A Highly Water-Stable meta-Carborane-Based Copper Metal–Organic Framework for Efficient High-Temperature Butanol Separation

Abstract

Biofuels are considered sustainable and renewable alternatives to conventional fossil fuels. Biobutanol has recently emerged as an attractive option compared to bioethanol and biodiesel, but a significant challenge in its production lies in the separation stage. The current industrial process for the production of biobutanol includes the ABE (acetone−butanol−ethanol) fermentation process from biomass; the resulting fermentation broth has a butanol concentration of no more than 2 wt% (the rest is essentially water). Therefore, the development of a cost-effective process for separation of butanol from dilute aqueous solutions is highly desirable. The use of porous materials for the adsorptive separation of ABE mixtures is considered a highly promising route, as these materials can potentially have high affinities for alcohols and low affinities for water. To date, zeolites have been tested toward this separation, but their hydrophilic nature makes them highly incompetent for this application. The use of metal−organic frameworks (MOFs) is an apparent solution; however, their low hydrolytic stabilities hinder their implementation in this application. So far, a few nanoporous zeolitic imidazolate frameworks (ZIFs) have shown excellent potential for butanol separation due to their good hydrolytic and thermal stabilities. Herein, we present a novel, porous, and hydrophobic MOF based on copper ions and carborane−carboxylate ligands, mCB-MOF-1, for butanol recovery. mCB-MOF-1 exhibits excellent stability when immersed in organic solvents, water at 90 °C for at least two months, and acidic and basic aqueous solutions. We found that, like ZIF-8, mCB-MOF-1 is non-porous to water (type II isotherm), but it has higher affinity for ethanol, butanol, and acetone compared to ZIF-8, as suggested by the shape of the vapor isotherms at the crucial low-pressure region. This is reflected in the separation of a realistic ABE mixture in which mCB-MOF-1 recovers butanol more efficiently compared to ZIF-8 at 333 K.

Synthesis, crystal structure and magnetic properties of poly[[diaqua{μ6-2-[bis(carboxylatomethyl)amino]terephthalato}dicobalt(II)] 1.6-hydrate]

“…Over the last two decades, coordination polymers (CPs) have become one of the most attractive fields in chemistry because of their fascinating structures and promising applications as solid functional materials in adsorption and separation (Gan et al, 2020;Yang et al, 2020;Qian et al, 2020;Islamoglu et al, 2020), catalysis (Bavykina et al, 2020), sensing (Allendorf et al, 2020), luminescence (Rice et al, 2020) and magnetism (Thorarinsdottir & Harris, 2020;Wang et al, 2019b). Multicarboxylic acids have been employed to synthesize compounds comprising of various dimensional structures such as chains, layers and three-dimensional frameworks.…”

Rational design of carborane-based Cu2-paddle wheel coordination polymers for increased hydrolytic stability

“…16,[18][19][20][21][22][23][24][25][26] In recent years we have reported that the introduction of hydrophobic carborane based linkers into MOFs greatly improve their hydrolytic stability for further practical application. 27 Icosahedral boranes [B 12 H 12 ] 2and carboranes 1,n-C 2 B 10 H 12 (n = 2, 7 or 12) are a class of commercially available and exceptionally stable 3D-aromatic boron-rich clusters that possess material-favorable properties such as thermal and chemical stability and high hydrophobicity. [28][29][30][31][32] The neutral carboranes are remarkably robust icosahedral boron clusters with two carbon and ten boron atoms.…”

Th-MOF showing six-fold imide-sealed pockets for middle-size-separation of propane from nature gas

“…Anchoring functionalized units on the pore wall of MOFs to enhance the host-guest interactions is also an effective method for separation [38][39][40] . This can theoretically selectively adsorb target molecule from the mixture under precise design on the functionalized units.…”