INVESTIGADORES
AZZARONI Omar
artículos
Título:
Temperature-Dependent Transport Properties of Poly [2-(methacryloyloxy)ethyl] Trimethylammonium Chloride Brushes Resulting from Ion Specific Effects
Autor/es:
T. ALONSO-GARCÍA; C. GERVASI; M.J. RODRÍGUEZ-PRESA; E. GUIÉRREZ-PINEDA; S.E. MOYA; O. AZZARONI
Revista:
JOURNAL OF PHYSICAL CHEMISTRY C
Editorial:
AMER CHEMICAL SOC
Referencias:
Lugar: Washington; Año: 2013 vol. 117 p. 26680 - 26688
ISSN:
1932-7447
Resumen:
Combined use of electrochemical techniques (electrochemical impedance
spectroscopy and cyclic voltammetry) and quartz crystal microbalance
with dissipation allowed to resolve separately the thermal effects on
diffusion and electron-transfer steps of the electrochemical reaction of
the [Fe(CN)6]3?/4? redox couple at a Au electrode
modified with poly[2-(methacryloyloxy)ethyl]trimethylammonium chloride
(PMETAC) brushes. Arrhenius-type dependences of the kinetic constant and
the diffusion coefficient with temperature were observed in different
electrolytes. Ion-paired collapsed polyelectrolyte brushes in NaClO4
result in compact stiff structures with less amount of entrapped water
and markedly different from the same brushes with a collapse driven by
pure Coulombic screening in NaCl. A remarkable difference related to the
type of counterion is the occurrence of a thermal transition for the
polyelectrolyte brush in the presence of ClO4? ions at near-ambient temperature (17
°C). Activation energies for electron-transfer and diffusion processes
become twice as large as those for temperatures above the thermal
transition. These electrochemical studies demonstrate not only the
critical role of ion-pairing interactions in determining the
physicochemical properties of the macromolecular system but also provide
experimental evidence of counterion-induced thermocontrolled transport
functionality in the polyelectrolyte brush layer.