Hydrothermal Synthesis of Sub-20 nm Amine-Functionalized MIL-101(Cr) Nanoparticles with High Surface Area and Enhanced CO2 Uptake

• Published in: Industrial & engineering chemistry research 2020-04, Vol.59 (16), p.7888-7900
• Main Authors: Han, Gang, Qian, Qihui, Mizrahi Rodriguez, Katherine, Smith, Zachary P
• Format: Article
• Language: English
• ISSN: 0888-5885; 1520-5045
• DOI: 10.1021/acs.iecr.0c00535

An assortment of hydrothermal reactions of chromic­(III) nitrate and 2-aminoterephthalic acid was systematically studied to yield high-quality amine-functionalized MIL-101­(Cr) nanoparticles (MIL-101­(Cr)-NH2). A comprehensive understanding of the role that synthesis conditions and basic modulators have on the formation of MIL-101­(Cr)-NH2 in aqueous media was extracted and reported herein. With the aid of a NaOH modulator at optimized concentration, sub-20 nm MIL-101­(Cr)-NH2 nanoparticles were prepared with good yield, minimized particle agglomeration, and a high Brunauer–Emmett–Teller (BET) surface area of 2800 ± 200 m2/g. To the best of our knowledge, these are the smallest particle sizes and the highest surface areas reported for directly synthesized MIL-101­(Cr)-NH2. Owing to their superior surface area and Lewis basic amine functionality, the MIL-101­(Cr)-NH2 nanoparticles exhibit a high CO2 adsorption of up to 3.4 mmol/g at 288 K and 1 bar and a superior CO2/N2 selectivity of 26.5 at 308 K and 0.1 bar. A high isosteric heat of −54.6 kJ/mol for CO2 adsorption implies the strong interaction between CO2 and the amine-functionalized framework. The successful synthesis of sub-20 nm amine-functionalized MIL-101­(Cr) nanoparticles offers a great opportunity to engineer advanced MIL-101­(Cr)-based functional adsorbents and membranes for CO2 capture and separation.