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From Polysaccharides to Functional Materials for Trace Pharmaceutical Adsorption
KTH, School of Engineering Sciences in Chemistry, Biotechnology and Health (CBH), Fibre- and Polymer Technology, Polymer Technology.ORCID iD: 0000-0002-8090-088X
2019 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

The transition to bioeconomy will reduce our dependency on fossil fuels as well as contribute to a more sustainable society. Within this framework, exploitation and development of renewable substitutes to petroleum-based products provides feasible roadmap for the material design. Here a perspective is provided to how the natural polysaccharides chitosan (CS) and/or cellulose (CL) could be elaborated and transformed to high-performance materials with the explicit aim of removing trace pharmaceutical contaminants from the wastewater, thus facilitating the sustainable development. In the first part of the thesis, chitosan and cellulose were converted to the carbon spheres (C-sphere) through a microwave-assisted hydrothermal carbonization process, and C-sphere was further broken down to the nanographene oxide (nGO) via a simple oxidation route. On this foundation, a green pathway was developed for fabrication of biobased materials for wastewater purification. First, macroporous chitosan-based composite hydrogels with controllable properties were developed, where chitosan-derived nGO worked as a functional property enhancer. Second, a further development changing from the bulky hydrogels to microgels consisting of CS composite particles in the microscopic size was achieved by a fast one-pot spraying-drying process. The crosslinking reaction occurred in situ during the spray-drying. Last, the C-sphere by-itself was also believed to be a potential adsorbent for wastewater contaminants. In the next step the prepared systems were evaluated for their capacity to adsorb pharmaceutical contaminants. Diclofenac sodium (DCF) was utilized as the model drug, and the three fabricated bio-adsorbents all demonstrated effective DCF adsorption performance, with the adsorption efficiency varying from 65.6 to 100%. Moreover, the DCF adsorption kinetics, isotherms and thermodynamic study were also investigated to reveal the nature of the adsorption process with the different materials. Finally, chitosan-based microspheres were selected for the reusability study, with the adsorption efficiency above 70% retained after six adsorption-desorption cycles, thus further endowing the promising potential of the fabricated bio-adsorbents for commercial applications.

Place, publisher, year, edition, pages
Stockholm: KTH Royal Institute of Technology, 2019. , p. 48
Series
TRITA-CBH-FOU ; 2019:21
Keywords [en]
Chitosan, cellulose, nanographene oxide, carbon spheres, hydrogel, microsphere, adsorbent, pharmaceutical, microwave, spray-drying
National Category
Environmental Engineering Nano Technology Textile, Rubber and Polymeric Materials Physical Chemistry Polymer Chemistry
Research subject
Fibre and Polymer Science
Identifiers
URN: urn:nbn:se:kth:diva-248454ISBN: 978-91-7873-167-1 (print)OAI: oai:DiVA.org:kth-248454DiVA, id: diva2:1303301
Public defence
2019-05-23, F3, Lindstedtsvägen 26, Stockholm, 10:00 (English)
Opponent
Supervisors
Note

QC 20190411

Available from: 2019-04-11 Created: 2019-04-09 Last updated: 2019-05-27Bibliographically approved
List of papers
1. Biobased Nanographene Oxide Creates Stronger Chitosan Hydrogels with Improved Adsorption Capacity for Trace Pharmaceuticals
Open this publication in new window or tab >>Biobased Nanographene Oxide Creates Stronger Chitosan Hydrogels with Improved Adsorption Capacity for Trace Pharmaceuticals
2017 (English)In: ACS Sustainable Chemistry & Engineering, ISSN 2168-0485, Vol. 5, no 12, p. 11525-11535Article in journal (Refereed) Published
Abstract [en]

A promising green strategy for the fabrication of fully biobased chitosan adsorbents for wastewater purification is presented. Nanographene oxide (nGO)-type carbon dots were derived from chitosan (nGOCS) or from cellulose (nGOCL) through a two-step process including microwave-assisted hydrothermal carbonization and oxidation. Finally, nGO were evaluated as biobased property enhancers in chitosan hydrogel adsorbents. Macroporous chitosan hydrogels were synthesized by cross-linking with genipin, and the incorporation of nGO into these hydrogels was shown to facilitate the cross-linking reaction leading to more robust 3D cross-linked networks. This was evidenced by the increased storage modulus and by the swelling ratio that decreased from 5.7 for pristine chitosan hydrogel to 2.6 for hydrogel with 5 mg/mL nGOCS and 3.3 for hydrogel with 5 mg/mL nGOCL. As a further proof of the concept the hydrogels were shown to be effective adsorbent for the common anti-inflammatory drug diclofenac sodium (DCF). Here, the addition of nGO promoted the DCF adsorption process leading to 100% removal of DCF after only 5 h. The synergistic effect of electrostatic interactions, hydrogen bonding, and pi-pi stacking could explain the high adsorption of DCF on the hydrogels. The developed biobased CS/nGO hydrogels are thus promising adsorbents with great potential for purification of trace pharmaceuticals from wastewater.

Place, publisher, year, edition, pages
American Chemical Society (ACS), 2017
Keywords
Graphene oxide, Carbon dot, Hydrogel, Diclofenac sodium, Genipin, Microwave, Waste water purification, Adsorbent
National Category
Polymer Chemistry Polymer Technologies
Identifiers
urn:nbn:se:kth:diva-220462 (URN)10.1021/acssuschemeng.7b02809 (DOI)000417341900044 ()2-s2.0-85042358833 (Scopus ID)
Note

QC 20171221

Available from: 2017-12-21 Created: 2017-12-21 Last updated: 2019-04-10Bibliographically approved
2. Tunable chitosan hydrogels for adsorption: Property control by biobased modifiers
Open this publication in new window or tab >>Tunable chitosan hydrogels for adsorption: Property control by biobased modifiers
2018 (English)In: Carbohydrate Polymers, ISSN 0144-8617, E-ISSN 1879-1344, Vol. 196, p. 135-145Article in journal (Refereed) Published
Abstract [en]

A sustainable strategy to fabricate chitosan-based composite hydrogels with tunable properties and controllable adsorption capacity of trace pharmaceuticals was demonstrated. Two biobased modifiers were utilized to tune the properties, nano-graphene oxide (nGO) derived from chitosan via microwave-assisted carbonization and oxidation, and genipin as the crosslinking agent. An increase in genipin content facilitated an increase in the degree of crosslinking as shown by improved storage modulus and decreased swelling ratio. Increasing nGO content changed the surface microtopography of the hydrogel which correlated with the surface wettability. nGO also catalyzed the genipin-crosslinking reaction. The hydrogel was further shown to be an effective adsorbent for a common anti-inflammatory drug, diclofenac sodium (DCF), with the removal efficiency ranging from 91 to 100% after 48 h. DCF adsorption efficiency could be tuned through simple alteration of nGO and genipin concentration, which provides promising potential for this environmental-friendly adsorbent in removal of DCF from pharmaceutical waste water.

Place, publisher, year, edition, pages
Elsevier Ltd, 2018
Keywords
Adsorbent, Biobased, Chitosan, Graphene oxide, Hydrogel, Pharmaceutical
National Category
Polymer Technologies
Identifiers
urn:nbn:se:kth:diva-228696 (URN)10.1016/j.carbpol.2018.05.029 (DOI)000436571600016 ()2-s2.0-85047074150 (Scopus ID)
Note

QC 20180530

Available from: 2018-05-30 Created: 2018-05-30 Last updated: 2019-04-10Bibliographically approved
3. Recyclable fully biobased chitosan adsorbents spray-dried in one-pot to microscopic size and enhanced adsorption capacity
Open this publication in new window or tab >>Recyclable fully biobased chitosan adsorbents spray-dried in one-pot to microscopic size and enhanced adsorption capacity
Show others...
2019 (English)In: Biomacromolecules, ISSN 1525-7797, E-ISSN 1526-4602, Vol. 20, no 5, p. 1956-1964Article in journal (Refereed) Published
Abstract [en]

A facile one-pot spray-drying process was developed for fabrication and in-situ crosslinking of chitosan microspheres to improve the adsorption capacity by microscopic design. A fully biobased nature was achieved by utilizing genipin (GP) as a crosslinking agent and chitosan derived nano-graphene oxide (nGO) as a property tuner. The produced chitosan microspheres were further proven as powerful adsorbents for common wastewater contaminants such as anionic dyes and pharmaceutical contaminants, here modelled by methyl orange (MO) and diclofenac sodium (DCF). By regulating the amount of GP and nGO, as well as by controlling the process parameters including the spraydrying inlet temperature and post-heat treatment, the surface morphology, size, zeta potential and adsorption efficiency of the microspheres could be tuned accordingly. The adsorption efficiency for MO and DCF reached 98.9 and 100 %, respectively. The microspheres retained high DCF adsorption efficiency after six adsorption and desorption cycles and the recyclability was improved by incorporated nGO. The fabricated microspheres, thus, have great potential as reusable and eco-friendly adsorbents.

Place, publisher, year, edition, pages
American Chemical Society (ACS), 2019
Keywords
In-situ crosslinking, microspheres, chitosan, spray drying, genipin, biobased, recyclable
National Category
Polymer Chemistry
Research subject
Fibre and Polymer Science
Identifiers
urn:nbn:se:kth:diva-248442 (URN)10.1021/acs.biomac.9b00186 (DOI)000468120800012 ()2-s2.0-85064830922 (Scopus ID)
Note

QC 20190410

Available from: 2019-04-09 Created: 2019-04-09 Last updated: 2019-11-11Bibliographically approved
4. Microwave carbonized cellulose for trace pharmaceutical adsorption
Open this publication in new window or tab >>Microwave carbonized cellulose for trace pharmaceutical adsorption
2018 (English)In: Chemical Engineering Journal, ISSN 1385-8947, E-ISSN 1873-3212, Vol. 346, p. 557-566Article in journal (Refereed) Published
Abstract [en]

A promising sustainable strategy to valorize cellulose to high-value adsorbents for trace pharmaceuticals, like diclofenac sodium (DCF), in the water is demonstrated. Carbon nanospheres (CN) as the DCF adsorbent were derived from cellulose through a one-pot microwave-assisted hydrothermal carbonization method. CN exhibited efficient DCF removal (100% removal of 0.001 mg/mL DCF in 30 s and 59% removal of 0.01 mg/mL DCF in 1 h). The adsorption kinetics and isotherm data were well-fitted with the pseudo-second-order kinetic model and Langmuir model, respectively. The adsorption process was endothermic and spontaneous as confirmed by the thermodynamic parameters. Multiple characterization techniques including SEM/EDS, FTIR, FTIR-imaging and zeta potential were applied to qualitatively investigate the adsorption process. π-π stacking and hydrogen bonding were proposed as the dominant adsorption interactions. CN also demonstrated effective adsorption capacity towards three other commonly-detected contaminants in the wastewater including ketoprofen (KP), benzophenone (BZP), and diphenylamine (DPA), each bearing partial structural similarity with DCF. The affinity of the contaminants towards CN followed the order DPA > BZP > DCF > KP, which could be explained by the different configurations and chemical units. It was speculated that for DCF and KP, the steric hindrance and electrostatic repulsion produced by dissociated carboxyl groups can impede the adsorption process as compared to DPA and BZP. This methodology could offer further insights into the drug adsorption on the cellulose-derived carbon adsorbents and the use of bioderived carbons for treatment of wastewaters contaminated with pharmaceuticals.

Place, publisher, year, edition, pages
Elsevier, 2018
Keywords
Adsorption, Carbon nanosphere, Carbonization, Cellulose, Diclofenac, Microwave
National Category
Chemical Sciences Polymer Technologies
Identifiers
urn:nbn:se:kth:diva-227509 (URN)10.1016/j.cej.2018.04.014 (DOI)000432878400057 ()2-s2.0-85045434362 (Scopus ID)
Note

QC 20180518

Available from: 2018-05-18 Created: 2018-05-18 Last updated: 2019-04-10Bibliographically approved

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The full text will be freely available from 2020-04-20 12:12
Available from 2020-04-20 12:12

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