Effects of ring substituents on electrocatalytic activity of manganese phthalocyanines towards the reduction of molecular oxygen

Reduction of oxygen electrocatalyzed by adsorbed films of manganese phthalocyanine complexes is reported. The complexes studied were: manganese phthalocyanine (MnPc, 1); manganese tetraamino phthalocyanine (MnTAPc, 2); manganese tetrapentoxy pyrrole phthalocyanine (MnTPePyrPc, 3); manganese tetra phenoxy pyrrole phthalocyanine (MnTPPyrPc, 4); manganese tetra mercaptopyrimidine phthalocyanine (MnTMPyPc, 5) and manganese tetra ethoxy thiophene phthalocyanine (MnTETPc, 6). The reaction was conducted in buffer solutions of pH range 1-12. Rotating disk electrode voltammetry revealed two electron reduction in acidic and slightly alkaline media due to the formation of hydrogen peroxide. In highly basic media, water is the major product formed via four electron transfer. The reaction was found to be first order in the diffusing analyte oxygen. (c) 2006 Elsevier B.V. All rights reserved.