The synthesis of stable and efficient porous adsorbents for adsorptive capture and recovery of SO2 from flue gas is of great importance for minimizing air pollution and reducing costs.Herein, by choosing trifluoroacetic acid as modulator, the single crystal UiO-67-(NH2)2 has been successfully synthesized benefitting crystal structure determinationThe stability tests, gas adsorption measurements, and breakthrough experiments demonstrated that single-crystal UiO-67-(NH2)2 possesses moderate acid-base and hydrothermal stability, and exhibited high SO2 uptake (19.72 mmol/g, 298 K and 1 bar), good SO2/CO2 separation selectivity (110.3∼33.3, SO2/CO2 = 10/90), and excellent SO2 recovery purity (93.3 %).However, the instability of the UiO-67-(NH2)2 framework, combined with the strong corrosive and reactive properties of SO2, can lead to partial collapse of the framework during the adsorption and capture process.This ultimately results in a decreased SO2 capture performance over time.In-situ DRIFT, GCMC simulation and DFT calculations revealed that the μ3-OH of Zr6O4(OH)4 clusters and the -NH2 groups of the ligand can form multiple hydrogen bonds with SO2 mols.This ensures that SO2 mols. are firmly grasped by UiO-67-(NH2)2 framework and facilitate the efficiently selective capture of SO2 at low concentration