Functionalization-Induced Breathing Control in Metal-Organic Frameworks for Methane Storage with High Deliverable Capacity

Metal–organic frameworks (MOFs) that can undergo structural flexibility upon gas sorption cycle bear enormous potential particularly as adsorbents for methane storage. A molecular level control over such flexibility can be advantageous for the development of smart adsorbents with increased deliverable capacity. Herein, we report the flexible and stable MIL-53(Al) type MOFs, whose breathing behavior can be controlled by systematic installation of hydrogen bonding sites into the frameworks. Such a control has been fine-tuned to induce high deliverable capacity in MOFs by changing gas pressure, temperature, and density. The establishment of a structure–property relationship for methane storage and successful pelletization of MOFs pave the way for MOF-based onboard natural gas storage.