Fine-Tuning a Robust Metal–Organic Framework toward Enhanced Clean Energy Gas Storage

Abstract

The development of adsorbents with molecular precision offers a promising strategy to enhance storage of hydrogen and methaneconsidered the fuel of the future and a transitional fuel, respectivelyand to realize a carbon-neutral energy cycle. Herein we employ a postsynthetic modification strategy on a robust metal–organic framework (MOF), MFU-4l, to boost its storage capacity toward these clean energy gases. MFU-4l-Li displays one of the best volumetric deliverable hydrogen capacities of 50.2 g L–1 under combined temperature and pressure swing conditions (77 K/100 bar → 160 K/5 bar) while maintaining a moderately high gravimetric capacity of 9.4 wt %. Moreover, MFU-4l-Li demonstrates impressive methane storage performance with a 5–100 bar usable capacity of 251 cm3 (STP) cm–3 (0.38 g g–1) and 220 cm3 (STP) cm–3 (0.30 g g–1) at 270 and 296 K, respectively. Notably, these hydrogen and methane storage capacities are significantly improved compared to those of its isoreticular analogue, MFU-4l, and place MFU-4l-Li among the best MOF-based materials for this application.

Computational Identification and Experimental Demonstration of High‐Performance Methane Sorbents

“…In contrast to previous studies, two separate sets of interatomic potential parameters were used for CUS and non‐CUS MOFs to identify high‐capacity materials that were previously overlooked due to limitations of general interatomic potentials (Table S1). Notably, very few studies employ both computational and experimental approaches to demonstrate record‐setting MOFs [27] . The potentials used here yielded superior agreement with the experimentally measured isotherms of the MOFs, as shown in Table 1.…”

“…Here, high‐throughput Grand Canonical Monte Carlo (GCMC) simulations are used to identify promising MOFs whose capacities for methane uptake exceeds that of state‐of‐the‐art materials. Experimental synthesis and methane uptake measurements reveal that three of these MOFs—UTSA‐76, UMCM‐152 and DUT‐23‐Cu—surpass the methane capacity of HKUST‐1 as well as for other noteworthy methane sorbents (Table S6), providing a new high‐water mark for methane storage materials [27] . An additional distinguishing feature of this work is the use of interatomic potentials that explicitly account for the presence of coordinatively unsaturated sites (CUS) [28–30] .…”

“…Experimental synthesis and methane uptake measurements reveal that three of these MOFs-UTSA-76, UMCM-152 and DUT-23-Cu-surpass the methane capacity of HKUST-1 as well as for other noteworthy methane sorbents (Table S6), providing a new high-water mark for methane storage materials. [27] An additional distinguishing feature of this work is the use of interatomic potentials that explicitly account for the presence of coordinatively unsaturated sites (CUS). [28][29][30] CUS MOFs used in our calculations were identified by the CoRE 2019 database based on a python code developed by Haldoupis (GitHub-Emmhald/Open_ metal_detector, n.d.).…”

Immobilization of Lewis Basic Nitrogen Sites into a Chemically Stable Metal–Organic Framework for Benchmark Water‐Sorption‐Driven Heat Allocations

“…In this regard, porous metal-organic frameworks (MOFs) have received immense attention as promising water adsorbents owing to their powerful predictability and tunability on pore size/shape and functionality. [14][15][16][17][18][19][20][21][22][23][24][25] Reticular chemistry of MOFs has enabled us to design and control of pore size, surface area, and hydrophilicity at the molecular level. [26][27][28][29][30][31][32][33][34][35][36] In the past two decades, a number of MOFs have been developed as water adsorbents for diverse water adsorption-related applications.…”

Two-dimensional metal-organic frameworks: from synthesis to bioapplications

“…Moreover, the functionalization of MOFs would be easily obtained either by modification of the building blocks previously or post-modification of pre-synthesized MOFs. Owing to these outstanding features, MOFs have been widely applied in the field of gas storage [ 2 ] and separations [ 3 , 4 ], nonlinear optics [ 5 ], catalysis [ 6 , 7 ], and sensing [ 8 , 9 ].…”