilize an up-and-coming technique in the field of heterogeneous materials, isothermal titration calorimetry (ITC), to obtain full thermodynamic profiles (ΔH, ΔS, ΔG, K a ) of POM binding. Six different 8-connected hexanuclear Zr-MOFs were investigated to determine the impact of MOF topology (csq, scu, the) on POM encapsulation thermodynamics.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Photogenerated Charge Separation in a CdSe Nanocluster Encapsulated in a Metal–Organic Framework for Improved Photocatalysis
Nanoclusters encapsulated in a metal–organic framework (MOF) are the subject of intense interest because of their high promise for photocatalysis. We show computationally that a CdSe nanocluster incorporated into NU-1000 (Cd 6 Se 6 @NU-1000) allows electron transfer from a visible-light photo-excited organic linker to the lowest unoccupied crystal orbital of the inorganic cluster, which can lead to charge separation. Substituents on the linker can be used to tune the band position and the band gap of the whole composite (Cd 6 Se 6 @NU-1000), and this makes it possible to perform the water splitting reaction under visible light. Here, the achievement of charge separation within the MOF leads to longer life of the excited states, and as a result, it can enhance the photocatalytic activity of the system.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Rapid Generation of Hierarchically Porous Metal–Organic Frameworks through Laser Photolysis
Abstract Hierarchically porous metal–organic frameworks (HP‐MOFs) facilitate mass transfer due to mesoporosity while preserving the advantage of microporosity. This unique feature endows HP‐MOFs with remarkable application potential in multiple fields. Recently, new methods such as linker labilization for the construction of HP‐MOFs have emerged. To further enrich the synthetic toolkit of MOFs, we report a controlled photolytic removal of linkers to create mesopores within microporous MOFs at tens of milliseconds. Ultraviolet (UV) laser has been applied to eliminate “photolabile” linkers without affecting the overall crystallinity and integrity of the original framework. Presumably, the creation of mesopores can be attributed to the missing‐cluster defects, which can be tuned through varying the time of laser exposure and ratio of photolabile/robust linkers. Upon laser exposure, MOF crystals shrank while metal oxide nanoparticles formed giving rise to the HP‐MOFs. In addition, photolysis can also be utilized for the fabrication of complicated patterns with high precision, paving the way towards MOF lithography, which has enormous potential in sensing and catalysis.
Wang, Kun‐Yu↗
Metal-Mediated Directional Capping of Rod-Packing Metal–Organic Frameworks
We report two new rod-packing metal–organic frameworks (RPMOF) are constructed by regulating the in situ formation of the capping agent. In CPM-s7, carboxylate linkers extend 1D manganese-oxide chains in four additional directions, forming 3D RPMOF. The substitution of Mn 2+ with a stronger Lewis acidic Co 2+ , leads to an acceleration of the hydrolysis-prone sulfonate linker, resulting in presence of sulfate ions to reduce two out of the four carboxylate-extending directions, and thus forming a new 2D rod-packing CPM-s8. Density functional theory calculations and magnetization measurements reveal ferrimagnetic ordering of CPM-s8, signifying the potential of exploring 2D RPMOF for effective low-dimensional magnetic materials.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Kinetic Separation of Siloxanes in Metal–Organic Frameworks
We present an in silico assessment of metal–organic frameworks (MOFs) for the kinetic separation of linear and cyclic siloxanes. We employed molecular dynamics simulations investigating both rigid and flexible 1D MOF frameworks to identify a specific range of pore parameters that enables the diffusion of linear siloxanes but leads to slow diffusion of cyclic siloxanes. We then extended our analysis to flexible 3D MOFs to select adsorbents for the kinetic separation of cyclic and linear siloxanes. Based on synthesizability metrics we identified four 3D MOFs capable of discriminating between cyclic and linear siloxanes. One of the MOFs with structure code WIYFAM stood out with the ability to distinguish between cyclic and linear siloxanes and facilitate the diffusion of all linear siloxanes investigated in this study. One of the other MOFs, IRMOF-6, is found to be capable of not only discriminating between cyclic and linear siloxanes, but even between shorter and longer linear siloxanes.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Novel in-capsule synthesis of metal–organic framework for innovative carbon dioxide capture system
Metal-Organic Frameworks (MOFs) have been developed as solid sorbents for CO2 capture applications and their properties can be controlled by tuning the chemical blocks of their crystalline units. A number of MOFs (e.g., HKUST-1) have been developed but the question remains how to deploy them for gas–solid contact. Unfortunately, the direct use of MOFs as nanocrystals would lead to serious problems and risks. Here, for the first time, we report a novel MOF-based hybrid sorbent that is produced via an innovative in-situ microencapsulated synthesis. Using a custom-made double capillary microfluidic assembly, double emulsions of the MOF precursor solutions and UV-curable silicone shell fluid are produced. Subsequently, HKUST-1 MOF is successfully synthesized within the droplets enclosed in the gas permeable microcapsules. The developed MOF-bearing microcapsules uniquely allow the deployment of functional nanocrystals without the challenge of handling ultrafine particles, and further, can selectively reject undesired compounds to protect encapsulated MOFs.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Cu[Ni(2,3-pyrazinedithiolate) 2 ] Metal–Organic Framework for Electrocatalytic Hydrogen Evolution
The application of metal–organic frameworks (MOFs) as electrocatalysts for small molecule activation has been an emerging topic of research. Previous studies have suggested that two-dimensional (2D) dithiolene-based MOFs are among the most active for the hydrogen evolution reaction (HER). Here, a three-dimensional (3D) dithiolene-based MOF, Cu[Ni(2,3-pyrazinedithiolate) 2 ] (1), is evaluated as an electrocatalyst for the HER. In pH 1.3 aqueous electrolyte solution, 1 exhibits a catalytic onset at –0.43 V vs the reversible hydrogen electrode (RHE), an overpotential (η 10 mA/cm 2 ) of 0.53 V to reach a current density of 10 mA/cm 2 , and a Tafel slope of 69.0 mV/dec. Interestingly, under controlled potential electrolysis, 1 undergoes an activation process that results in a more active catalyst with a 200 mV reduction in the catalytic onset and η 10 mA/cm 2 . It is proposed that the activation process is a result of the cleavage of Cu–N bonds in the presence of protons and electrons. Furthermore, this hypothesis is supported by various experimental studies and density functional theory calculations.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Optimizing iodine adsorption in functionalized metal-organic frameworks via an unprecedented positional isomerism strategy
Porous metal–organic frameworks (MOFs) have emerged as highly promising adsorbents for capturing radioiodine, a predominant fission product released during nuclear fuel reprocessing. However, systematic investigations into the correlation between MOF structure and iodine uptake capacity remain scarce. Here, we present a novel approach to enhance the iodine adsorption capacity of MOFs by optimizing linker functionalization. Using ligand-functionalized thorium-based MOFs as a structural platform, we demonstrate that ortho-amino-substitution near the node of the dicarboxylate linker significantly increases iodine adsorption capacity compared to meta-amino-substitution, where the amino groups are directed away from the node. Specifically, ortho-substituted Th-UiO-68-3,3”-(NH 2 ) 2 exhibits higher iodine uptake capacities than the meta-substituted Th-UiO-68-2,2”-(NH 2 ) 2 via both vapor diffusion-based (2.042 vs. 1.087 g/g) and solution-based (0.841 vs. 0.784 g/g) processes. Notably, the I 2 vapor adsorption capacity (2.042 g/g) of Th-UiO-68-3,3”-(NH 2 ) 2 represents the second highest among all reported Th-MOFs. Pair distribution function (PDF) studies reveal that the superior iodine uptake performance of ortho-functionalized MOFs can be attributed to the reduced steric hindrance of the amino groups compared with the meta-substituted variants. Finally, this research highlights how positional isomerism and its subtle alterations can significantly influence host–guest interactions, extending beyond simple structural considerations.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Equilibrium Separation of Siloxanes in Metal–Organic Frameworks
We present an in silico assessment of metal–organic frameworks (MOFs) for the equilibrium separation of linear and cyclic siloxanes. Using a combination of configurational bias/continuous fractional component Monte Carlo (CB/CFCMC) simulations and Ideal Adsorbed Solution Theory (IAST), we investigated the adsorption of both equimolar and nonequimolar mixtures of linear and cyclic siloxanes in a selection of synthesizable MOFs with medium to large pore volumes. We showed that configurational entropy effects drive the preferential adsorption of linear siloxanes over cyclic siloxanes. Based on synthesizability metrics we identified ZIF-70 as a promising adsorbent for the separation of linear and cyclic siloxanes. Self-diffusivities of linear and cyclic siloxanes in ZIF-70 calculated from molecular dynamics simulations show that equilibrium can be reached on reasonable time scales. We explored vacuum-temperature swing adsorption (VTSA) as a potential method for the recovery of adsorbed linear siloxanes from ZIF-70, achieving a 75% reduction in adsorbed phase concentration. Additionally, we demonstrated that supercritical CO 2 offers an alternative desorption strategy by displacing adsorbed linear siloxanes in ZIF-70 at pressures above 200 bar driven by entropy effects.
Adsorption↗
Meniscus Guided Coating and Evaporative Crystallization of UiO-66 Metal Organic Framework Thin Films
Thin-film fabrication of metal organic frameworks (MOFs) has been explored for a range of applications, including separations, catalysis, sensing, and charge transport. However, many fabrication techniques have obstacles, including slow crystallization, control over film thickness, and control over crystallinity. Recently, a meniscus-guided coating technique, called solution shearing, has been shown to create MOF thin films within minutes and with control over the film thickness. However, there have been no previous reports of solution shearing based evaporative crystallization of zirconium-based MOFs, which have been widely studied for the aforementioned applications. In this work, for the first time, we show that (i) the zirconium 1,4-dicarboxybenzene MOF, UiO-66, can be formed using evaporative crystallization during solution shearing, and (ii) a wide range of parameters can be tuned to control the film thickness, coverage, and crystallinity. Finally, we bring the solution shearing technique closer to separation applications by growing a full film of UiO-66 crystals up to the resolution of scanning electron microscopy (SEM) on anodic alumina oxide (AAO). This is the first instance of UiO-66 crystals being formed using an evaporative crystallization-based flow coating method, and solution shearing shows the promise to be applicable to form large area zirconium-based MOF crystals in a rapid manner (within seconds to minutes).
42 ENGINEERING↗
Tunable Metal–Organic Frameworks Based on 8-Connected Metal Trimers for High Ethane Uptake
Metal trimers [M 3 (O/OH)](OOCR) 6 are among the most important structural building blocks. From these trimers, a great success has been achieved in the design of 6- or 9-connected framework materials with various topological features and outstanding gas-sorption properties. In comparison, 8-connected trimer-based MOFs are rare. Given multiple competitive pathways for the formation of 6- or 9-connected frameworks, it remains challenging to identify synthetic or structural parameters that can be used to direct self-assembly process towards trimer-based 8-connected materials. Here, we reveal a viable strategy called angle bending modulation for creating a prototypical MOF type based on 8-connected M 3 (OH)(OOCR) 5 (Py-R) 3 trimers, M = Zn, Co, Fe). As a proof of concept, we synthesized six members in this family using three types of ligands (CPM-80, -81, and -82). These materials do not possess open-metal sites and show excellent uptake capacity for various hydrocarbon gas molecules and inverse C 2 H 6 /C 2 H 4 selectivity. CPM-81-Co, made from 2,5-furandicarboxylate and isonicotinate, features selectivity of 1.80 with high uptake capacity for ethane (123 cm 3 /g -1 ) and ethylene (113 cm 3 /g -1 ) at 298 K and 1 bar.
36 MATERIALS SCIENCE↗