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Updated: Jun 6, 2025

Author Spotlight: Functionalizing Metal-Organic Frameworks: Advancements, Challenges, and the Power of Post-Synthetic Ligand Exchange
Published on: June 23, 2023
Catenation Control in Stable Zr-MOFs for Fine-Tuning LNG-ANG-Related Methane Storage
Si Ma1,2, Le Shi1,2, Yuanlong Zhong1,2
1Department of Chemistry, Stoddart Institute of Molecular Science, Zhejiang Key Laboratory of Excited-State Energy Conversion and Energy Storage, State Key Laboratory of Silicon and Advanced Semiconductor Materials, Zhejiang University, Hangzhou, 310058, P. R. China.
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.
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