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

Abstract

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.