Pore engineering in cost-effective and stable Al-MOFs for efficient capture of the greenhouse gas SF6

Abstract

The capture and separation of the greenhouse gas sulfur hexafluoride (SF6) from nitrogen (N2) holds significant potential for mitigating the greenhouse effect and yielding economic advantages for the semiconductor industry. In this study, a pair of isoreticular cost-effective and stable metal–organic frameworks (MOFs) with slightly different pore environments (CAU-10-H and CAU-10-Py) were prepared at >10 g scale for SF6/N2 separation. CAU-10-Py exhibited a remarkable improvement in SF6 uptake capacity at both low pressure (1.13 mmol/g at 0.1 bar and 298 K, compared to 0.68 mmol/g) and elevated pressure (2.11 mmol/g at 1 bar and 278 K, compared to 1.07 mmol/g). The ideal adsorbed solution theory (IAST) selectivity of SF6/N2 (10/90) was found to be 204 for CAU-10-Py and 123 for CAU-10-H. These enhanced capacities and selectivity endow CAU-10-Py a highly promising candidate for SF6 capture. Single crystal structural analysis, 77 K N2 adsorption data and theoretical calculations indicated that the substitution of benzene by pyridine slightly expand the pore diameter, facilitating more efficient accommodation of SF6 within the channel pores. The SF6 molecule is adsorbed around four benzene rings in CAU-10-H but trapped by two pyridine rings in CAU-10-py, resulting in one fold increase in adsorption capacity. Intriguingly, time-dependant adsorption experiments revealed that CAU-10-Py exhibited a higher SF6 adsorption rate and a lower N2 adsorption rate compared to CAU-10-H, further highlighting the benefit of CAU-10-Py for SF6/N2 separation. Dynamic breakthrough experiments conducted under simulated working conditions further confirmed the outstanding SF6/N2 separation performance of CAU-10-Py. Considering its excellent regeneration ability and cycling performance, this cost-effective and easily scalable MOF demonstrates great promise for SF6/N2 separation.