Diamine Functionalization of a Metal-Organic Framework by Exploiting Solvent Polarity for Enhanced CO2 Adsorption.

Diamine-appended metal-organic frameworks (MOFs) exhibit exceptional CO2 adsorption capacities over a wide pressure range because of the strong interaction between basic amine groups and acidic CO2. Given that their high CO2 working capacity is governed by solvent used during amine functionalization, a systematic investigation on solvent effect is essential but not yet demonstrated. Herein, we report a facile one-step solvent exchange route for the diamine functionalization of MOFs with open metal sites, using an efficient method to maximize diamine loading. We employed an MOF, Mg2(dobpdc) (dobpdc4- = 4,4'-dioxido-3,3'-biphenyldicarboxylate), which contains high-density open metal sites. Indirect grafting with N-ethylethylenediamine (een) was performed with a minimal amount of methanol (MeOH) via multiple MeOH exchanges and diamine functionalization, resulting in a top-tier CO2 adsorption capacity of 16.5 wt %. We established the correlation between N,N-dimethylformamide (DMF) loading and infrared peaks, which provides a simple method for determining the amount of the remaining DMF in Mg2(dobpdc). All interactions among Mg, DMF, diamine, and solvent were analyzed by van der Waals (vdw)-corrected density functional theory (DFT) calculations to elucidate the effect of chemical potential on diamine grafting.

Shaping of a Metal-Organic Framework-Polymer Composite and Its CO2 Adsorption Performances from Humid Indoor Air.

Diamine-functionalized metal-organic frameworks (MOFs) are known as desirable adsorbents that can capture CO2 even at low pressures, but the humidity instability of bare MOF powders as well as their shaping have not yet adequately addressed for practical applications. Herein, we report an effective synthetic strategy for fabricating millimeter-sized MOF/poly(vinylidene fluoride) (PVDF) composite beads with different amounts of PVDF binders (30, 40, and 50 wt %) via a phase inversion method, followed by the postfunctionalization of 1-ethylpropane-1,3-diamine (epn). Compared with the pristine MOF powder, the diamine-grafted bead, epn-MOF/PVDF40, upon mixing with 40% binder polymers, exhibited a superior long-term performance without structural collapse for up to 1 month. The existence of the hydrophobic PVDF polymer in the composite material is responsible for such durability. This work provides a promising preparative route toward developing stable and shaped MOFs for the removal of indoor CO2.

High Ammonia Uptake of a Metal-Organic Framework Adsorbent in a Wide Pressure Range.

Although numerous porous adsorbents have been investigated for NH3 capture applications, these materials often exhibit insufficient NH3 uptake, low NH3 affinity at the ppm level, and poor chemical stability against wet NH3 conditions. The NH3 capture properties of M2 (dobpdc) complexes (M=Mg2+ , Mn2+ , Co2+ , Ni2+ , and Zn2+ ; dobpdc4- =4,4-dioxidobiphenyl-3,3-dicarboxylate) that contain open metal sites is presented. The NH3 uptake of Mg2 (dobpdc) at 298 K was 23.9 mmol g-1 at 1 bar and 8.25 mmol g-1 at 570 ppm, which are record high capacities at both pressures among existing porous adsorbents. The structural stability of Mg2 (dobpdc) upon exposure to wet NH3 was superior to that of the other M2 (dobpdc) and the frameworks tested. Overall, these results demonstrate that Mg2 (dobpdc) is a recyclable compound that exhibits significant NH3 affinity and capacity, making it a promising candidate for real-world NH3 -capture applications.