Brønsted Acidity in Metal–Organic Frameworks

Brønsted Acidity in Metal–Organic Framework

Deconstructing the Crystal Structures of Metal–Organic Frameworks and Related Materials into Their Underlying Nets

Deconstructing the Crystal Structures of Metal–Organic Frameworks and Related Materials into Their Underlying Net

Isomers of Metal–Organic Complex Arrays

Three metal–organic complex arrays (MOCAs) with a specific sequence of metal centers as well as that of amino acid units were synthesized. These MOCAs are also isomers exhibiting a gelation capability dependent on the location of the metal complexes in the arrays

High Methane Storage Capacity in Aluminum Metal–Organic Frameworks

The use of porous materials to store natural gas in vehicles requires large amounts of methane per unit of volume. Here we report the synthesis, crystal structure and methane adsorption properties of two new aluminum metal–organic frameworks, MOF-519 and MOF-520. Both materials exhibit permanent porosity and high methane volumetric storage capacity: MOF-519 has a volumetric capacity of 200 and 279 cm³ cm^–3 at 298 K and 35 and 80 bar, respectively, and MOF-520 has a volumetric capacity of 162 and 231 cm³ cm^–3 under the same conditions. Furthermore, MOF-519 exhibits an exceptional working capacity, being able to deliver a large amount of methane at pressures between 5 and 35 bar, 151 cm³ cm^–3, and between 5 and 80 bar, 230 cm³ cm^–3

Modular Synthesis of Metal–Organic Complex Arrays Containing Precisely Designed Metal Sequences

A modular synthetic approach is reported for the synthesis of heterometallic metal–organic complex arrays (MOCAs). Modules of four metal centers containing three different metals copper­(II), nickel­(II), platinum­(II), or ruthenium­(II) are prepared using a solid-phase polypeptide synthesis technique and then linked in solution to make MOCAs of eight metal centers as linear, T-branched, and H-branched compounds. The MOCA molecular topologies thus have specific unique linear and branched sequences of metals along the peptide backbone

High Methane Storage Working Capacity in Metal–Organic Frameworks with Acrylate Links

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-β-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 cm³ cm^–3 at 80 bar and 298 K, a value rivaling that of HKUST-1 (200 cm³ 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

Molecular Retrofitting Adapts a Metal–Organic Framework to Extreme Pressure

Despite numerous studies on chemical and thermal stability of metal–organic frameworks (MOFs), mechanical stability remains largely undeveloped. To date, no strategy exists to control the mechanical deformation of MOFs under ultrahigh pressure. Here, we show that the mechanically unstable MOF-520 can be retrofitted by precise placement of a rigid 4,4′-biphenyldicarboxylate (BPDC) linker as a “girder” to afford a mechanically robust framework: MOF-520-BPDC. This retrofitting alters how the structure deforms under ultrahigh pressure and thus leads to a drastic enhancement of its mechanical robustness. While in the parent MOF-520 the pressure transmitting medium molecules diffuse into the pore and expand the structure from the inside upon compression, the girder in the new retrofitted MOF-520-BPDC prevents the framework from expansion by linking two adjacent secondary building units together. As a result, the modified MOF is stable under hydrostatic compression in a diamond-anvil cell up to 5.5 gigapascal. The increased mechanical stability of MOF-520-BPDC prohibits the typical amorphization observed for MOFs in this pressure range. Direct correlation between the orientation of these girders within the framework and its linear strain was estimated, providing new insights for the design of MOFs with optimized mechanical properties

Molecular Retrofitting Adapts a Metal–Organic Framework to Extreme Pressure

Despite numerous studies on chemical and thermal stability of metal–organic frameworks (MOFs), mechanical stability remains largely undeveloped. To date, no strategy exists to control the mechanical deformation of MOFs under ultrahigh pressure. Here, we show that the mechanically unstable MOF-520 can be retrofitted by precise placement of a rigid 4,4′-biphenyldicarboxylate (BPDC) linker as a “girder” to afford a mechanically robust framework: MOF-520-BPDC. This retrofitting alters how the structure deforms under ultrahigh pressure and thus leads to a drastic enhancement of its mechanical robustness. While in the parent MOF-520 the pressure transmitting medium molecules diffuse into the pore and expand the structure from the inside upon compression, the girder in the new retrofitted MOF-520-BPDC prevents the framework from expansion by linking two adjacent secondary building units together. As a result, the modified MOF is stable under hydrostatic compression in a diamond-anvil cell up to 5.5 gigapascal. The increased mechanical stability of MOF-520-BPDC prohibits the typical amorphization observed for MOFs in this pressure range. Direct correlation between the orientation of these girders within the framework and its linear strain was estimated, providing new insights for the design of MOFs with optimized mechanical properties

Impact of Disordered Guest–Framework Interactions on the Crystallography of Metal–Organic Frameworks

It is a general and common practice to carry out single-crystal X-ray diffraction experiments at cryogenic temperatures in order to obtain high-resolution data. In this report, we show that this practice is not always applicable to metal–organic frameworks (MOFs), especially when these structures are highly porous. Specifically, two new MOFs are reported here, MOF-1004 and MOF-1005, for which the collection of the diffraction data at lower temperature (100 K) did not give data of sufficient quality to allow structure solution. However, collection of data at higher temperature (290 K) gave atomic-resolution data for MOF-1004 and MOF-1005, allowing for structure solution. We find that this inverse behavior, contrary to normal practice, is also true for some well-established MOFs (MOF-177 and UiO-67). Close examination of the X-ray diffraction data obtained for all four of these MOFs at various temperatures led us to conclude that disordered guest–framework interactions play a profound role in introducing disorder at low temperature, and the diminishing strength of these interactions at high temperatures reduces the disorder and gives high-resolution diffraction data. We believe our finding here is more widely applicable to other highly porous MOFs and crystals containing highly disordered molecules

Chemical Environment Control and Enhanced Catalytic Performance of Platinum Nanoparticles Embedded in Nanocrystalline Metal–Organic Frameworks

Chemical environment control of the metal nanoparticles (NPs) embedded in nanocrystalline metal–organic frameworks (nMOFs) is useful in controlling the activity and selectivity of catalytic reactions. In this report, organic linkers with two functional groups, sulfonic acid (−SO₃H, S) and ammonium (−NH₃⁺, N), are chosen as strong and weak acidic functionalities, respectively, and then incorporated into a MOF [Zr₆O₄(OH)₄(BDC)₆ (BDC = 1,4-benzenedicarboxylate), termed UiO-66] separately or together in the presence of 2.5 nm Pt NPs to build a series of Pt NPs-embedded in UiO-66 (Pt⊂nUiO-66). We find that these chemical functionalities play a critical role in product selectivity and activity in the gas-phase conversion of methylcyclopentane (MCP) to acyclic isomer, olefins, cyclohexane, and benzene. Pt⊂nUiO-66-S gives the highest selectivity to C₆-cyclic products (62.4% and 28.6% for cyclohexane and benzene, respectively) without acyclic isomers products. Moreover, its catalytic activity was doubled relative to the nonfunctionalized Pt⊂nUiO-66. In contrast, Pt⊂nUiO-66-N decreases selectivity for C₆-cyclic products to <50% while increases the acyclic isomer selectivity to 38.6%. Interestingly, the Pt⊂nUiO-66-SN containing both functional groups gave different product selectivity than their constituents; no cyclohexane was produced, while benzene was the dominant product with olefins and acyclic isomers as minor products. All Pt⊂nUiO-66 catalysts with different functionalities remain intact and maintain their crystal structure, morphology, and chemical functionalities without catalytic deactivation after reactions over 8 h