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Multiple physicochemical characterizations were conducted to illuminate the NO2 filtration mechanisms. Analysis on adsorption kinetics and mass transfer patterns in Zr-MOF xerogels was further performed to visualize the underlying structure-activity relationship using the gravimetric uptake and zero length column methods with cyclohexane and acetaldehyde as probes. The results revealed that the synergy of hierarchical porosities and nanosized crystals could effectively expedite the intracrystalline diffusion for the G66-NH2 xerogel as wel