Mechanistic insights into CO₂ capture in metal–organic frameworks: from framework dynamics to molecular interactions

The urgent need to mitigate atmospheric CO₂ has driven the exploration of advanced materials for carbon capture, with metal-organic frameworks (MOFs) emerging as frontrunners due to their structural versatility, high surface areas, and tunable functionalities. This review presents a comprehensive mechanistic perspective on CO₂ adsorption in MOFs, linking molecular-level interactions such as metal CO₂ binding, hydrogen bonding, and electrostatics with macroscopic structural responses including gate-opening, breathing, and negative gas adsorption (NGA). This review presents a systematic, application-oriented mechanistic framework for CO₂ adsorption in MOFs, categorizing adsorption behavior into framework-responsive, site-specific, and guest-induced cooperative mechanisms, and linking these mechanisms to practical capture scenarios. Framework-responsive mechanisms highlight the dynamic adaptability of MOFs, while site-specific mechanisms leverage open metal sites, functional groups, and engineered defects to create high-affinity adsorption centers. Guest-induced cooperative mechanisms enhance uptake via synergistic host–guest interactions, and rotational dynamics are shown to influence diffusion and selectivity. By integrating synthetic design principles, structural flexibility, and mechanistic insight, this review bridges chemistry, physics, and materials design, offering tutorial value for early-career researchers and forward-looking strategies for next-generation sorbents tailored to post-combustion, pre-combustion, and direct air CO₂ capture. • MOFs exhibit diverse CO₂ adsorption mechanisms beyond simple physisorption. • Framework-responsive mechanisms include gate-opening, breathing, and NGA (negative gas adsorption). • Site-specific interactions involve OMSs (open metal sites), functional groups, and engineered defects. • Guest-induced cooperative effects enhance uptake via synergistic interactions. • Rotational dynamics influence diffusion, selectivity, and adsorption efficiency. • Mechanistic understanding enables rational design of MOFs for targeted CO₂ capture.