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Development of Cellulose-Based, Nanostructured, Conductive Paper for Biomolecular Extraction and Energy Storage Applications
Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Engineering Sciences, Nanotechnology and Functional Materials.
2011 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

Conductive paper materials consisting of conductive polymers and cellulose are promising for high-tech applications (energy storage and biosciences) due to outstanding aspects of environmental friendliness, mechanical flexibility, electrical conductivity and efficient electroactive behavior. Recently, a conductive composite paper material was developed by covering the individual nanofibers of cellulose from the green algae Cladophora with a polypyrrole (PPy) layer. The PPy-Cladophora cellulose composite paper is featured with high surface area (80 m2 g-1), electronic conductivity (~2 S cm-1), thin conductive layer (~50 nm) and easily up-scalable manufacturing process. This doctoral thesis reports the development of the PPy-Cladophora composite as an electrode material in electrochemically controlled solid phase ion-exchange of biomolecules and all-polymer based energy storage devices. First, electrochemical ion-exchange properties of the PPy-Cladophora cellulose composite were investigated in electrolytes containing three different types of anions, and it was found that smaller anions (nitrate and chloride) are more readily extracted by the composite than lager anions (p-toluene sulfonate). The influence of differently sized oxidants used during polymerization on the anion extraction capacity of the composite was also studied. The composites synthesized with two different oxidizing agents, i.e. iron (III) chloride and phosphomolybdic acid (PMo), were investigated for their ability to extract anions of different sizes. It was established that the number of absorbed ions was larger for the iron (III) chloride-synthesized sample than for the PMo-synthesized sample for all four electrolytes studied. Further, PPy-Cladophora cellulose composites have shown remarkable electrochemically controlled ion extraction capacities when investigated as a solid phase extraction material for batch-wise extraction and release of DNA oligomers. In addition, composite paper was also investigated as an electrode material in the symmetric non-metal based energy storage devices. The salt and paper based energy storage devices exhibited charge capacities (38−50 mAh g−1) with reasonable cycling stability, thereby opening new possibilities for the production of environmentally friendly, cost efficient, up-scalable and lightweight energy storage systems. Finally, micron-sized chopped carbon fibers (CCFs) were incorporated as additives to improve the charge-discharge rates of paper-based energy storage devices and to enhance the DNA release efficiency. The results showed the independent cell capacitances of ~60-70 F g-1 (upto current densities of 99 mA cm2) and also improved the efficiency of DNA release from 25 to 45%.

Place, publisher, year, edition, pages
Uppsala: Acta Universitatis Upsaliensis , 2011. , 65 p.
Series
Digital Comprehensive Summaries of Uppsala Dissertations from the Faculty of Science and Technology, ISSN 1651-6214 ; 852
Keyword [en]
Polypyrrole, Cladophora cellulose, Conductive paper, Electrochemically controlled ion-exchange, DNA extraction, Paper-based energy storage devices, Chopped Carbon fibers
Research subject
Engineering Science with specialization in Nanotechnology and Functional Materials
Identifiers
URN: urn:nbn:se:uu:diva-158444ISBN: 978-91-554-8150-6 (print)OAI: oai:DiVA.org:uu-158444DiVA: diva2:439468
Public defence
2011-10-21, Polhemsalen, Ångström laboratory, Uppsala, 10:15 (English)
Opponent
Supervisors
Available from: 2011-09-30 Created: 2011-09-07 Last updated: 2011-11-03Bibliographically approved
List of papers
1. Potential controlled anion absorption in a novel high surface area composite of Cladophora cellulose and polypyrrole
Open this publication in new window or tab >>Potential controlled anion absorption in a novel high surface area composite of Cladophora cellulose and polypyrrole
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2009 (English)In: Electrochimica Acta, ISSN 0013-4686, E-ISSN 1873-3859, Vol. 54, no 12, 3394-3401 p.Article in journal (Refereed) Published
Abstract [en]

The electrochemical properties of a novel composite paper material of high surface area consisting of polypyrrole (PPy) deposited on cellulose derived from Cladophora sp. algae have been investigated in electrolytes containing different concentrations of nitrate, chloride and p-toluene sulfonate, as well as in solutions containing both p-toluene sulfonate and chloride. The oxidation mechanism and the dependence of the oxidation behavior of the polypyrrole, which was obtained by oxidation of pyrrole with iron(III) chloride, on the anion type and concentration have been studied. Current nucleation maxima, appearing at different times depending on the anion concentration, were obtained during the oxidation of the reduced polymers as a result of the combined action of the formation and growth of conducting polymer strands and anion diffusion. No loss of capacity was seen during repeated oxidation and reduction of the polymer indicating that trapping of anions in the reduced polymer did not limit the electroactivity of the present material. The latter can be explained by the thin polymer layer present on the cellulose substrate. During the oxidation of the polymer, the anions most likely first cover most of the surface of the composite before diffusing into the bulk of the polymer. The estimated distance between these surface sites was also found to match the size of the anions. For electrolytes containing a mixture of anions, the oxidation charge depends on the concentration and size of the different anions.

The combination of the thin polymer coating and the large specific surface area of the composite give rise to a high ion absorption capacity even for large anions. Hence, the investigated material should be well-suited for use in biotechnological applications involving, e.g., desalting and extraction of proteins and DNA from biological samples.

Place, publisher, year, edition, pages
Elsevier Ltd, 2009
Keyword
Polypyrrole, Cladophora cellulose, Oxidation, Anion exchange, Nucleation, Diffusion, Nitrate, Chloride and p-toluene sulfonate
National Category
Engineering and Technology
Research subject
Engineering Science with specialization in Nanotechnology and Functional Materials; Inorganic Chemistry
Identifiers
urn:nbn:se:uu:diva-102117 (URN)10.1016/j.electacta.2009.01.010 (DOI)000265011700021 ()
Available from: 2009-05-05 Created: 2009-05-05 Last updated: 2017-12-13Bibliographically approved
2. Influence of the type of oxidant on anion exchange properties of fibrous Cladophora cellulose/polypyrrole composites
Open this publication in new window or tab >>Influence of the type of oxidant on anion exchange properties of fibrous Cladophora cellulose/polypyrrole composites
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2009 (English)In: Journal of Physical Chemistry B, ISSN 1520-6106, E-ISSN 1520-5207, Vol. 113, no 2, 426-433 p.Article in journal (Refereed) Published
Abstract [en]

The electrochemically controlled anion absorption properties of a novel large surface area composite paper material composed of polypyrrole (PPy) and cellulose derived from Cladophora sp. algae, synthesized with two oxidizing agents, iron(III) chloride and phosphomolybdic acid (PMo), were analyzed in four different electrolytes containing anions (i.e., chloride, aspartate, glutamate, and p-toluenesulfonate) of varying size. The composites were characterized with scanning and transmission electron microscopy, N2 gas adsorption, and conductivity measurements. The potential-controlled ion exchange properties of the materials were studied by cyclic voltammetry and chronoamperometry at varying potentials. The surface area and conductivity of the iron(III) chloride synthesized sample were 58.8 m2/g and 0.65 S/cm, respectively, while the corresponding values for the PMo synthesized sample were 31.3 m2/g and 0.12 S/cm. The number of absorbed ions per sample mass was found to be larger for the iron(III) chloride synthesized sample than for the PMo synthesized one in all four electrolytes. Although the largest extraction yields were obtained in the presence of the smallest anion (i.e., chloride) for both samples, the relative degree of extraction for the largest ions (i.e., glutamate and p-toluenesulfonate) was higher for the PMo sample. This clearly shows that it is possible to increase the extraction yield of large anions by carrying out the PPy polymerization in the presence of large anions. The results likewise show that high ion exchange capacities, as well as extraction and desorption rates, can be obtained for large anions with high surface area composites coated with relatively thin layers of PPy.

National Category
Chemical Sciences Engineering and Technology
Research subject
Engineering Science with specialization in Nanotechnology and Functional Materials; Inorganic Chemistry
Identifiers
urn:nbn:se:uu:diva-88165 (URN)10.1021/jp806517h (DOI)000262324400006 ()19099422 (PubMedID)
Available from: 2009-01-22 Created: 2009-01-22 Last updated: 2017-12-14Bibliographically approved
3. High-capacity Conductive Nanocellulose Paper Sheets for Electrochemically Controlled Extraction of DNA Oligomers
Open this publication in new window or tab >>High-capacity Conductive Nanocellulose Paper Sheets for Electrochemically Controlled Extraction of DNA Oligomers
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2011 (English)In: PLoS ONE, ISSN 1932-6203, E-ISSN 1932-6203, Vol. 6, no 12, e29243- p.Article in journal (Refereed) Published
Abstract [en]

Highly porous polypyrrole (PPy)-nanocellulose paper sheets have been evaluated as inexpensive and disposable electrochemically controlled three-dimensional solid phase extraction materials. The composites, which had a total anion exchange capacity of about 1.1 mol kg(-1), were used for extraction and subsequent release of negatively charged fluorophore tagged DNA oligomers via galvanostatic oxidation and reduction of a 30-50 nm conformal PPy layer on the cellulose substrate. The ion exchange capacity, which was, at least, two orders of magnitude higher than those previously reached in electrochemically controlled extraction, originated from the high surface area (i.e. 80 m(2) g(-1)) of the porous composites and the thin PPy layer which ensured excellent access to the ion exchange material. This enabled the extractions to be carried out faster and with better control of the PPy charge than with previously employed approaches. Experiments in equimolar mixtures of (dT)(6), (dT)(20), and (dT)(40) DNA oligomers showed that all oligomers could be extracted, and that the smallest oligomer was preferentially released with an efficiency of up to 40% during the reduction of the PPy layer. These results indicate that the present material is very promising for the development of inexpensive and efficient electrochemically controlled ion-exchange membranes for batch-wise extraction of biomolecules.

National Category
Analytical Chemistry Inorganic Chemistry Engineering and Technology
Research subject
Analytical Chemistry; Engineering Science with specialization in Nanotechnology and Functional Materials; Chemistry with specialization in Inorganic Chemistry
Identifiers
urn:nbn:se:uu:diva-158441 (URN)10.1371/journal.pone.0029243 (DOI)000298370400043 ()
Available from: 2011-09-07 Created: 2011-09-07 Last updated: 2017-12-08Bibliographically approved
4. Spatial Mapping of Elemental Distributions in Polypyrrole-Cellulose Nanofibers using Energy-Filtered Transmission Electron Microscopy
Open this publication in new window or tab >>Spatial Mapping of Elemental Distributions in Polypyrrole-Cellulose Nanofibers using Energy-Filtered Transmission Electron Microscopy
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2010 (English)In: Journal of Physical Chemistry B, ISSN 1520-6106, E-ISSN 1520-5207, Vol. 114, no 43, 13644-13649 p.Article in journal (Refereed) Published
Abstract [en]

The energy-filtered transmission electron microscopy (EFTEM) technique has been used to study ion-exchange processes in conductive polymer composite nanofibers. The elemental distributions of carbon, nitrogen, oxygen, chlorine, boron, phosphorus, molybdenum, and sulfur within polypyrrole-cellulose nanofibers, used as potential controlled electrochemical solid phase extraction media, have been studied by EFTEM. The distribution of ions within the polypyrrole-cellulose nanofibers and the penetration depth of ions into the material as a function of the size and charge of the latter were investigated. Further, the spatial distribution of single stranded DNA hexamers inside polypyrrole-cellulose nanofibers was mapped subsequent to the electrochemically controlled extraction of DNA from a borate buffer solution. The results show that the EFTEM mapping technique provides unpreceded possibilities for studies of the distribution of ions inside conductive polymer composites.

National Category
Engineering and Technology Inorganic Chemistry
Research subject
Engineering Science with specialization in Materials Science; Engineering Science with specialization in Nanotechnology and Functional Materials
Identifiers
urn:nbn:se:uu:diva-147126 (URN)10.1021/jp106317p (DOI)000283519600004 ()
Available from: 2011-02-24 Created: 2011-02-24 Last updated: 2017-12-11
5. Ultrafast All-Polymer Paper-Based Batteries
Open this publication in new window or tab >>Ultrafast All-Polymer Paper-Based Batteries
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2009 (English)In: Nano letters (Print), ISSN 1530-6984, E-ISSN 1530-6992, Vol. 9, no 10, 3635-3639 p.Article in journal (Refereed) Published
Abstract [en]

Conducting polymers for battery applications have been subject to numerous investigations during the last two decades. However, the functional charging rates and the cycling stabilities have so far been found to be insufficient for practical applications. These shortcomings can, at least partially, be explained by the fact that thick layers of the conducting polymers have been used to obtain sufficient capacities of the batteries. In the present letter, we introduce a novel nanostructured high-surface area electrode material for energy storage applications composed of cellulose fibers of algal origin individually coated with a 50 nm thin layer of polypyrrole. Our results show the hitherto highest reported charge capacities and charging rates for an all polymer paper-based battery. The composite conductive paper material is shown to have a specific surface area of 80 m(2) g(-1) and batteries based on this material can be charged with currents as high as 600 mA cm(-2) with only 6% loss in capacity over 100 subsequent charge and discharge cycles. The aqueous-based batteries, which are entirely based on cellulose and polypyrrole and exhibit charge capacities between 25 and 33 mAh g(-1) or 38-50 mAh g(-1) per weight of the active material, open up new possibilities for the production of environmentally friendly, cost efficient, up-scalable and lightweight energy storage systems.

Place, publisher, year, edition, pages
American Chemical Society, 2009
National Category
Engineering and Technology
Research subject
Engineering Science with specialization in Nanotechnology and Functional Materials
Identifiers
urn:nbn:se:uu:diva-108553 (URN)10.1021/nl901852h (DOI)000270670500045 ()19739594 (PubMedID)
Available from: 2009-09-22 Created: 2009-09-22 Last updated: 2017-12-13Bibliographically approved
6. Carbon fiber-reinforced polypyrrole-Cladophora nanocellulose composites for paper-based energy storage devices
Open this publication in new window or tab >>Carbon fiber-reinforced polypyrrole-Cladophora nanocellulose composites for paper-based energy storage devices
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(English)Manuscript (preprint) (Other academic)
Identifiers
urn:nbn:se:uu:diva-158442 (URN)
Available from: 2011-09-07 Created: 2011-09-07 Last updated: 2011-11-03
7. Electrochemically Controlled Separation of DNA Oligomers with High Surface Area Conducting Paper Electrode
Open this publication in new window or tab >>Electrochemically Controlled Separation of DNA Oligomers with High Surface Area Conducting Paper Electrode
2011 (English)In: Bioelectronics, Biointerfaces, and Biomedical Applications 4 / [ed] M. Madou, A. Hoff, D. Landheer, L. Nagahara, K. Sode, T. Thundat, C. Wang, Pennington, N.J.: Electrochemical Society, 2011, 135-142 p.Conference paper, Published paper (Refereed)
Place, publisher, year, edition, pages
Pennington, N.J.: Electrochemical Society, 2011
Series
ECS Transactions, ISSN 1938-6737 ; 35:7
National Category
Inorganic Chemistry Engineering and Technology
Research subject
Chemistry with specialization in Inorganic Chemistry; Engineering Science with specialization in Nanotechnology and Functional Materials
Identifiers
urn:nbn:se:uu:diva-153464 (URN)
Conference
219th ECS Meeting, May 1 - May 6, 2011 , Montreal, QC, Canada
Available from: 2011-05-13 Created: 2011-05-13 Last updated: 2016-11-30Bibliographically approved

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