Catenation Control in Stable Zr‐MOFs for Fine‐Tuning LNG‐ANG‐Related Methane Storage

Abstract The liquefied natural gas and adsorbed natural gas (LNG‐ANG) coupling systems are emerging as an attractive solution to solve boil‐off gases generated by LNG tanks. Metal‐organic frameworks (MOFs) are promising candidates for methane storage and delivery owing to their high porosity, large specific surface area, and tunable pore structures. However, systematically tuning LNG‐ANG‐related methane adsorption performance of MOFs has yet to be explored. In this context, an interpenetrated zirconium‐based (3,8)‐connected the‐MOF, Zr‐TTB‐1, with limited porosity is synthesized. The further delicate modulation of reaction conditions allows the assembly of a non‐interpenetrated counterpart, Zr‐TTB‐2, with significantly improved porosity. Such molecular‐level catenation control results in a substantial increase in low‐temperature methane adsorption performance related to LNG‐ANG. The volumetric working capacity of non‐interpenetrated Zr‐TTB‐2 is up to 255 cm³ (standard temperature and pressure, STP) cm⁻³ under LNG‐ANG condition (159 K, 6 bar, and 298 K, 5 bar), outperforms more than twice that of interpenetrated counterpart—Zr‐TTB‐1 (115 cm³ (STP) cm⁻³). To this end, the investigation provides an efficacious example of regulating the methane working capacity in LNG‐ANG systems through molecular‐level structural control of designed porous frameworks.