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Porous solids can accommodate and release molecular hydrogen readily, making them attractive for minimizing the energy requirements for hydrogen storage relative to physical storage systems. However, H2 adsorption enthalpies in such materials are generally weak (-3 to -7 kJ/mol), lowering capacities at ambient temperature. Metal-organic frameworks with well-defined structures and synthetic modularity could allow for tuning adsorbent-H2 interactions for ambient-temperature storage. Recently, Cu2.2Zn2.8Cl1.8(btdd)3 (H2btdd = bis(1H-1,2,3-triazolo-[4,5-b],[4',5'-i])dibenzo[1,4]dioxin; CuI-MFU-4l) was reported to show a large H2 adsorption enthalpy of -32 kJ/mol owing to π-backbonding from CuI to H2, exceeding the optimal binding strength for ambient-temperature storage (-15 to -25 kJ/mol). Toward realizing optimal H2 binding, we sought to modulate the π-backbonding interactions by tuning the pyramidal geometry of the trigonal CuI sites. A series of isostructural frameworks, Cu2.7M2.3X1.3(btdd)3 (M = Mn, Cd; X = Cl, I; CuIM-MFU-4l), was synthesized through postsynthetic modification of the corresponding materials M5X4(btdd)3 (M = Mn, Cd; X = CH3CO2, I). This strategy adjusts the H2 adsorption enthalpy at the CuI sites according to the ionic radius of the central metal ion of the pentanuclear cluster node, leading to -33 kJ/mol for M = ZnII (0.74 Å), -27 kJ/mol for M = MnII (0.83 Å), and -23 kJ/mol for M = CdII (0.95 Å). Thus, CuICd-MFU-4l provides a second, more stable example of optimal H2 binding energy for ambient-temperature storage among reported metal-organic frameworks. Structural, computational, and spectroscopic studies indicate that a larger central metal planarizes trigonal CuI sites, weakening the π-backbonding to H2.
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Materials-based H2 storage plays a critical role in facilitating H2 as a low-carbon energy carrier, but there remains limited guidance on the technical performance necessary for specific applications. Metal-organic framework (MOF) adsorbents have shown potential in power applications, but need to demonstrate economic promises against incumbent compressed H2 storage. Herein, we evaluate the potential impact of material properties, charge/discharge patterns, and propose targets for MOFs' deployment in long-duration energy storage applications including backup, load optimization, and hybrid power. We find that state-of-the-art MOF could outperform cryogenic storage and 350 bar compressed storage in applications requiring ≤8 cycles per year, but need ≥5 g/L increase in uptake to be cost-competitive for applications that require ≥30 cycles per year. Existing challenges include manufacturing at scale and quantifying the economic value of lower-pressure storage. Lastly, future research needs are identified including integrating thermodynamic effects and degradation mechanisms.
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A detailed chemical understanding of H2 interactions with binding sites in the nanoporous crystalline structure of metal-organic frameworks (MOFs) can lay a sound basis for the design of new sorbent materials. Computational quantum chemical calculations can aid in this quest. To set the stage, we review general thermodynamic considerations that control the usable storage capacity of a sorbent. We then discuss cluster modeling of H2 ligation at MOF binding sites using state-of-the-art density functional theory (DFT) calculations, and how the binding can be understood using energy decomposition analysis (EDA). Employing these tools, we illustrate the connections between the character of the MOF binding site and the associated adsorption thermodynamics using four experimentally characterized MOFs, highlighting the role of open metal sites (OMSs) in accessing binding strengths relevant to room temperature storage. The sorbents are MOF-5, with no open metal sites, Ni2(m-dobdc), containing Lewis acidic Ni(II) sites, Cu(I)-MFU-4l, containing π basic Cu(I) sites and V2Cl2.8(btdd), also containing π-basic V(II) sites. We next explore the potential for binding multiple H2 molecules at a single metal site, with thermodynamics useful for storage at ambient temperature; a materials design goal which has not yet been experimentally demonstrated. Computations on Ca2+ or Mg2+ bound to catecholate or Ca2+ bound to porphyrin show the potential for binding up to 4 H2; there is precedent for the inclusion of both catecholate and porphyrin motifs in MOFs. Turning to transition metals, we discuss the prediction that two H2 molecules can bind at V(II)-MFU-4l, a material that has been synthesized with solvent coordinated to the V(II) site. Additional calculations demonstrate binding three equivalents of hydrogen per OMS in Sc(I) or Ti(I)-exchanged MFU-4l. Overall, the results suggest promising prospects for experimentally realizing higher capacity hydrogen storage MOFs, if nontrivial synthetic and desolvation challenges can be overcome. Coupled with the unbounded chemical diversity of MOFs, there is ample scope for additional exploration and discovery.
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High or enriched-purity O2 is used in numerous industries and is predominantly produced from the cryogenic distillation of air, an extremely capital- and energy-intensive process. There is significant interest in the development of new approaches for O2-selective air separations, including the use of metal-organic frameworks featuring coordinatively unsaturated metal sites that can selectively bind O2 over N2 via electron transfer. However, most of these materials exhibit appreciable and/or reversible O2 uptake only at low temperatures, and their open metal sites are also potential strong binding sites for the water present in air. Here, we study the framework CuI-MFU-4l (CuxZn5-xCl4-x(btdd)3; H2btdd = bis(1H-1,2,3-triazolo[4,5-b],[4',5'-i])dibenzo[1,4]dioxin), which binds O2 reversibly at ambient temperature. We develop an optimized synthesis for the material to access a high density of trigonal pyramidal CuI sites, and we show that this material reversibly captures O2 from air at 25 °C, even in the presence of water. When exposed to air up to 100% relative humidity, CuI-MFU-4l retains a constant O2 capacity over the course of repeated cycling under dynamic breakthrough conditions. While this material simultaneously adsorbs N2, differences in O2 and N2 desorption kinetics allow for the isolation of high-purity O2 (>99%) under relatively mild regeneration conditions. Spectroscopic, magnetic, and computational analyses reveal that O2 binds to the copper(I) sites to form copper(II)-superoxide moieties that exhibit temperature-dependent side-on and end-on binding modes. Overall, these results suggest that CuI-MFU-4l is a promising material for the separation of O2 from ambient air, even without dehumidification.
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Materials that simultaneously exhibit permanent porosity and high-temperature magnetic order could lead to advances in fundamental physics and numerous emerging technologies. Herein, we show that the archetypal molecule-based magnet and magnonic material V(TCNE)2 (TCNE = tetracyanoethylene) can be desolvated to generate a room-temperature microporous magnet. The solution-phase reaction of V(CO)6 with TCNE yields V(TCNE)2·0.95CH2Cl2, for which a characteristic temperature of T* = 646 K is estimated from a Bloch fit to variable-temperature magnetization data. Removal of the solvent under reduced pressure affords the activated compound V(TCNE)2, which exhibits a T* value of 590 K and permanent microporosity (Langmuir surface area of 850 m2/g). The porous structure of V(TCNE)2 is accessible to the small gas molecules H2, N2, O2, CO2, ethane, and ethylene. While V(TCNE)2 exhibits thermally activated electron transfer with O2, all the other studied gases engage in physisorption. The T* value of V(TCNE)2 is slightly modulated upon adsorption of H2 (T* = 583 K) or CO2 (T* = 596 K), while it decreases more significantly upon ethylene insertion (T* = 459 K). These results provide an initial demonstration of microporosity in a room-temperature magnet and highlight the possibility of further incorporation of small-molecule guests, potentially even molecular qubits, toward future applications.
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Step-shaped adsorption-desorption of gaseous payloads by flexible metal-organic frameworks can facilitate the delivery of large usable capacities with significantly reduced energetic penalties. This is desirable for the storage, transport, and delivery of H2, as prototypical adsorbents require large swings in pressure and temperature to achieve usable capacities approaching their total capacities. However, the weak physisorption of H2 typically necessitates undesirably high pressures to induce the framework phase change. As de novo design of flexible frameworks is exceedingly challenging, the ability to intuitively adapt known frameworks is required. We demonstrate that the multivariate linker approach is a powerful tool for tuning the phase change behavior of flexible frameworks. In this work, 2-methyl-5,6-difluorobenzimidazolate was solvothermally incorporated into the known framework CdIF-13 (sod-Cd(benzimidazolate)2), resulting in the multivariate framework sod-Cd(benzimidazolate)1.87(2-methyl-5,6-difluorobenzimidazolate)0.13 (ratio = 14:1), which exhibited a considerably reduced stepped adsorption threshold pressure while maintaining the desirable adsorption-desorption profile and capacity of CdIF-13. At 77 K, the multivariate framework exhibits stepped H2 adsorption with saturation below 50 bar and minimal desorption hysteresis at 5 bar. At 87 K, saturation of step-shaped adsorption occurs by 90 bar, with hysteresis closing at 30 bar. These adsorption-desorption profiles enable usable capacities in a mild pressure swing process above 1 mass %, representing 85-92% of the total capacities. This work demonstrates that the desirable performance of flexible frameworks can be readily adapted through the multivariate approach to enable efficient storage and delivery of weakly physisorbing species.
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Ammonia is a critical chemical in agriculture and industry that is produced on a massive scale via the Haber-Bosch process1. The environmental impact of this process, which uses methane as a fuel and feedstock for hydrogen, has motivated the need for more sustainable ammonia production2-5. However, many strategies that use renewable hydrogen are not compatible with existing methods for ammonia separation6-9. Given their high surface areas and structural and chemical versatility, metal-organic frameworks (MOFs) hold promise for ammonia separations, but most MOFs bind ammonia irreversibly or degrade on exposure to this corrosive gas10,11. Here we report a tunable three-dimensional framework that reversibly binds ammonia by cooperative insertion into its metal-carboxylate bonds to form a dense, one-dimensional coordination polymer. This unusual adsorption mechanism provides considerable intrinsic thermal management12, and, at high pressures and temperatures, cooperative ammonia uptake gives rise to large working capacities. The threshold pressure for ammonia adsorption can further be tuned by almost five orders of magnitude through simple synthetic modifications, pointing to a broader strategy for the development of energy-efficient ammonia adsorbents.
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Densifying hydrogen in a metal-organic framework (MOF) at moderate pressures can circumvent challenges associated with high-pressure compression. The highly tunable structural and chemical composition in MOFs affords vast possibilities to optimize binding interactions. At the heart of this search are the nanoscale characteristics of molecular adsorption at the binding site(s). Using density functional theory (DFT) to model binding interactions of hydrogen to the exposed metal site of cation-exchanged MFU-4l, we predict multiple hydrogen ligation of H2 at the first coordination sphere of V(II) in V(II)-exchanged MFU-4l. We find that the strength of this binding between the metal site and H2 molecules can be tuned by altering the halide counterion adjacent to the metal site and that the fluoride containing node affords the most favorable interactions for high-density H2 storage. Using energy decomposition analysis, we delineate electronic contributions that enable multiple hydrogen ligation and demonstrate its benefits for hydrogen adsorption and release at modest pressures.
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Estructuras Metalorgánicas , Compuestos Organometálicos , Hidrógeno/química , Vanadio , Compuestos Organometálicos/química , AdsorciónRESUMEN
Metal-organic frameworks (MOFs) are an emerging class of materials employed for custom-designed purposes by judicious selection of linkers and metal ions. Among the MOFs composed of carboxylate linkers, Zr-based MOFs have attracted great attention due to their high thermal and chemical stabilities, which are important for practical applications, including capturing CO2 from a point source. UiO-67(bipy) containing 2,2'-bipyridine-5,5'-dicarboxylate is particularly useful among the Zr-MOF family due to the Lewis basic sites of the linker; however, the hydrolytic stability of UiO-67(bipy) does not seem to be as high as those of UiO-66 and UiO-67. To improve the hydrolytic stability without sacrificing the adsorption enthalpy of CO2 for selective CO2 capture, in this study, we added hydrophobic methyl groups to the backbone of the bipyridine linker. The synthesized 6,6'-dimethyl-2,2'-bipyridine-5,5'-dicarboxylic acid (H2Me2bipy) was used to prepare a Zr-based MOF [MOF-553, Zr6O4(OH)4(Me2Bipy)6]. In addition, the water stability and CO2 adsorption capacity of MOF-553 were compared to those of UiO-67(bipy). We revealed that MOF-553 is more robust and has a higher CO2 adsorption capacity than UiO-67(bipy), indicating that the methylation of the linker improves the water stability of the framework, which is advantageous for point-source CO2 capture.
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The widespread implementation of H2 as a fuel is currently hindered by the high pressures or cryogenic temperatures required to achieve reasonable storage densities. In contrast, the realization of materials that strongly and reversibly adsorb hydrogen at ambient temperatures and moderate pressures could transform the transportation sector and expand adoption of fuel cells in other applications. To date, however, no adsorbent has been identified that exhibits a binding enthalpy within the optimal range of -15 to -25 kJ/mol for ambient-temperature hydrogen storage. Here, we report the hydrogen adsorption properties of the metal-organic framework (MOF) V2Cl2.8(btdd) (H2btdd, bis(1H-1,2,3-triazolo[4,5-b],[4',5'-i])dibenzo[1,4]dioxin), which features exposed vanadium(II) sites capable of backbonding with weak π acids. Significantly, gas adsorption data reveal that this material binds H2 with an enthalpy of -21 kJ/mol. This binding energy enables usable hydrogen capacities that exceed that of compressed storage under the same operating conditions. The Kubas-type vanadium(II)-dihydrogen complexation is characterized by a combination of techniques. From powder neutron diffraction data, a V-D2(centroid) distance of 1.966(8) Å is obtained, the shortest yet reported for a MOF. Using in situ infrared spectroscopy, the H-H stretch was identified, and it displays a red shift of 242 cm-1. Electronic structure calculations show that a main contribution to bonding stems from the interaction between the vanadium dπ and H2 σ* orbital. Ultimately, the pursuit of MOFs containing high densities of weakly π-basic metal sites may enable storage capacities under ambient conditions that far surpass those accessible with compressed gas storage.
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The design of stable adsorbents capable of selectively capturing dioxygen with a high reversible capacity is a crucial goal in functional materials development. Drawing inspiration from biological O2 carriers, we demonstrate that coupling metal-based electron transfer with secondary coordination sphere effects in the metal-organic framework Co2(OH)2(bbta) (H2bbta = 1H,5H-benzo(1,2-d:4,5-d')bistriazole) leads to strong and reversible adsorption of O2. In particular, moderate-strength hydrogen bonding stabilizes a cobalt(III)-superoxo species formed upon O2 adsorption. Notably, O2-binding in this material weakens as a function of loading, as a result of negative cooperativity arising from electronic effects within the extended framework lattice. This unprecedented behavior extends the tunable properties that can be used to design metal-organic frameworks for adsorption-based applications.
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Iron is one of the most abundant elements in the environment and in the human body. As an essential nutrient, iron homeostasis is tightly regulated, and iron dysregulation is implicated in numerous pathologies, including neuro-degenerative diseases, atherosclerosis, and diabetes. Endogenous iron pool concentrations are directly linked to iron ion uptake from environmental sources such as drinking water, providing motivation for developing new technologies for assessing iron(ii) and iron(iii) levels in water. However, conventional methods for measuring aqueous iron pools remain laborious and costly and often require sophisticated equipment and/or additional processing steps to remove the iron ions from the original environmental source. We now report a simplified and accurate chemical platform for capturing and quantifying the iron present in aqueous samples through use of a post-synthetically modified porous aromatic framework (PAF). The ether/thioether-functionalized network polymer, PAF-1-ET, exhibits high selectivity for the uptake of iron(ii) and iron(iii) over other physiologically and environmentally relevant metal ions. Mössbauer spectroscopy, XANES, and EXAFS measurements provide evidence to support iron(iii) coordination to oxygen-based ligands within the material. The polymer is further successfully employed to adsorb and remove iron ions from groundwater, including field sources in West Bengal, India. Combined with an 8-hydroxyquinoline colorimetric indicator, PAF-1-ET enables the simple and direct determination of the iron(ii) and iron(iii) ion concentrations in these samples, providing a starting point for the design and use of molecularly-functionalized porous materials for potential dual detection and remediation applications.
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A Zr(IV)-based metal-organic framework (MOF), termed reo-MOF-1 [Zr6O8(H2O)8(SNDC)4], composed of 4-sulfonaphthalene-2,6-dicarboxylate (HSNDC2-) linkers and Zr6O8(H2O)8(CO2)8 clusters was synthesized by solvothermal synthesis. Structural analysis revealed that reo-MOF-1 adopts the reo topology highlighted with large cuboctahedral cages (23 Å). This structure is similar to that found in DUT-52 (fcu topology), however, reo-MOF-1 lacks the body-centered packing of the 12-connected Zr6O4(OH)4(CO2)12 clusters, which is attributed to the subtle, but crucial influence in the bulkiness of functional groups on the linkers. The control experiments, where the ratio of H3SNDC/naphthalene-2,6-dicarboxylate linkers was varied, also support our finding that the bulky functionalities play a key role for defect-controlled synthesis. The reo-MOF-1A framework was obtained by linker exchange to yield a chemically and thermally stable material despite its large pores. Remarkably, reo-MOF-1A exhibits permanent porosity (Brunauer-Emmett-Teller and Langmuir surface areas of 2104 and 2203 m2 g-1, respectively). Owing to these remarkable structural features, reo-MOF-1A significantly enhances the yield in Brønsted acid-catalyzed reactions.
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In their comment, Bui et al argue that the approach we described in our report is vastly inferior in efficiency to alternative off-the-shelf technologies. Their conclusion is invalid, as they compare efficiencies in completely different operating conditions. Here, using heat transfer and thermodynamics principles, we show how Bui et al's conclusions about the efficiencies of off-the-shelf technologies are fundamentally flawed and inaccurate for the operating conditions described in our study.
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Luz Solar , Agua , Estructuras MetalorgánicasRESUMEN
The Comment by Meunier states that the process we described in our report cannot deliver the claimed amount of liquid water in an arid climate. This statement is not valid because the parameters presented in our study were inappropriately combined to draw misguided conclusions.
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Luz Solar , Agua , Clima Desértico , Estructuras MetalorgánicasRESUMEN
A combined inelastic neutron scattering (INS) and theoretical study was carried out on H2 adsorbed in two covalent organic framework (COF) materials: COF-1 and COF-102. These COFs are synthesized from self-condensation reactions of 1,4-benzenediboronic acid (BDBA) and tetra(4-(dihydroxy)borylphenyl)methane (TBPM) molecules, respectively. Molecular simulations of H2 adsorption in COF-1 revealed that the H2 molecules occupy the region between two eclipsed layers of the COF. The most favorable H2 binding site in COF-1 is located between two B3O3 clusters of the eclipsed layers. Two distinct H2 binding sites were identified in COF-102 from the simulations: the B3O3 clusters and the phenyl rings of the tetraphenylmethyl units. Two-dimensional quantum rotation calculations for H2 adsorbed at the considered sites in both COFs resulted in rotational transitions that are in good agreement with those that appear in the corresponding INS spectra. Such calculations were important for interpreting the INS spectra in these materials. Calculation of the rotational potential energy surface for H2 bound at the most favorable adsorption site in COF-1 and COF-102 revealed unusually high rotational barriers that are attributed to the nature of the B3O3 rings. The values for these barriers to rotation are greater than or comparable to those observed in some metal-organic frameworks (MOFs) that possess open-metal sites. This study demonstrates the power of using INS experiments in conjunction with theoretical calculations to gain valuable insights into the nature of the binding sites and, for the first time, the rotational dynamics of H2 adsorbed in COFs.
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Atmospheric water is a resource equivalent to ~10% of all fresh water in lakes on Earth. However, an efficient process for capturing and delivering water from air, especially at low humidity levels (down to 20%), has not been developed. We report the design and demonstration of a device based on a porous metal-organic framework {MOF-801, [Zr6O4(OH)4(fumarate)6]} that captures water from the atmosphere at ambient conditions by using low-grade heat from natural sunlight at a flux of less than 1 sun (1 kilowatt per square meter). This device is capable of harvesting 2.8 liters of water per kilogram of MOF daily at relative humidity levels as low as 20% and requires no additional input of energy.
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High methane storage capacity in porous materials is important for the design and manufacture of vehicles powered by natural gas. Here, we report the synthesis, crystal structures and methane adsorption properties of five new zinc metal-organic frameworks (MOFs), MOF-905, MOF-905-Me2, MOF-905-Naph, MOF-905-NO2, and MOF-950. All these MOFs consist of the Zn4O(-CO2)6 secondary building units (SBUs) and benzene-1,3,5-tri-ß-acrylate, BTAC. The permanent porosity of all five materials was confirmed, and their methane adsorption measured up to 80 bar to reveal that MOF-905 is among the best performing methane storage materials with a volumetric working capacity (desorption at 5 bar) of 203 cm(3) cm(-3) at 80 bar and 298 K, a value rivaling that of HKUST-1 (200 cm(3) cm(-3)), the benchmark compound for methane storage in MOFs. This study expands the scope of MOF materials with ultrahigh working capacity to include linkers having the common acrylate connectivity.
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A presynthesized, square planar copper imidazole complex, [Cu(imidazole)4](NO3)2, was utilized as a precursor in the synthesis of a new series of zeolitic imidazolate frameworks, termed ZIF-202, -203, and -204. The structures of all three members were solved by single-crystal X-ray diffraction analysis, which revealed ZIF-203 and -204 having successfully integrated square planar units within the backbones of their respective frameworks. As a result of this unit, the structures of both ZIF-203 and -204 were found to adopt unprecedented three-dimensional nets, namely, ntn and thl, respectively. One member of this series, ZIF-204, was demonstrated to be highly porous, exhibit exceptional stability in water, and selectively capture CO2 over CH4 under both dry and wet conditions without any loss in performance over three cycles. Remarkably, the regeneration of ZIF-204 was performed under the mild conditions of flowing a pure N2 gas through the material at ambient temperature.
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The design of enzyme-like complexity within metal-organic frameworks (MOFs) requires multiple reactions to be performed on a MOF crystal without losing access to its interior. Here, we show that seven post-synthetic reactions can be successfully achieved within the pores of a multivariate MOF, MTV-IRMOF-74-III, to covalently incorporate tripeptides that resemble the active sites of enzymes in their spatial arrangement and compositional heterogeneity. These reactions build up H2N-Pro-Gly-Ala-CONHL and H2N-Cys-His-Asp-CONHL (where L = organic struts) amino acid sequences by covalently attaching them to the organic struts in the MOFs, without losing porosity or crystallinity. An enabling feature of this chemistry is that the primary amine functionality (-CH2NHBoc) of the original MOF is more reactive than the commonly examined aromatic amines (-NH2), and this allowed for the multi-step reactions to be carried out in tandem within the MOF. Preliminary findings indicate that the complexity thus achieved can affect reactions that were previously accomplished only in the presence of enzymes.