| 1. |
- Carlsson, Daniel O., et al.
(författare)
-
A Comparative Study of the Effects of Rinsing and Aging of Polypyrrole/Nanocellulose Composites on Their Electrochemical Properties
- 2013
-
Ingår i: Journal of Physical Chemistry B. - : American Chemical Society (ACS). - 1520-6106 .- 1520-5207. ; 117:14, s. 3900-3910
-
Tidskriftsartikel (refereegranskat)abstract
- The effects of polymerization conditions, rinsing, and storage on composites composed of polypyrrole (PPy) and Cladophora nanocellulose in terms of purity, chemical composition, conductivity, and electroactivity were investigated using conductivity measurements, cyclic voltammetry, FTIR-ATR, XPS, and ICP-AES. A clear correlation between rinsing volume and PPy degradation was found using water- or NaCl-rinsing solutions as evidenced by conductivity and electroactivity losses. It was further found, through FTIR-ATR as well as XPS-measurements, that this degradation was caused by incorporation of hydroxyl groups in the PPy-layer. The extent of degradation correlated with a shift in the FTIR-ATR peak around 1300 cm(-1), showing that FTIR-ATR may be used as a quick diagnostic tool to evaluate the extent of degradation. By the use of acidic rinsing solution, this degradation effect was eliminated and resulted in superior samples in terms of both conductivity and electroactivity and also in a more efficient removal of reactants. Upon ambient storage, over a period of 200 days, a gradual decrease in conductivity was found for initially highly conductive samples. The electroactivity, on the other hand, was relatively unaffected by storage, showing that conductivity measurements alone are ineffective to determine the degree of polymer degradation if the water content is not controlled. Also, FTIR-ATR measurements indicated that the oxidation state did not change to any large extent upon storage and that only minor degradation of PPy occurred. The results presented herein thus offer valuable guidelines on how to develop simple and reliable postsynthesis treatments of conducting polymer paper composites with performance fulfilling requirements on stability, electroactivity, and purity in applications such as environmentally friendly energy storage devices and biomedical applications.
|
|
| 2. |
|
|
| 3. |
|
|
| 4. |
- Carlsson, Daniel O., et al.
(författare)
-
Cooxidant-free TEMPO-mediated oxidation of highly crystalline nanocellulose in water
- 2014
-
Ingår i: RSC Advances. - : Royal Society of Chemistry (RSC). - 2046-2069. ; 4:94, s. 52289-52298
-
Tidskriftsartikel (refereegranskat)abstract
- Selective oxidation of C6 hydroxyls to carboxyls through 2,2,6,6,-tetramethylpiperidine-1-oxyl (TEMPO)-mediated oxidation, where the oxidizing species (TEMPO+) is generated by cooxidants, such as NaBrO, NaClO or NaClO2, has become a popular way to modify the surfaces of nanocellulose fibrils in aqueous solutions. Employing highly crystalline nanocellulose from Cladophora sp. algae we demonstrate that the same degree of oxidation (D.O.) can be achieved within approximately the same time by replacing the cooxidants with electrogeneration of TEMPO+ in a bulk electrolysis setup. The D.O. is controlled by the oxidation time and the maximum D.O. achieved (D.O. 9.8%, 0.60 mmol g-1 of carboxylic acids and 0 mmol g-1 aldehydes) corresponds to complete oxidation of the surface-confined C6. This shows that TEMPO+ is not sterically hindered from completely oxidizing the fibril surface of Cladophora nanocellulose, in contrast to earlier hypotheses that were based on results with wood-derived nanocellulose. The oxidation does not significantly affect the morphology, the specific surface area (>115 m2 g-1) or the pore characteristics of the water-insoluble fibrous particles that were obtained after drying, but depolymerization corresponding to ∼20% was observed. For extensive oxidation times, the product recovery of water-insoluble fibrils decreased significantly while significant amounts of charge passed through the system. This could indicate that the oxidation proceeds beyond the fibril surface, in contrast to the current view that TEMPO-mediated oxidation is confined only to the surface.
|
|
| 5. |
- Carlsson, Daniel O., et al.
(författare)
-
Cooxidant-free TEMPO-mediated oxidation of highly crystalline nanocellulose in water
- 2014
-
Ingår i: RSC Advances. - 2046-2069. ; 4:94, s. 52289-52298
-
Tidskriftsartikel (refereegranskat)abstract
- Selective oxidation of C6 hydroxyls to carboxyls through 2,2,6,6,-tetramethylpiperidine-1-oxyl (TEMPO)-mediated oxidation, where the oxidizing species (TEMPO+) is generated by cooxidants, such as NaBrO, NaClO or NaClO2, has become a popular way to modify the surfaces of nanocellulose fibrils in aqueous solutions. Employing highly crystalline nanocellulose from Cladophora sp. algae we demonstrate that the same degree of oxidation (D.O.) can be achieved within approximately the same time by replacing the cooxidants with electrogeneration of TEMPO+ in a bulk electrolysis setup. The D.O. is controlled by the oxidation time and the maximum D.O. achieved (D.O. 9.8%, 0.60 mmol g-1 of carboxylic acids and 0 mmol g-1 aldehydes) corresponds to complete oxidation of the surface-confined C6. This shows that TEMPO+ is not sterically hindered from completely oxidizing the fibril surface of Cladophora nanocellulose, in contrast to earlier hypotheses that were based on results with wood-derived nanocellulose. The oxidation does not significantly affect the morphology, the specific surface area (>115 m2 g-1) or the pore characteristics of the water-insoluble fibrous particles that were obtained after drying, but depolymerization corresponding to [similar]20% was observed. For extensive oxidation times, the product recovery of water-insoluble fibrils decreased significantly while significant amounts of charge passed through the system. This could indicate that the oxidation proceeds beyond the fibril surface, in contrast to the current view that TEMPO-mediated oxidation is confined only to the surface.
|
|
| 6. |
|
|
| 7. |
- Carlsson, Daniel O., et al.
(författare)
-
Electroactive nanofibrillated cellulose aerogel composites with tunable structural and electrochemical properties
- 2012
-
Ingår i: Journal of Materials Chemistry. - : Royal Society of Chemistry (RSC). - 0959-9428 .- 1364-5501. ; 22:36, s. 19014-19024
-
Tidskriftsartikel (refereegranskat)abstract
- This work presents conductive aerogel composites of nanofibrillated cellulose (NFC) and polypyrrole (PPy) with tunable structural and electrochemical properties. The conductive composites are prepared by chemically polymerizing pyrrole onto TEMPO-oxidized cellulose nanofibers dispersed in water and the various nanostructures are obtained employing different drying methods. Supercritical CO2 drying is shown to generate high porosity aerogel composites with the largest surface area (246 m(2) g(-1)) reported so far for a conducting polymer-paper based material, whereas composites produced by ambient drying attain high density structures with mechanical properties significantly surpassing earlier reported values for cellulose-conducting polymer composites when normalized with respect to the content of reinforcing cellulose (Young's modulus = 0.51 GPa, tensile strength = 10.93 MPa and strain to failure = 2.5%). Electrochemical measurements clearly show that differences in the porosity give rise to dramatic changes in the voltammetric and chronoamperometric behavior of the composites. This indicates that mass transport rate limitations also should be considered, in addition to the presence of a distribution of PPy redox potentials, as an explanation for the shapes of the voltammetric peaks. A specific charge capacity of similar to 220 C g(-1) is obtained for all composites in voltammetric experiments performed at a scan rate of 1 mV s(-1) and this capacity is retained also at scan rates up to 50 mV s(-1) for the high porosity composites. The composites should be applicable as electrodes in structural batteries and as membranes in ion exchange applications requiring exchange membranes of high mechanical integrity or high porosity.
|
|
| 8. |
|
|
| 9. |
|
|
| 10. |
|
|
