We have previously reported that [Co(CR)Br2]+, where CR is the redox-active macrocycle 2,12-dimethyl-3,7,11,17-tetraazabicyclo-[11.3.1]-heptadeca-1(17),2,11,13,15-pentaene, is capable of electrocatalytically reducing aqueous NO2–. Here we report that buffered solutions induce a new catalytic process at a significantly more anodic potential. In addition, there is an increase in the rate of catalysis, with the largest catalytic current at pH 7. This activity is enabled by a number of buffers, with MOPS (3-(N-morpholino)propanesulfonic acid) showing the largest catalytic current. In addition to more favorable catalytic activity, the presence of buffer changes the reduction products change, with both ammonium and hydroxylamine being formed.

Enhancement of electrochemical nitrite reduction by a cobalt macrocycle assisted by buffer

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