Adsorption of Natural Gas in Metal-Organic Frameworks: Selectivity, Cyclability, and Comparison to Methane Adsorption.

Evaluation of metal-organic frameworks (MOFs) for adsorbed natural gas (ANG) technology employs pure methane as a surrogate for natural gas (NG). This approximation is problematic, as it ignores the impact of other heavier hydrocarbons present in NG, such as ethane and propane, which generally have more favorable adsorption interactions with MOFs compared to methane. Herein, using quantitative Raman spectroscopic analysis and Monte Carlo calculations, we demonstrate the adsorption selectivity of high-performing MOFs, such as MOF-5, MOF-177, and SNU-70, for a methane and ethane mixture (95:5) that mimics the composition of NG. The impact of selectivity on the storage and deliverable capacities of these adsorbents during successive cycles of adsorption and desorption, simulating the filling and emptying of an ANG tank, is also demonstrated. The study reveals a gradual reduction in the storage performance of MOFs, particularly with smaller pore volumes, due to ethane accumulation over long-term cycling, until a steady state is reached with substantially degraded storage performance.

Superior Metal-Organic Framework Activation with Dimethyl Ether.

Metal-organic frameworks (MOFs) are demonstrated to be readily activated by treatment with the low surface tension, low boiling point solvent dimethyl ether (DME). The mildness of the method enables access to high surface areas by avoiding structural changes in the framework that often plague thermal activation methods. A distinction from previous methods is that DME activation succeeds for materials with coordinatively unsaturated sites (CUS) and non-CUS MOFs as well. DME displaces solvent molecules occupying the pores of the MOF as well as those coordinated to metal centers; reducing evacuation temperature by using a coordinating, yet highly volatile guest enables low temperature activation with structural retention as demonstrated surface area measurements that match or exceed existing activation protocols.

Ultra-photostable DNA FluoroCubes: Mechanism of Photostability and Compatibility with FRET and Dark Quenching.

DNA-based FluoroCubes were recently developed as a solution to photobleaching, a ubiquitous limitation of fluorescence microscopy (Niekamp; ; Stuurman; ; Vale Nature Methods, 2020). FluoroCubes, that is, compact ∼4 × 4 × 5.4 nm3 four-helix bundles coupled to ≤6 fluorescent dyes, remain fluorescent up to ∼50× longer than single dyes and emit up to ∼40× as many photons. The current work answers two important questions about the FluoroCubes. First, what is the mechanism by which photostability is enhanced? Second, are FluoroCubes compatible with Förster resonance energy transfer (FRET) and similar techniques? We use single particle photobleaching studies to show that photostability arises through interactions between the fluorophores and the four-helix DNA bundle. Supporting this, we discover that smaller ∼4 × 4 × 2.7 nm3 FluoroCubes also confer ultraphotostability. However, we find that certain dye-dye interactions negatively impact FluoroCube performance. Accordingly, 4-dye FluoroCubes lacking these interactions perform better than 6-dye FluoroCubes. We also demonstrate that FluoroCubes are compatible with FRET and dark quenching applications.

Linker Deprotonation and Structural Evolution on the Pathway to MOF-74.

The synthesis of MOF-74 (MOF = metal-organic framework) proceeds first through the generation of chemically and topologically distinct materials, referred to as phases, displaying exclusively carboxylate coordination, followed by further deprotonation to enable oxo coordination and MOF-74 formation. The synthesis of Mg-MOF-74 at high concentrations of linker and metal enables the stabilization and characterization of the previously unobserved, exclusively carboxylate coordinating phases. Ex situ and in situ approaches are leveraged to provide the time-resolved observation of Mg-MOF-74 synthesis and the formation of phases that precede Mg-MOF-74 formation as well as metastable phase dissolution. These data support dissolution and redeposition as the mechanism of MOF-74 formation and provide insight into the formation mechanism of MOFs with multiple linker coordination types.