resumo
Amorphous poly(epsilon-caprolactone) (PCL(530))/siloxane ormolytes doped with manganese perchlorate (Mn(ClO4)(2)) (d-PCL(530)/siloxane(n)Mn(ClO4)(2) with n = 20, 50, and 100), thermally stable up to at least 200 degrees C, were synthesized by the sol-gel method. Ionic conductivity values up to 4.8 x 10(-8) and 2.0 x 10(-6) S cm(-1) at about 25 and 100 degrees 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 Mn2+ ions bonded to all the "free" C = O 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 Mn2+ ions along a bidentate configuration. The magnitude of the electron paramagnetic resonance (EPR) hyperfine constant of the analyzed samples (A approximate to 90 x 10(-4)cm(-1)) suggested that the bonding between Mn2+ ions and the surrounding ligands is moderately ionic. The synthetized d-PCL(530)/siloxanenMn (ClO4)(2) biohybrids have potential application in paramagnetic, photoelectrochemical and electrochromic devices. (C) 2016 Elsevier Ltd. All rights reserved.
palavras-chave
ELECTROCHEMICAL IMPEDANCE SPECTROSCOPY; ELECTROCHROMIC DEVICES; MANGANESE IONS; LITHIUM PERCHLORATE; SMART WINDOWS; DI-UREASILS; X-RAY; ELECTROLYTES; GLASSES; GREEN
categoria
Electrochemistry
autores
Pereira, RFP; Donoso, JP; Magon, CJ; Silva, IDA; Cardoso, MA; Goncalves, MC; Sabadini, RC; Pawlicka, A; Bermudez, VD; Silva, MM
nossos autores
Marita Alves Cardoso
Estudante de doutoramentoGrupos
Projectos
agradecimentos
This work was supported by Fundacao para a Ciencia e a Tecnologia (FCT) and Feder (contracts PTDC/CTM-BPC/112774/2009, PEst-OE/QUI/UI0616/2014 and PEst-C/QUI/UI0686/2013) and COST Action MP1202 "Rational design of hybrid organic-inorganic interfaces". R.F.P.P. acknowledges FCT for a grant (SFRH/BPD/87759/2012). M.M.S. acknowledges CNPq (PVE grant 406617/2013-9), for a mobility grant. The financial support of the Brazilian agencies Capes and CNPq are gratefully acknowledged. Research was partially financed by the CeRTEV, Center for Research, Technology and Education in Vitreous Materials, FAPESP 2013/07793-6.