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Microporous Humins Prepared from Sugars and Bio-Based Polymers in Concentrated Sulfuric Acid
Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).ORCID iD: 0000-0002-7284-2974
Number of Authors: 22019 (English)In: ACS Sustainable Chemistry and Engineering, ISSN 2168-0485, Vol. 7, no 1, p. 1018-1027Article in journal (Refereed) Published
Abstract [en]

Highly microporous humins were synthesized from readily available sugars and bio-based polymers (monosaccharides, disaccharides, and polysaccharides) in sulfuric acid followed by a diethyl ether wash and heat treatment at 400 degrees C. The relative sustainability, costs of production, and availability of the starting materials were improved significantly as compared with the 5-hydroxymethyl-furfural-based microporous humins recently studied by us. A multipronged approach was used to study the detailed characteristics of the adsorbents. Results from H-1 NMR, C-13 NMR, FTIR, WAXS, and elemental analysis were combined and showed that the adsorbents predominantly consisted of amorphous and aromatic carbon structures being rich in oxygen. They were highly porous, and the micropore volumes varied among the compositions as could be observed by analyzing CO2 and N-2 gas adsorption data. Comparably high CO2 uptakes of 4.25 and 1.94 mmol/g at 0 degrees C and 1 and 0.15 bar were observed. With the synthesis of microporous humins with varying porosities, the domain of potential applications of this class of materials could be expanded.

Place, publisher, year, edition, pages
2019. Vol. 7, no 1, p. 1018-1027
Keywords [en]
Adsorbents, Biomass conversion, Carbon dioxide capture, Saccharides, Glucose, Starch, Cellulose, Green & Sustainable Science & Technology
National Category
Chemical Sciences
Research subject
Materials Chemistry
Identifiers
URN: urn:nbn:se:su:diva-165763DOI: 10.1021/acssuschemeng.8b04658ISI: 000455288800107OAI: oai:DiVA.org:su-165763DiVA, id: diva2:1285458
Available from: 2019-02-04 Created: 2019-02-04 Last updated: 2019-04-21Bibliographically approved
In thesis
1. Sustainable porous organic materials: Synthesis, sorption properties and characterization
Open this publication in new window or tab >>Sustainable porous organic materials: Synthesis, sorption properties and characterization
2018 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

The resources available to us humans, including metals, minerals, biomass, air, water, and anything else on the planet, are being used at an increasing rate. This anthropogenic use of resources both depletes the resources and has negative impacts on other resources, e.g. the biosphere. Thus, developing (more) sustainable chemical and industrial processes are of the utmost importance for the well-being of the creatures of Earth and for the long-term sustainability of human society.

This thesis focuses on organic porous materials, and more specifically their synthesis and characterization. Porous materials are, for example, used in detergents, water treatment, bio gas upgrading, carbon dioxide capture, as catalysts, in sensors, and in various biological applications. The application of porous materials can contribute to the drive towards a more sustainable society. However, porous materials are typically not sustainable themselves. Thus, there is a need to develop more sustainable porous materials. The synthesis and characterization of three different groups of porous organic materials are described in this thesis.

In pulp- and paper manufacturing, lignin is separated from desirable products and is typically combusted for heat. In one section of this thesis, lignin was used to produce bio-oil for potential use in fuels and chemicals. However, the bio-oil process produced a solid by-product. The by-product was used to synthesize and study activated carbons with very high porosities and magnetic properties, a combination of properties that may prove to be useful in applications.

Sugar is known to produce solid and unwanted compounds through reactions with acids. It is shown here that it is possible to produce highly microporous humins, i.e. organic porous materials with a large amount of small pores, using sulphuric acid and a range of saccharides and bio-based polymers. This work supports that solid by-products in a wide range of biomass conversion processes can be of high value, both economically and as replacements for less sustainable alternatives.

The biosphere contains vast amounts of molecules with aromatic structures. The last section of this thesis shows how such aromatic molecules can be used to produce highly porous materials through Friedel-Crafts type chemistry using sulfolane as a solvent and iron chloride as a catalyst. This synthesis strategy produces high-performance materials, improves upon the sustainability of traditional Friedel-Crafts chemistry, and makes use of typically underutilized and abundant bio-based molecules.

Place, publisher, year, edition, pages
Stockholm: Department of Materials and Environmental Chemistry, Stockholm University, 2018. p. 64
Keywords
porous materials, sorbents, microporous, CO2 capture and separation, gas adsorption, activated carbon, humins, hypercrosslinked polymers, sustainable
National Category
Materials Chemistry
Research subject
Materials Chemistry
Identifiers
urn:nbn:se:su:diva-159468 (URN)978-91-7797-428-4 (ISBN)978-91-7797-429-1 (ISBN)
Public defence
2018-10-29, Magnélisalen, Kemiska övningslaboratoriet, Svante Arrhenius väg 16 B, Stockholm, 13:00 (English)
Opponent
Supervisors
Note

At the time of the doctoral defense, the following papers were unpublished and had a status as follows: Paper 3: Manuscript. Paper 4: Manuscript.

Available from: 2018-10-04 Created: 2018-08-30 Last updated: 2019-04-21Bibliographically approved

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