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A highly water stable meta-carborane based copper-metal-organic framework for efficient high-temperature butanol separation

A highly water stable meta-carborane based copper-metal-organic framework for efficient high-temperature butanol separation
A highly water stable meta-carborane based copper-metal-organic framework for efficient high-temperature butanol separation

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.

Carborane, Hydrophobicity, butanol recovery, metal-organic frameworks, water stability
0002-7863
8299-8311
Gan, Lei
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Chidambaram, Arunraj
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Fonquernie, Pol G.
c0ab6e80-cdf8-4f04-aa69-01c04e253e34
Light, Mark
cf57314e-6856-491b-a8d2-2dffc452e161
Choquesillo-Lazarte, Duane
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Huang, Hongliang
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Solano, Eduardo
ffb9e57b-8537-47f8-bb1a-df30f13b7433
Fraile, Julio
b156bd1b-1d41-4296-b54c-2baa0134c6e1
Viñas, Clara
636b5d2e-fefb-4e83-93df-9615eee8e771
Teixidor, Francesc
d24b81b5-5d82-42ca-bd30-fd9c73d0ee68
Navarro, Jorge A. R.
3c2fb88d-37df-4a3d-ac48-32f4c310d695
Stylianou, Kyriakos C.
0536c485-b0e9-4135-9f47-506bf5d51c1b
Planas, José Giner
98b21b50-1c21-4265-bd3c-67afe28ef652
Gan, Lei
e361ae76-bd0b-4847-b4ce-3e6cd5241ce5
Chidambaram, Arunraj
2bc4620b-7b65-4279-9f35-c68e49a9359e
Fonquernie, Pol G.
c0ab6e80-cdf8-4f04-aa69-01c04e253e34
Light, Mark
cf57314e-6856-491b-a8d2-2dffc452e161
Choquesillo-Lazarte, Duane
b96b9413-2131-44ce-880c-243a1c00e234
Huang, Hongliang
33b83238-696c-4620-9fa5-f1e99b457076
Solano, Eduardo
ffb9e57b-8537-47f8-bb1a-df30f13b7433
Fraile, Julio
b156bd1b-1d41-4296-b54c-2baa0134c6e1
Viñas, Clara
636b5d2e-fefb-4e83-93df-9615eee8e771
Teixidor, Francesc
d24b81b5-5d82-42ca-bd30-fd9c73d0ee68
Navarro, Jorge A. R.
3c2fb88d-37df-4a3d-ac48-32f4c310d695
Stylianou, Kyriakos C.
0536c485-b0e9-4135-9f47-506bf5d51c1b
Planas, José Giner
98b21b50-1c21-4265-bd3c-67afe28ef652

Gan, Lei, Chidambaram, Arunraj, Fonquernie, Pol G., Light, Mark, Choquesillo-Lazarte, Duane, Huang, Hongliang, Solano, Eduardo, Fraile, Julio, Viñas, Clara, Teixidor, Francesc, Navarro, Jorge A. R., Stylianou, Kyriakos C. and Planas, José Giner (2020) A highly water stable meta-carborane based copper-metal-organic framework for efficient high-temperature butanol separation. Journal of the American Chemical Society, 142 (18), 8299-8311. (doi:10.1021/jacs.0c01008).

Record type: Article

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.

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ms CuDABCO_JACS_REVISED_11_4_20 (1) - Accepted Manuscript
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More information

Accepted/In Press date: 12 April 2020
e-pub ahead of print date: 27 April 2020
Published date: 6 May 2020
Keywords: Carborane, Hydrophobicity, butanol recovery, metal-organic frameworks, water stability

Identifiers

Local EPrints ID: 440650
URI: http://eprints.soton.ac.uk/id/eprint/440650
ISSN: 0002-7863
PURE UUID: b3a06627-6774-453b-a28b-da87ee363789
ORCID for Mark Light: ORCID iD orcid.org/0000-0002-0585-0843

Catalogue record

Date deposited: 13 May 2020 16:31
Last modified: 13 Nov 2021 05:29

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Contributors

Author: Lei Gan
Author: Arunraj Chidambaram
Author: Pol G. Fonquernie
Author: Mark Light ORCID iD
Author: Duane Choquesillo-Lazarte
Author: Hongliang Huang
Author: Eduardo Solano
Author: Julio Fraile
Author: Clara Viñas
Author: Francesc Teixidor
Author: Jorge A. R. Navarro
Author: Kyriakos C. Stylianou
Author: José Giner Planas

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