Abstract
ABSTRACT
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.