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Lignin-Based Nano/Microfibers and Colloidal Particles: Applications in Adsorption and Biocatalysis
Stockholm University, Faculty of Science, Department of Chemistry.ORCID iD: 0000-0002-3748-3822
2026 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

Lignin is one of the most abundant aromatic biomacromolecules and is generated in large quantities as a by-product of industrial pulping processes, with an estimated annual production of 70−80 million tons. Its complex and heterogeneous structure has historically limited its utilization in high-value applications. However, its rich and diverse chemical functionality makes lignin a promising renewable feedstock for the development of value-added functional materials. Over the past decade, substantial advances in lignin extraction, chemical functionalization, and conversion strategies have enabled the development of a wide range of lignin-derived functional materials. 

This thesis investigates multiple approaches for transforming softwood kraft lignin (SKL) into functional materials, including fibers, nanoparticles and hybrid material systems, with a particular focus on environmental and catalytic applications. The developed materials were explored for water purification through adsorption of organic dyes using lignin-based nano- and microfibers, carbon dioxide (CO2) capture through solid-state adsorption using carbonized lignin nanofibers and liquid-state absorption using lignin dispersions catalyzed by carbonic anhydrase, and protease-assisted biofouling mitigation using lignin nanoparticles (LNPs) and lignin nanofibers (LNFs).

SKL was chemically modified through esterification, enabling solvent-free melt-spinning into microfibers using a cotton candy machine. The incorporation of magnetite nanoparticles (MNPs) into the lignin-based microfibers improved their thermal stability while retaining their dye-adsorption performance in aqueous solutions. Furthermore, the incorporation of MNPs facilitated the magnetic recovery of the adsorbent over multiple adsorption cycles.

Electrospun nanofibers comprising unfractionated, unmodified SKL and cellulose acetate were produced at lignin loadings up to 80 wt%. The materials exhibited dual functionality, enabling dye adsorption from aqueous solutions followed by CO2 capture after carbonization. This sequential utilization demonstrated the potential of lignin-based nanofibers as multifunctional materials, with their performance strongly dependent on the precursor composition. 

Stabilized lignin nanoparticles (sLNPs), prepared by the hydrothermal curing of hydroxymethylated lignin, were used as a support for the immobilization of carbonic anhydrase. The resulting biocatalytic system enabled enzymatic CO2 hydration under varying pH and temperature conditions. Enzyme immobilization enhanced CO2 absorption while improving the storage stability of carbonic anhydrase.

Finally, protease-functionalized LNPs and LNFs membranes were developed with 67% lignin content, as biocatalytic antifouling systems for membrane filtration. This lignin-based platform enabled rapid hydrolysis of bovine serum albumin (BSA), used as a model protein foulant, and improved membrane permeate flux. 

Overall, this thesis demonstrates the versatility of SKL as a renewable feedstock for the development of multifunctional materials, highlighting its potential for applications in water purification, CO2 capture, and biocatalysis. 

Place, publisher, year, edition, pages
Stockholm: Department of Chemistry, Stockholm University , 2026. , p. 112
Keywords [en]
Softwood kraft lignin, melt-spinning, electrospinning, microfibers, nanofibers, nanoparticles, dye adsorption, carbon dioxide capture, biocatalysis
National Category
Materials Chemistry
Research subject
Materials Chemistry
Identifiers
URN: urn:nbn:se:su:diva-258021ISBN: 978-91-8107-700-1 (print)ISBN: 978-91-8107-701-8 (electronic)OAI: oai:DiVA.org:su-258021DiVA, id: diva2:2091565
Public defence
2026-09-25, Magnelisalen, Kemiska Övningslaboratoriet, Svante Arrhenius Väg 16B, Stockholm, 14:00 (English)
Opponent
Supervisors
Funder
Swedish Research Council, 2020-03752European Commission, 101075487Available from: 2026-09-02 Created: 2026-08-12 Last updated: 2026-08-27Bibliographically approved
List of papers
1. Mechanically recyclable melt-spun fibers from lignin esters and iron oxide nanoparticles: towards circular lignin materials
Open this publication in new window or tab >>Mechanically recyclable melt-spun fibers from lignin esters and iron oxide nanoparticles: towards circular lignin materials
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2023 (English)In: Green Chemistry, ISSN 1463-9262, E-ISSN 1463-9270, Vol. 25, no 24, p. 10424-10435Article in journal (Refereed) Published
Abstract [en]

The inferior thermoplastic properties have limited production of melt-spun fibers from lignin. Here we report on the controlled esterification of softwood kraft lignin (SKL) to enable scalable, solvent-free melt spinning of microfibers using a cotton candy machine. We found that it is crucial to control the esterification process as melt-spun fibers could be produced from lignin oleate and lignin stearate precursors with degrees of esterification (DE) ranging from 20-50%, but not outside this range. To fabricate a functional hybrid material, we incorporated magnetite nanoparticles (MNPs) into the lignin oleate fibers by melt blending and subsequent melt spinning. Thermogravimetric analysis and X-ray diffraction studies revealed that increasing the weight fraction of MNPs led to improved thermal stability of the fibers. Finally, we demonstrated adsorption of organic dyes, magnetic recovery, and recycling via melt spinning of the regular and magnetic fibers with 95% and 83% retention of the respective adsorption capacities over three adsorption cycles. The mechanical recyclability of the microfibers represents a new paradigm in lignin-based circular materials.

National Category
Paper, Pulp and Fiber Technology
Identifiers
urn:nbn:se:su:diva-223041 (URN)10.1039/d3gc02381h (DOI)001067497500001 ()2-s2.0-85173027246 (Scopus ID)
Available from: 2023-10-18 Created: 2023-10-18 Last updated: 2026-08-12Bibliographically approved
2. Electrospinning of Softwood Kraft Lignin With Cellulose Acetate: Dye Adsorption, Carbonization, and Carbon Dioxide Capture
Open this publication in new window or tab >>Electrospinning of Softwood Kraft Lignin With Cellulose Acetate: Dye Adsorption, Carbonization, and Carbon Dioxide Capture
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2026 (English)In: ChemSusChem, ISSN 1864-5631, E-ISSN 1864-564X, Vol. 19, no 10, article id e70717Article in journal (Refereed) Published
Abstract [en]

The development of bio-based materials capable of addressing multiple environmental challenges is critical for advancing sustainable materials design. Herein, we report electrospun nanofibers from unfractionated, chemically unmodified softwood kraft lignin and cellulose acetate, where cellulose acetate acts as a carrier polymer, enabling the formation of uniform precursor fibers with lignin contents of up to 80%. The resulting nanofibers enable sequential dye adsorption from water (methylene blue removal capacity of 19 mg/g) and carbon dioxide (CO2) capture (2.2 mmol/g) after carbonization. When evaluated solely for CO2 capture, the pristine carbonized materials show sorption capacities of 3.1–3.9 mmol/g, which increase as lignin content in the precursor fibers decreases, underscoring the importance of tuning carbon yield and capture performance. The sequential utilization of a single precursor material demonstrates a stepwise transformation that aligns with resource efficiency and sustainable material design. Overall, this study demonstrates a viable route for the direct valorization of industrial lignin into functional materials for both water purification and carbon capture applications.

Keywords
carbonization, CO2sorption, dye adsorption, electrospinning, softwood kraft lignin
National Category
Materials Chemistry
Identifiers
urn:nbn:se:su:diva-256155 (URN)10.1002/cssc.70717 (DOI)42137940 (PubMedID)2-s2.0-105038787221 (Scopus ID)
Available from: 2026-06-04 Created: 2026-06-04 Last updated: 2026-08-12Bibliographically approved
3. Carbonic anhydrase immobilization on stabilized lignin nanoparticles for aqueous phase carbon dioxide capture
Open this publication in new window or tab >>Carbonic anhydrase immobilization on stabilized lignin nanoparticles for aqueous phase carbon dioxide capture
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2026 (English)In: ACS sustainable resource management, E-ISSN 2837-1445Article in journal (Refereed) Epub ahead of print
Abstract [en]

The continuous rise in atmospheric carbon dioxide (CO2) concentrations and its contribution to global climate change necessitates the development of sustainable CO2 capture technologies. Enzyme-based CO2 capture systems, particularly those using carbonic anhydrase (CA), offer high catalytic efficiency, but their practical use is limited by high enzyme costs, reduced enzyme stability and the difficulty of recovering them from water-based systems. Here, we report the immobilization of CA via straightforward adsorption onto sustainable and covalently stabilized lignin nanoparticles (sLNPs) for catalyzing aqueous-phase CO2 capture. The immobilized enzyme exhibited slightly higher specific activity than free enzyme at technically important pH 9.0, which suggests that pH-stable sLNPs may contribute to stabilizing carbonic anhydrase within its microenvironment. The catalytic performance of the system was evaluated in a stopped-flow reactor by measuring CO2 hydration at pH 7.1 and 9.4 across temperatures between 30−60 °C, using the colorimetric response of pH-sensitive dyes. The reaction kinetics at pH 7.1 showed an Arrhenius-type temperature dependence, while non-Arrhenius behavior was observed at pH 9.4. Enzyme immobilization enhanced aqueous absorption of CO2, as shown by stirred-cell fall-in-pressure measurements at 40 and 60 °C. These results support the development of scalable biocatalytic systems for CO2 capture in aqueous media using CA.

Keywords
Softwood kraft lignin, Nanoparticles, Enzyme immobilization, Aqueous phase CO2 capture, Stopped-flow reactor
National Category
Materials Chemistry
Research subject
Materials Chemistry
Identifiers
urn:nbn:se:su:diva-258018 (URN)10.1021/acssusresmgt.6c00267 (DOI)
Funder
Swedish Research Council, 2020-03752Swedish Research Council, 2021-04472European Commission, 101075487
Available from: 2026-08-12 Created: 2026-08-12 Last updated: 2026-08-12
4. Surface-confined protein hydrolysis by protease immobilized on lignin nanoparticles and nanofiber networks
Open this publication in new window or tab >>Surface-confined protein hydrolysis by protease immobilized on lignin nanoparticles and nanofiber networks
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(English)Manuscript (preprint) (Other academic)
Abstract [en]

Biofouling remains a critical challenge in filtration systems, leading to reduced efficiency and lifespan of membranes and, consequently, increased operational costs. In this study, enzymatic protein hydrolysis using protease immobilized on lignin nanoparticles (LNPs) and lignin nanofibers (LNFs) was investigated as an approach to mitigate fouling. Bovine serum albumin (BSA) was selected as a model foulant. Proteolytic degradation of BSA was carried out using protease adsorbed on LNPs (Protease@LNPs) as such and further immobilized into an electrospun LNFs membrane (Protease@LNPs@LNFs). Activity assays showed that protease immobilization on LNPs, as well as on combined LNP-LNF systems, resulted in comparable activity retention. Quartz Crystal Microbalance with Dissipation monitoring (QCM-D) and Scanning Electron Microscopy (SEM) was used to study the hydrolysis process in real-time, while SDS-PAGE analysis was used to resolve the hydrolytic products from BSA. Densitometric analysis of the bands indicated a degree of hydrolysis of 84% after 30 minutes for both Protease@LNPs and Protease@LNPs@LNFs. Finally, we demonstrate a proof-of-concept biocatalytic membrane composed of protease adsorbed onto LNPs (Protease@LNPs) and further embedded within a three-dimensional network of LNFs for antifouling applications.

Keywords
Softwood kraft lignin, Lignin nanoparticles, Lignin nanofibers, Enzyme immobilization, Antifouling, Protein hydrolysis
National Category
Materials Chemistry
Identifiers
urn:nbn:se:su:diva-258020 (URN)
Funder
Swedish Research Council, 2020-03752European Commission, 101075487Swedish Foundation for Strategic Research, FFL21-0006
Available from: 2026-08-12 Created: 2026-08-12 Last updated: 2026-08-12

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Thalakkale Veettil, Unnimaya

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