Ultrahigh and Selective SO2 Uptake in Inorganic Anion-Pillared Hybrid Porous Materials

4 years ago

Ultrahigh and Selective SO2 Uptake in Inorganic Anion-Pillared Hybrid Porous Materials

Rajamani Krishna, Qilong Ren, Banglin Chen, Wei Zhou, Hui Wu, Zongbi Bao, Xili Cui, Qiwei Yang, Huabin Xing, Zhiguo Zhang, Lifeng Yang

The efficient capture of SO2 is of great significance in gas-purification processes including flue-gas desulfurization and natural-gas purification, but the design of porous materials with high adsorption capacity and selectivity of SO2 remains very challenging. Herein, the selective recognition and dense packing of SO2 clusters through multiple synergistic host–guest and guest–guest interactions by controlling the pore chemistry and size in inorganic anion (SiF62−, SIFSIX) pillared metal–organic frameworks is reported. The binding sites of anions and aromatic rings in SIFSIX materials grasp every atom of SO2 firmly via Sδ+···Fδ− electrostatic interactions and Oδ−···Hδ+ dipole–dipole interactions, while the guest–guest interactions between SO2 molecules further promote gas trapping within the pore space, which is elucidated by first-principles density functional theory calculations and powder X-ray diffraction experiments. These interactions afford new benchmarks for the highly efficient removal of SO2 from other gases, even if at a very low SO2 concentration. Exceptionally high SO2 capacity of 11.01 mmol g−1 is achieved at atmosphere pressure by SIFSIX-1-Cu, and unprecedented low-pressure SO2 capacity is obtained in SIFSIX-2-Cu-i (4.16 mmol g−1 SO2 at 0.01 bar and 2.31 mmol g−1 at 0.002 bar). More importantly, record SO2/CO2 selectivity (86–89) and excellent SO2/N2 selectivity (1285–3145) are also achieved. Experimental breakthrough curves further demonstrate the excellent performance of these hybrid porous materials in removing low-concentration SO2. Selective recognition and dense packing of SO2 clusters through multiple synergistic host–guest and guest–guest interactions within SiF62−-anion-pillared hybrid porous materials sets new benchmarks for SO2 capture. The binding sites of anions and aromatic rings in SIFSIX materials grasp every atom of SO2 firmly via Sδ+···Fδ− electrostatic interactions and Oδ−···Hδ+ dipole–dipole interactions.

Publisher URL: http://onlinelibrary.wiley.com/resolve/doi

DOI: 10.1002/adma.201606929