Hydrofluoric Acid-Free Synthesis of MIL-101(Cr)-SO3H

Abstract

The conventional synthesis of the Metal–Organic Framework (MOF) MIL-101(Cr)-SO3H employs hydrofluoric acid as the modulator, posing handling challenges due to its irritating, corrosive, and toxic nature, as well as its reactivity with glass and metals. This study aims to find a new hydrofluoric acid-free synthesis route for MIL-101(Cr)-SO3H, proposing acetic acid and nitric acid as modulator alternatives. Four MIL-101(Cr)-SO3H samples were prepared: one without any modulator and the other three using a similar volume of either hydrofluoric acid, acetic acid, or nitric acid as the modulator. The so-obtained mass yield ranked as follows: without any modulator (32.6%) > acetic acid (29.6%) > nitric acid (25.2%) >> hydrofluoric acid (2.2%), whereas the total pore volume and BET surface area followed the order: hydrofluoric acid (0.87 cm3 g−1, 1862 m2 g−1) > nitric acid (0.81 cm3 g−1, 1554 m2 g−1) > acetic acid (0.72 cm3 g−1, 1374 m2 g−1) > without any modulator (0.69 cm3 g−1, 1342 m2 g−1). Despite the superior texture parameters obtained using hydrofluoric acid, the low synthesis yield and associated risks make this route non-viable. Acetic or nitric acid-based synthesis offers a promising alternative with a drastically higher yield, safer handling, and reduced environmental impact. In an attempt to improve the textural properties of the hydrofluoric acid-free MOFs, a series of samples were produced with increasing amounts of acetic acid, achieving BET surface areas of up to 1504 m2 g−1 and pore volumes of up to 0.81 cm3 g−1.