Amino-Functionalized Microporous MOFs for Capturing Greenhouse Gases CF₄ and NF₃ with Record Selectivity

The capture and separation of fluorinated gases (F-gases) from N2 has the potential to not only reduce greenhouse gas emissions but also provide economic benefits for the semiconductor industry. In this work, two Ni-based metal–organic frameworks (MOFs), Ni-MOF (Ni(ina)2, ina = isonicotinic acid) and amine-functionalized NH2–Ni-MOF (Ni(3-ain)2, 3-ain = 3-aminoisonicotinic acid), were constructed for capturing F-gases (CF4 and NF3). At ambient conditions, both materials exhibit very high CF4 sorption capacities (2.92 mmol g–1 for Ni-MOF and 2.69 mmol g–1 for NH2–Ni-MOF). In addition, NH2–Ni-MOF exhibited a record selectivity of 46.3 for the CF4/N2 mixture at 298 K and 100 kPa, surpassing all benchmark adsorbents, including Ni-MOF (34.7). The kinetic adsorption tests demonstrated that Ni-MOF and NH2–Ni-MOF performed well for CF4/N2 and NF3/N2 mixtures. According to grand canonical Monte Carlo (GCMC) simulations, CF4 or NF3 interacts with NH2–Ni-MOF by multiple van der Waals interactions, resulting in stronger interaction than N2. More importantly, dynamic breakthrough experiments verified the practical separation potential of the two materials for CF4/N2 and NF3/N2 mixtures.