Abstract
The combination of scanning electrochemical microscopy (SECM) with piezoelectric quartz crystal impedance (PQCI) analysis was proposed as a novel multiparameter method for investigating the cyclic voltammetric growth of poly(o-phenylenediamine) (PoPD) thin films at Au electrodes in aqueous solutions of various pH values and the potentiostatic microetching (localized degradation) of these films in 0.10 mol/L aqueous H2SO4 for comparative examinations on polymer porosity and stability. Two potential-sweep ranges, -0.4 to 0.9 (I) and 0 to 0.9 (II) V versus SCE, and four solutions, acidic (A, 0.20 mol/L H2SO4 + 0.10 mol/L Na2SO4; B, 0.10 mol/L H2SO4 + 0.20 mol/L Na2SO4), neutral (C, 0.10 mol/L PBS + 0.20 mol/L Na2SO4, pH 7.2), and alkaline (D, 0.20 mol/L NaOH + 0.20 mol/L Na2SO4) aqueous solutions, were selected for PoPD growth. The pH increase for the polymerization solution increased the molar percentage of polyaniline-like chains in PoPD, as quantified from the current peaks at approximately 0.6 V versus a saturated calomel electrode (SCE) for the oxidation of -NH2 groups in as-prepared PoPD (grown from solutions C and D) during their redox switching in 0.10 mol/L aqueous H2SO4 for the first time. The unusual PQCI responses observed at negative potentials (potential range I) in the first several potential cycles during the cyclic voltammetric growth of PoPD in acidic and neutral solutions have been reasonably explained as being due to the precipitation/dissolution of the poorly soluble phenazinehydrine charge-transfer complexes developed during redox switching of oligomers for the first time, which brought about much less compact PoPD films and their higher degradability than those grown in the same solution but over potential range II. SECM, scanning electron microscopy (SEM), and piezoelectric quartz crystal (PQC) frequency were used to estimate the sizes of etched microscale spots. In addition, the x-, y-, or z-axis movement of a Pt microelectrode of 25-mum diameter near the PQC electrode was found to influence negligibly the PQCI responses in 1.0 mol/L aqueous Na2SO4 containing K4Fe(CN)6 up to 0.10 mol/L, and a new protocol of dynamically electrodepositing silver microwires via the chemical-lens method was proposed for examining the local mass-sensitivity distribution on the PQC surface.
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