Electrochemical and thermodynamic properties of hexacyanoferrate(II)/(III) redox system on multi-walled carbon nanotubes

Novel films consist of multi-walled carbon nanotubes (MWCNT) were fabricated by means of catalytic chemical vapor deposition (CVD) technique with decomposition of either acetonitrile (ACN) or benzene (BZ) using ferrocene (FeCp2) as catalyst. The electrochemical and thermodynamic behavior of the ferrocyanide/ferricyanide, [Fe(CN)6]3−/4− redox couple on synthesized MWCNT-based films was investigated by means of cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) techniques at T = (278.15, 283.15, 293.15, and 303.15) K. The redox couple [Fe(CN)6]3−/4− behaves quasi-reversibly on fabricated MWCNT-based films and its reversibility is enhanced upon increasing temperature. Namely, the findings establish that with the rise in temperature the barrier for interfacial electron transfer decreases, leading, consequently, to an enhancement of the kinetics of the charge transfer process. According to thermodynamics the equilibrium of the redox process is shifted towards the formation of [Fe(CN)6]3− at elevated temperatures.

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► MWCNT-based films were produced.
► [Fe(CN)6]3−/4− is reversible on MWCNTs.
► Barrier for electron transfer decreases with rise in temperature.
► Reversibility of [Fe(CN)6]3−/4− is enhanced with rise in temperature.
► Equilibrium of redox process shifts towards [Fe(CN)6]3− at elevated temperatures.