Water-Stable etb-MOFs for Methane and Carbon Dioxide Storage

Abstract

We utilized the etb platform of MOFs for the synthesis of two new water-stable compounds based on amide functionalized trigonal tritopic organic linkers H3BTBTB (L1), H3BTCTB (L2) and Al3+ metal ions, namely, Al(L1) and Al(L2). The mesoporous Al(L1) material exhibits an impressive methane (CH4) uptake at high pressures and ambient temperature. The corresponding values of 192 cm3 (STP) cm–3, 0.254 g g–1 at 100 bar, and 298 K are among the highest reported for mesoporous MOFs, while the gravimetric and volumetric working capacities (between 80 bar and 5 bar) can be well compared to the best MOFs for CH4 storage. Furthermore, at 298 K and 50 bar, Al(L1) adsorbs 50 wt % (304 cm3 (STP) cm–3) CO2, values among the best recorded for CO2 storage using porous materials. To gain insight into the mechanism accounting for the resultant enhanced CH4 storage capacity, theoretical calculations were performed, revealing the presence of strong CH4 adsorption sites near the amide groups. Our work demonstrates that amide functionalized mesoporous etb-MOFs can be valuable for the design of versatile coordination compounds with CH4 and CO2 storage capacities comparable to ultra-high surface area microporous MOFs.

High Pore Volume Hyper-Cross-Linked Polymers via Mixed-Solvent Knitting: A Route to Superior Hierarchical Porosity for Methane Storage and Delivery

“…As a result, HCP-MS-3 exhibited superior physicochemical stability against either high-pressure operation or harsh chemical environments, making it more suitable for long-term practical ANG applications. In particular, HCP-MS-3 achieves an impressive 5–100 bar gravimetric methane working capacity of 0.381 g g –1 with a useable delivery rate of 89%, surpassing numerous benchmark MOF adsorbents that have been extensively studied and used in methane storage applications (Figure c), including HKUST-1 (0.16 g g –1 , 64%), Ni-MOF-74 (0.08 g g –1 , 44%), PCN-14 (0.136 g g –1 , 69%), UTSA-20 (0.134 g g –1 , 74%), MOF-905 (0.260 g g –1 , 86%), and so on. ,,,,− As mentioned previously, HCPs-MS offer several additional advantages of cost, synthesis, and properties. These include readily available monomers, diverse external cross-linkers, affordable catalysts, high synthetic yields, moderate reaction conditions, simple modification strategies, tunable textural properties, and excellent structural stability.…”

Development of a Mixed Multinuclear Cluster Strategy in Metal–Organic Frameworks for Methane Purification and Storage

“…To fully evaluate the performance of the adsorbents for methane storage applications, it is crucial to consider the amount (gravimetric and volumetric) of CH 4 that can be delivered, which is commonly referred to as the “working capacity” or “deliverable capacity”. In this study, the working capacity is taken as the difference between the adsorbing pressure (35 bar or above) and 5 bar as the desorbing pressure. , The working volumetric capacities of SNNU-329 are calculated at 5–35, 5–65, and 5–80 bar. These values are 117 and 105 cm 3 (STP) cm –3 at 35 bar, 147 and 145 cm 3 (STP) cm –3 at 65 bar, and 153 and 156 cm 3 (STP) cm –3 at 80 bar at 273 and 298 K, which have surpassed many famous MOFs, such as MOF-210 (69 cm 3 cm –3 at 35 bar); UiO-66_B (∼80 cm 3 cm –3 at 65 bar); Ni-MOF-74 (129 cm 3 (STP) cm –3 ; 5 to 65 bar at 298 K), and is comparable with those benchmark MOFs such as Al (L1) (150 cm 3 (STP) cm –3 ; 5 to 80 bar at 298 K), NU-1501-Al (174 cm 3 (STP) cm –3 ; 5 to 80 bar at 296 K), Cu-tbo-MOF-5 (175 cm 3 (STP) cm –3 ; 5 to 80 bar at 298 K) (Figure d).…”

“…High-pressure CH 4 adsorption and desorption isotherms (a–c) at 273 and 298 K for SNNU-328–330, and the comparison of CH 4 working capacity of SNNU-329 with the best methane storage MOF candidates: MOF-519, NUJ-Bai 43, HKUST-1, Al-soc-MOF-1, PCN-14, NU-1501-Al (at 296 K), Al (L1), MOF-210 in terms of at 5–65 and 5–80 bar and 298 K.…”

“…In this study, the working capacity is taken as the difference between the adsorbing pressure (35 bar or above) and 5 bar as the desorbing pressure. , The working volumetric capacities of SNNU-329 are calculated at 5–35, 5–65, and 5–80 bar. These values are 117 and 105 cm 3 (STP) cm –3 at 35 bar, 147 and 145 cm 3 (STP) cm –3 at 65 bar, and 153 and 156 cm 3 (STP) cm –3 at 80 bar at 273 and 298 K, which have surpassed many famous MOFs, such as MOF-210 (69 cm 3 cm –3 at 35 bar); UiO-66_B (∼80 cm 3 cm –3 at 65 bar); Ni-MOF-74 (129 cm 3 (STP) cm –3 ; 5 to 65 bar at 298 K), and is comparable with those benchmark MOFs such as Al (L1) (150 cm 3 (STP) cm –3 ; 5 to 80 bar at 298 K), NU-1501-Al (174 cm 3 (STP) cm –3 ; 5 to 80 bar at 296 K), Cu-tbo-MOF-5 (175 cm 3 (STP) cm –3 ; 5 to 80 bar at 298 K) (Figure d). Therefore, SNNU-329 is a very hopeful porous material candidate to be used as high-pressure methane storage materials under environmental conditions.…”