Ion conducting and paramagnetic d-PCL(530)/siloxane-based biohybrids doped with Mn2+ ions. (1st September 2016)

• Record Type: Journal Article
• Authors: Pereira, R.F.P.; Donoso, J.P.; Magon, C.J.; Silva, I.D.A.; Cardoso, M.A.; Gonçalves, M.C.; Sabadini, R.C.; Pawlicka, A.; de Zea Bermudez, V.; Silva, M.M.
• Is Part Of: Electrochimica acta. Volume 211(2016)
• Page Start: 804
• Page End: 813
• Publication Date: 2016-09-01
• Subjects: poly(e-caprolactone)/siloxane biohybrids -- manganese perchlorate -- sol-gel -- ionic conductivity -- paramagnetism; Electrochemistry -- Periodicals; Electrochemistry, Industrial -- Periodicals; 541.37
• DOI: 10.1016/j.electacta.2016.06.088
• Languages: English
• ISSNs: 0013-4686

Abstract

Highlights: New d-PCL(530)/siloxanen Mn(ClO4 )2 biohybrids were synthesized by the sol-gel method. Hydrogen bonding interactions were significantly influenced by the inclusion of the salt. Mn 2+ ions are coordinated to carbonyl groups of the d-PCL(530)/siloxane matrix and to the perchlorate ions. Interesting ionic conductivity and paramagnetic properties were attained. These new biohybrids present potential application as solid electrolytes. Abstract: Amorphous poly(ε-caprolactone) (PCL(530))/siloxane ormolytes doped with manganese perchlorate (Mn(ClO4 )2 ) (d-PCL(530)/siloxanen Mn(ClO4 )2 with n = 20, 50, and 100), thermally stable up to at least 200 °C, were synthesized by the sol-gel method. Ionic conductivity values up to 4.8 × 10 −8 and 2.0 × 10 −6 S cm −1 at about 25 and 100 °C, respectively, were obtained for n = 20. FT-IR data demonstrated that the hydrogen bonding interactions present in the non-doped d-PCL(530)/siloxane host hybrid matrix were significantly influenced by the inclusion of Mn(ClO4 )2 which promoted the formation of more oxyethylene/urethane and urethane/urethane aggregates. In addition, the Mn 2+ ions bonded to all the "free" CO groups of the urethane cross-links and to some of the "free" ester groups of the amorphous PCL(530) chains. In the electrolytes, the ClO4 − ions were found "free" and bonded to the Mn 2+ ions along a bidentate configuration. The magnitude of the electron paramagnetic resonance (EPR) hyperfine constant of the analyzed samples ( A ≈ 90×10 −4 cm −1 ) suggested that the bonding between Mn 2+ ions and the surrounding ligands is moderately ionic. The synthetized d-PCL(530)/siloxanen Mn(ClO4 )2 biohybrids have potential application in paramagnetic, photoelectrochemical and electrochromic devices.