In this work a titration technique was used to determine the aniphoteric surface properties of a series of heat-treated electrolytic manganese dioxide (EMD) samples (Lip to 500 degrees C). The surface of each sample was found to consist of independent acidic and basic hydroxyl sites. which could be characterized by their respective equilibrium constants and site concentrations. It was found that the acidic sites Could not be characterized by a single equilibrium constant, but rather by a distribution indicating the Subtle differences between individual sites. while a single equilibrium constant adequately, represented the basic sites. For EMD. K-a varied between 0.1 and 6.3 x 10(-5). with a corresponding a [equivalent to Mn-OH(a)T] value varying between 9.1 and 6.4 x 10(-6) mol m(-2) over the pH range considered. K-b and [equivalent to Mn-OH(b)T] were found to he 1.81 x 10(-9) and 1.93 x 10(-5) mol m(-2), respectively. With heat treatment K-a increased suggesting a strengthening of the Mn-O bond via the removal of defects Such as Mn3+ ions and cation vacancies. The fact that K-b also increased was initially counterintuitive because it suggested that the Mn-O bond had been weakened by heat treatment. However. assuming,, that the acidic and basic hydroxyl groups are independent. the trends in Kb Could be rationalized in terms of oxygen ion coordination in the progressively heat-treated samples. The number of surface sites (N-s) was determined crystallographically and from the sum [equivalent to Mn-OH(a)T] + [equivalent to Mn-OH(b)T]. The data from both methods were of the same order of magnitude but exhibited different trends due to certain inadequacies in both methods. However, the data trends did indicate that the crystal planes at the particle Surface Could be changing with heat treatment due to a decrease in the value of Ns determined from the surface titrations. Electrochemical analysis of the samples in 9 M KOH indicated that their performance degraded considerably with heat treatment. In comparison with the surface titration data. it was Concluded that proton insertion into the Structure Occurred Only through basic surface sites. the decreasing number of which could limit performance.
Journal of Colloid and Interface Science Vol. 285, no. 2, p. 653-664