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Functionalization, Characterization and Applications of Oxidized Nanocellulose Derivatives
Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Engineering Sciences, Nanotechnology and Functional Materials.ORCID iD: 0000-0001-8142-0565
2017 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

Cellulose, a sustainable raw material derived from nature, can be used for various applications following its functionalization and oxidation. Nanocellulose, inheriting the properties of cellulose, can offer new properties due to nanoscale effects, in terms of high specific surface area and porosity. The oxidation of cellulose can provide more active sites on the cellulose chains, improving its functionalization and broadening applications. Two kinds of oxidation and their corresponding applications are described in this thesis: periodate oxidation and Oxone® oxidation.

2,3-dialdehyde cellulose (DAC) beads were prepared from Cladophora nanocellulose via periodate oxidation, and were further modified with amines via reductive amination. Several diamines were selected as possible crosslinkers to produce porous DAC beads, which showed higher porosity, stability in alkaline solution and enhanced thermal stability.

After functionalization of DAC beads with L-cysteine (DAC-LC), thiol, amine and carboxyl groups were introduced into the DAC beads, endowing the DAC-LC beads with high adsorption capacity for palladium. The synthesized DAC-LC beads were character­ized with SEM, FTIR, XPS, TGA, BET and XRD and the palladium adsorption process was investigated.

Chitosan was employed as a crosslinker in functionalization of DAC beads (DAC-CS). The conditions for the synthesis of DAC-CS beads were screened and verifying the stability of the beads in alkaline solution. The DAC-CS beads produced were investigated using SEM, FTIR, XPS, TGA and BET, and the adsorption and desorption capacity of Congo red was studied, indicating DAC-CS beads have potential as sorbent.

Oxone oxidation of cellulose is a novel one-pot oxidation method in which mainly the hydroxyl groups on C6 are oxidized to produce carboxylic acid groups on the cellulose chains. To increase the efficiency of Oxone oxidation, several reaction parameters were studied. Cellulose pulp and Cladophora nanocellulose were chosen as prototypes to investigate the effects of oxidation, and the physico­chemical properties of the oxidized products were characterized. Cellulose pulp, pretreated with Oxone oxidation, was disintegrated by homogenization to prepare cellulose nanofibers (CNF). The effect of pre­treat­ment on the preparation of CNF was studied, and the results indicated that Oxone oxidation was efficient in the production of CNF.

Place, publisher, year, edition, pages
Uppsala: Acta Universitatis Upsaliensis, 2017. , p. 68
Series
Digital Comprehensive Summaries of Uppsala Dissertations from the Faculty of Science and Technology, ISSN 1651-6214 ; 1548
Keywords [en]
Nanocellulose, Periodate oxidation, Oxone oxidation, Adsorption, Palladium, Congo red dye, Cellulose nanofibers
National Category
Nano Technology
Research subject
Engineering Science with specialization in Nanotechnology and Functional Materials
Identifiers
URN: urn:nbn:se:uu:diva-328388ISBN: 978-91-513-0048-1 (print)OAI: oai:DiVA.org:uu-328388DiVA, id: diva2:1135438
Public defence
2017-10-13, Polhemsalen, Ångströmlaboratoriet, Lägerhyddsvägen 1, Uppsala, 09:30 (English)
Opponent
Supervisors
Available from: 2017-09-21 Created: 2017-08-23 Last updated: 2017-10-17
List of papers
1. Preparation of Porous Cellulose Beads via Introduction of Diamine Spacers
Open this publication in new window or tab >>Preparation of Porous Cellulose Beads via Introduction of Diamine Spacers
2016 (English)In: Langmuir, ISSN 0743-7463, E-ISSN 1520-5827, Vol. 32, no 22, p. 5600-5607Article in journal (Refereed) Published
Abstract [en]

The current work presents a synthesis route based on the reductive amination of 2,3-dialdehyde cellulose beads with diamines to render micrometer-sized beads with increased specific surface area (SSA) and porosity in the mesoporous range. Specifically, the influence of the reductive amination of 2,3-dialdehyde cellulose (DAC) using aliphatic and aromatic tethered mono- and diamines on bead microstructure was investigated. Aliphatic and aromatic tethered monoamines were found to have limited utility for producing porous beads whereas the introduction of diamines provided beads with a porous texture and an SSA increasing from <1 to >30 m(2)/g. Both aliphatic and aromatic diamines were found to be useful in producing porous beads having a pore size distribution range of 10 to 100 nm, as verified by N-2 gas adsorption and mercury intrusion porosimetry analyses. The true density of the functionalized DAC beads decreased to an average of about 1.36 g/cm(3) as compared to 1.48 g/cm(3) for the unfunctionalized, fully oxidized DAC beads. The total porosity of the beads was, according to mercury porosimetry, in the range of 54-64%. Reductive amination with 1,7-diaminoheptane provided beads that were stable under alkaline conditions (I M NaOH). It was concluded that the introduction of tethered diamines into DAC beads is a facile method for producing mesoporous beads.

National Category
Nano Technology Materials Engineering
Identifiers
urn:nbn:se:uu:diva-299045 (URN)10.1021/acs.langmuir.6b01288 (DOI)000377631300017 ()27181427 (PubMedID)
Funder
Knut and Alice Wallenberg FoundationGöran Gustafsson Foundation for promotion of scientific research at Uppala University and Royal Institute of Technology
Available from: 2016-07-13 Created: 2016-07-13 Last updated: 2017-08-23Bibliographically approved
2. A green and simple method for preparation of an efficient palladium adsorbent based on cysteine functionalized2,3-dialdehyde cellulose
Open this publication in new window or tab >>A green and simple method for preparation of an efficient palladium adsorbent based on cysteine functionalized2,3-dialdehyde cellulose
2016 (English)In: Cellulose (London), ISSN 0969-0239, E-ISSN 1572-882X, Vol. 23, no 4, p. 2627-2638Article in journal (Refereed) Published
Abstract [en]

A green and efficient adsorbent for adsorption of palladium ions was prepared from 2,3-dialdehyde cellulose (DAC) originating from nanocellulose from the green algae Cladophora. The DAC was functionalized with cysteine via reductive amination in a convenient one-pot procedure to provide the adsorbent. The adsorption properties for adsorbing palladium(II) ions, including capacity, adsorption isotherm and kinetics, were studied. The successful reductive amination of cysteine with 2,3-dialdehyde cellulose was confirmed by FT-IR, elemental analysis and XPS. The adsorbent was characterized by SEM, XRD, gas adsorption and TGA. The adsorbent had a high adsorption capacity (130 mg palladium per gram adsorbent) and enabled fast adsorption of palladium(II) ions from solution (80 % of maximum capacity reached in 2 h). Adsorbent materials suitable for both filters (fibrous) and column matrixes (spherical particles) could be obtained in an efficient manner by controlling the degree of oxidation while producing the DAC material.

Keywords
2, 3-dialdehyde cellulose, Palladium adsorption, Cellulose beads, Nanocellulose
National Category
Nano Technology
Identifiers
urn:nbn:se:uu:diva-303299 (URN)10.1007/s10570-016-0976-0 (DOI)000380089300028 ()
Available from: 2016-09-15 Created: 2016-09-15 Last updated: 2017-08-23Bibliographically approved
3. On the preparation of porous 2,3-dialdehyde cellulose beads crosslinked with chitosan and their adsorption of Congo red
Open this publication in new window or tab >>On the preparation of porous 2,3-dialdehyde cellulose beads crosslinked with chitosan and their adsorption of Congo red
2017 (English)In: Article in journal (Refereed) Submitted
National Category
Nano Technology
Identifiers
urn:nbn:se:uu:diva-328386 (URN)
Available from: 2017-08-22 Created: 2017-08-22 Last updated: 2017-10-13
4. Favored Surface-limited Oxidation of Cellulose with Oxone® in Water
Open this publication in new window or tab >>Favored Surface-limited Oxidation of Cellulose with Oxone® in Water
2017 (English)In: RSC Advances, ISSN 2046-2069, E-ISSN 2046-2069, Vol. 7, no 64, p. 40600-40607Article in journal (Refereed) Published
Abstract [en]

A novel method for favored primary alcohol oxidation of cellulose was developed. Cellulose pulp andCladophora nanocellulose were oxidized in a one-pot procedure by Oxone® (2KHSO5$KHSO4$K2SO4)and efficient reaction conditions were identified. The effects of the reaction on the morphology,viscosity and chemical structure of the products obtained were studied. The primary alcohol groupswere oxidized to carboxyl groups and the content of carboxyl groups was determined byconductometric titration. SEM, capillary-type viscometry and XRD were applied to characterize theproducts and to investigate the influence of oxidation. For the first time, low-cost and stable Oxone®was used as a single oxidant to oxidize cellulose into carboxyl cellulose. The oxidation is an inexpensiveand convenient process to produce carboxylic groups on the surface of the cellulose fibers and to makethe cellulose fibers charged. Particularly, this method can avoid the use of halogens and potentially toxicradicals and constitute a green route to access carboxylated cellulose. Further, sodium bromide could beused as a co-oxidant to the Oxone® and increase the carboxylic acid content by 10–20%. The Oxone®oxidation is a promising method for oxidation of cellulose and might facilitate the production of CNC.

Keywords
Cellulose, Oxone, Tempo-Mediated Oxidation, 2, 3-Dialdehyde Cellulose, Periodate-Oxidation, Chemistry, Efficient, Bromide, Delignification, Nanocellulose, Transparent, Nanofibers
National Category
Nano Technology
Research subject
Engineering Science with specialization in Nanotechnology and Functional Materials
Identifiers
urn:nbn:se:uu:diva-328237 (URN)10.1039/c7ra06141b (DOI)000408043100065 ()
Funder
Knut and Alice Wallenberg Foundation
Available from: 2017-08-21 Created: 2017-08-21 Last updated: 2020-01-29Bibliographically approved
5. Cellulose nanofibers prepared via pretreatment based on Oxone® oxidation
Open this publication in new window or tab >>Cellulose nanofibers prepared via pretreatment based on Oxone® oxidation
Show others...
2017 (English)In: Molecules, ISSN 1420-3049, E-ISSN 1420-3049, Vol. 22, no 12, article id 2177Article in journal (Refereed) Published
Abstract [sv]

Softwood sulfite bleached cellulose pulp was oxidized with Oxone (R) and cellulose nanofibers (CNF) were produced after mechanical treatment with a high-shear homogenizer. UV-vis transmittance of dispersions of oxidized cellulose with different degrees of mechanical treatment was recorded. Scanning electron microscopy (SEM) micrographs and atomic force microscopy (AFM) images of samples prepared from the translucent dispersions showed individualized cellulose nanofibers with a width of about 10 nm and lengths of a few hundred nm. All results demonstrated that more translucent CNF dispersions could be obtained after the pretreatment of cellulose pulp by Oxone (R) oxidation compared with the samples produced without pretreatment. The intrinsic viscosity of the cellulose decreased after oxidation and was further reduced after mechanical treatment. Almost translucent cellulose films were prepared from the dispersions of individualized cellulose nanofibers. The procedure described herein constitutes a green, novel, and efficient route to access CNF.

Place, publisher, year, edition, pages
MDPI AG, 2017
National Category
Nano Technology
Research subject
Engineering Science with specialization in Nanotechnology and Functional Materials
Identifiers
urn:nbn:se:uu:diva-328387 (URN)10.3390/molecules22122177 (DOI)000419242400142 ()
Available from: 2017-08-23 Created: 2017-08-23 Last updated: 2020-02-07Bibliographically approved

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