Pore Compartmentalization of CO 2 and H 2 O in a Redox‐Active Adsorbent
Ankit K. Yadav, Emmanuel N. Musa, Ah‐Young Song, Alireza Pourghaderi, Micah Lee Wilson, Chun‐Wai Chang, Kai Shen Choong, Casey R. Simons, Zhenxing Feng, Jeffrey A. Reimer, Ammar Alahmed, Mourad Younes, Aqil Jamal, Andrzej Gładysiak, Kyriakos C. StylianouABSTRACT
Achieving sustainable carbon capture under realistic, humid conditions remains a central challenge for decarbonization technologies. Here we report an ultramicroporous oxofluorovanadate metal‐organic framework, Ni(pyrazine) 2 (VOF 4 ), that dynamically regulates competitive adsorption through reversible redox chemistry. Under humid dilute CO 2 streams (4 vol%), water chemisorbs at vanadium centers in the form of hydroxide ligands and induces a reversible V(+4)|V(+5) transformation to an isoreticular phase, Ni(pyrazine) 2 (VO(OH)F 4 ), while CO 2 is engaged in strong physisorption within pyrazine‐lined pore regions. This redox‐driven compartmentalization of H 2 O and CO 2 results in a dynamic breakthrough CO 2 capacity of 2.04 ± 0.07 mmol/g, sustained for up to 50 cycles and showing resilience under intense humidification or steam exposure. These findings establish redox‐adaptive adsorption in BVR‐X as a unique design paradigm, enabling scalable and durable carbon capture under realistic operating conditions.