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Nanocellulose and Its Biohybrids for Water Purification: Atomic Force Microscopy as a Tool to Probe Surface Properties and Interactions
Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
2018 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

Nanocellulose has been explored extensively in recent years as an adsorbent due to its promising performance in the removal of charged contaminants from water. In this thesis, various atomic force microscopy (AFM) techniques are used to understand the surface characteristics and specific interactions of nanocellulose with water contaminants (heavy metal ions and dyes) and nanoscale entities (Graphene Oxide (GO) and Graphene Oxide nanocolloids (nanoGO)), and explain the mechanisms related to adsorption, metal ion clustering, self-assembly and mechanical reinforcement.

AFM probes functionalised with microscale and nanoscale celluloses were used as colloidal probes to study specific surface interactions with heavy metal ions and dyes in the aqueous medium. This approach enabled quantitative measurements of the adhesion force between nanocellulose and the water pollutants under in situ conditions by direct or in-direct methods. Adhesion forces, including the piconewton range, were measured, and the forces depended on the surface groups present on the nanocellulose.

AFM imaging in dry and/or wet conditions was successfully used to investigate the adsorption, self-assembly, morphology and mechanical properties of nanocellulose and its bio-hybrids. The self-assembly, the metal nanolayer and the nanoclusters on the surface of nanocellulose and its biohybrids after adsorption were confirmed and explained by advanced microscopy, spectroscopy and computational modelling.

The adhesion and stiffness measurement of single nanocellulose fibers using in situ PeakForce Quantitative Nanomechanical (PF-QNM) characterization confirmed the adsorption of metal ions on the surface in the liquid medium. PF-QNM mapping of the freestanding biohybrid membranes also revealed the enhanced modulus of the biohybrid membrane compared with the TEMPO(2,2,6,6-tetramethylpiperidine-1-oxylradical)-mediated oxidation nanofibers (TOCNF) membrane, which explained the hydrolytic stability and recyclability of these membranes.

The established methodology, which combines advanced microscopy with spectroscopy and modelling techniques, can be extended to other biobased macromolecular systems to investigate the adsorption behaviour and/or surface interactions in bio nanotechnology.

Place, publisher, year, edition, pages
Stockholm: Department of Materials and Environmental Chemistry (MMK), Stockholm University , 2018. , p. 23
Keywords [en]
Atomic force microscopy, nanocellulose, water purification, surface interaction, biohybrids, self-assembly, metal ion clustering
National Category
Materials Chemistry
Research subject
Materials Chemistry
Identifiers
URN: urn:nbn:se:su:diva-155373ISBN: 978-91-7797-260-0 (print)ISBN: 978-91-7797-261-7 (electronic)OAI: oai:DiVA.org:su-155373DiVA, id: diva2:1199020
Public defence
2018-06-08, Magnéli Hall, Arrhenius Laboratory, Svante Arrhenius väg 16 B, Stockholm, 09:30 (English)
Opponent
Supervisors
Note

At the time of the doctoral defense, the following papers were unpublished and had a status as follows: Paper 4: Manuscript. Paper 5: Manuscript.

Available from: 2018-05-16 Created: 2018-04-19 Last updated: 2018-05-09Bibliographically approved
List of papers
1. Adsorption Behavior of Cellulose and Its Derivatives toward Ag(I) in Aqueous Medium: An AFM, Spectroscopic, and DFT Study
Open this publication in new window or tab >>Adsorption Behavior of Cellulose and Its Derivatives toward Ag(I) in Aqueous Medium: An AFM, Spectroscopic, and DFT Study
Show others...
2015 (English)In: Langmuir, ISSN 0743-7463, E-ISSN 1520-5827, Vol. 31, no 45, p. 12390-12400Article in journal (Refereed) Published
Abstract [en]

The aim of this study was to develop a fundamental understanding of the adsorption behavior of metal ions on cellulose surfaces using experimental techniques supported by computational modeling, taking Ag(I) as an example. Force interactions among three types of cellulose microspheres (native cellulose and its derivatives with sulfate and phosphate groups) and the silica surface in AgNO3 solution were studied with atomic force microscopy (AFM) using the colloidal probe technique. The adhesion force between phosphate cellulose microspheres (PCM) and the silica surface in the aqueous AgNO3 medium increased significantly with increasing pH while the adhesion force slightly decreased for sulfate cellulose microspheres (SCM), and no clear adhesion force was observed for native cellulose microspheres (CM). The stronger adhesion enhancement for the PCM system is mainly attributed to the electrostatic attraction between Ag(I) and the negative silica surface. The observed force trends were in good agreement with the measured zeta potentials. The scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), and attenuated total reflectance-Fourier transform infrared spectroscopy (ATR-FTIR) analyses confirmed the presence of silver on the surface of cellulose microspheres after adsorption. This study showed that PCM with a high content of phosphate groups exhibited a larger amount of adsorbed A(I) than CM and SCM and possible clustering of Ag(I) to nanoparticles. The presence of the phosphate group and a wavenumber shift of the P-OH vibration caused by the adsorption of silver ions on the phosphate groups were further confirmed with computational studies using density functional theory (DFT), which gives support to the above findings regarding the adsorption and clustering of Ag(I) on the cellulose surface decorated with phosphate groups as well as IR spectra.

National Category
Chemical Sciences
Research subject
Materials Chemistry
Identifiers
urn:nbn:se:su:diva-124757 (URN)10.1021/acs.langmuir.5b03228 (DOI)000365150700009 ()26501836 (PubMedID)
Available from: 2016-01-08 Created: 2016-01-04 Last updated: 2018-04-23Bibliographically approved
2. Advanced microscopy and spectroscopy reveal the adsorption and clustering of Cu(II) onto TEMPO-oxidized cellulose nanofibers
Open this publication in new window or tab >>Advanced microscopy and spectroscopy reveal the adsorption and clustering of Cu(II) onto TEMPO-oxidized cellulose nanofibers
2017 (English)In: Nanoscale, ISSN 2040-3364, E-ISSN 2040-3372, Vol. 9, no 22, p. 7419-7428Article in journal (Refereed) Published
Abstract [en]

TEMPO (2,2,6,6-tetramethylpiperidine-1-oxylradical)-mediated oxidation nanofibers (TOCNF), as a biocompatible and bioactive material, have opened up a new application of nanocellulose for the removal of water contaminants. This development demands extremely sensitive and accurate methods to understand the surface interactions between water pollutants and TOCNF. In this report, we investigated the adsorption of metal ions on TOCNF surfaces using experimental techniques atthe nano and molecular scales with Cu(II) as the target pollutant in both aqueous and dry forms. Imaging with in situ atomic force microscopy (AFM), together with a study of the physiochemical properties of TOCNF caused by adsorption with Cu(II) in liquid, were conducted using the PeakForce Quantitative NanoMechanics (PF-QNM) mode at the nano scale. The average adhesion force between the tip and the target single TOCNF almost tripled after adsorption with Cu(II) from 50 pN to 140 pN. The stiffness of the TOCNF was also enhanced because the Cu(II) bound to the carboxylate groups and hardened the fiber. AFM topography, scanning electron microscopy-energy dispersive X-ray spectroscopy (SEM-EDS) mapping and X-ray photoelectron spectroscopy (XPS) indicated that the TOCNF were covered by copper nanolayers and/or nanoparticles after adsorption. The changes in the molecular structure caused by the adsorption were demonstrated by Raman and attenuated total reflectance-Fourier transform infrared spectroscopy (ATR-FTIR). This methodology will be of great assistance to gain qualitative and quantitative information on the adsorption process and interaction between charged entities in aqueous medium.

National Category
Chemical Sciences
Research subject
Materials Chemistry
Identifiers
urn:nbn:se:su:diva-144778 (URN)10.1039/c7nr01566f (DOI)000402881600009 ()
Available from: 2017-07-17 Created: 2017-07-17 Last updated: 2018-04-23Bibliographically approved
3. Self-Assembled TEMPO Cellulose Nanofibers: Graphene Oxide-Based Biohybrids for Water Purification
Open this publication in new window or tab >>Self-Assembled TEMPO Cellulose Nanofibers: Graphene Oxide-Based Biohybrids for Water Purification
2017 (English)In: ACS Applied Materials and Interfaces, ISSN 1944-8244, E-ISSN 1944-8252, Vol. 9, no 24, p. 21048-21058Article in journal (Refereed) Published
Abstract [en]

Nanocellulose, graphene oxide (GO), and their combinations there off have attracted great attention for the application of water purification recently because of their unique adsorption capacity, mechanical characteristics, coordination with transition metal ions, surface charge density, and so on. In the current study, (2,2,6,6-tetramethylpiperidine-1-oxylradical) (TEMPO)-mediated oxidized cellulose nanofibers (TOCNF) and GO sheets or graphene oxide nanocolloid (nanoGO) biohybrids were prepared by vacuum filtration method to obtain self-assembled adsorbents and membranes for water purification. The porous biohybrid structure, studied using advanced microscopy techniques, revealed a unique networking and self-assembling of TOCNF, GO, and nanoGO, driven by the morphology of the GO phase and stabilized by the intermolecular H-bonding between carboxyl groups and hydroxyl groups. The biohybrids exhibited a promising adsorption capacity toward Cu(II) due to TOCNF and formed a unique arrested state in water because of ionic cross-linking between adsorbed Cu(II) and the negatively charged TOCNF and GO phase. The mechanical performance of the freestanding biohybrid membranes investigated using PeakForce Quantative NanoMechanics characterization confirmed the enhanced modulus of the hybrid membrane compared to that of the TOCNF membrane. Besides, the TOCNF+nanoGO membrane shows unique hydrolytic stability and recyclability even under several cycles of adsorption and desorption and strong sonication. This study shows that TOCNF and nanoGO hybrids can generate new water-cleaning membranes with synergistic properties because of their high adsorption capacity, flexibility, hydrolytic stability, and mechanical robustness.

Keywords
TEMPO cellulose nanofibers, graphene oxide nanocolloids, biohybrid, water purification, PF-QNM
National Category
Chemical Sciences
Research subject
Materials Chemistry
Identifiers
urn:nbn:se:su:diva-145202 (URN)10.1021/acsami.7b06358 (DOI)000404090000087 ()28557432 (PubMedID)
Available from: 2017-07-31 Created: 2017-07-31 Last updated: 2018-04-23Bibliographically approved
4. Nanocellulose-Functionalized AFM Probes for Investigating Surface Interactions by Force Spectroscopy
Open this publication in new window or tab >>Nanocellulose-Functionalized AFM Probes for Investigating Surface Interactions by Force Spectroscopy
(English)Manuscript (preprint) (Other academic)
National Category
Materials Chemistry
Research subject
Materials Chemistry
Identifiers
urn:nbn:se:su:diva-155369 (URN)
Available from: 2018-04-19 Created: 2018-04-19 Last updated: 2018-04-23Bibliographically approved
5. TEMPO Cellulose Nanofiber - Graphene Oxide Biohybrids: Disclosing Self-Assembly and Cu(II) Adsorption using Advanced Microscopy and ReaxFF Molecular Dynamics Simulations
Open this publication in new window or tab >>TEMPO Cellulose Nanofiber - Graphene Oxide Biohybrids: Disclosing Self-Assembly and Cu(II) Adsorption using Advanced Microscopy and ReaxFF Molecular Dynamics Simulations
(English)Manuscript (preprint) (Other academic)
National Category
Materials Chemistry
Research subject
Materials Chemistry
Identifiers
urn:nbn:se:su:diva-155370 (URN)
Available from: 2018-04-19 Created: 2018-04-19 Last updated: 2018-04-23Bibliographically approved

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