A Metal–Organic Framework with Optimized Porosity and Functional Sites for High Gravimetric and Volumetric Methane Storage Working Capacities

Abstract Extensive research has been devoted to developing new porous materials with high methane storage capacity. While great progress has been made in recent years, it still remains very challenging to target simultaneously high gravimetric and volumetric methane (CH₄) working capacities (deliverable amount between 5.8 and 65 bar) in a single material. Here, a novel metal–organic framework (termed as UTSA‐110a) constructed by an extended linker containing a high density of functional nitrogen sites, exhibiting both very high gravimetric and volumetric working capacities of 317 cm³ (STP: 273.15 K, 1 atm) g⁻¹ and 190 cm³ (STP) cm⁻³, respectively, for robust MOFs, is reported. Both of these values are higher than those of two benchmark materials: HKUST‐1 (207 cm³ (STP) g⁻¹ or 183 cm³ (STP) cm⁻³) and UTSA‐76a (267 cm³ (STP) g⁻¹ or 187 cm³ (STP) cm⁻³). Computational studies reveal that it is the combination of optimized porosity and favorable binding sites that leads to the simultaneously high gravimetric and volumetric working capacities in this material.