Graphite-conjugated pyrazines obtained from the same condensation method displayed high activity in oxygen reduction, which was not observed for the molecular analogues of pyrazines. The catalytic activity of graphite-conjugated pyrazines for oxygen reduction in an alkaline aqueous electrolyte can be controlled by changing the electrophilicity of pyrazines. Although unmodified glassy carbon electrodes showed activity in oxygen reduction at 0.6 V, graphite-conjugated pyrazines displayed a much higher current at the same voltage, suggesting they were better catalysts under the same conditions. However, the surface site density of electroactive pyrazines, ranging from 14 to 250 pmol cm -2 , was relatively low. Tafel studies revealed that the difference in activity in oxygen reduction catalyzed by graphite-conjugated pyrazines could be easily tuned by modifying the substituents on pyrazines. An increased turnover frequency was observed by switching from methyl (0.12 ± 0.01 s -1 ) to a more electron-withdrawing fluoro-substituted graphite-conjugated pyrazine (0.35 ± 0.01 s -1 ) as depicted in Figure . In a later study, a stepwise mechanism in which a proton-decoupled oxygen activation involves an electron transfer along with oxygen adsorption at the conjugated pyrazine surface, followed by several electron/proton transfers, was proposed. This example further proved that the covalent conjugation of pyrazines on glassy carbon electrodes is an opportunity to combine the advantages of homogenous and heterogeneous catalysis. The catalytic activity of graphite-conjugated pyrazines can be easily adjusted by modifying the electronic properties of the molecular attachments on the active site. Secondly, efficient electron transfer and a higher catalytic rate can be achieved only in the hybrid system, suggesting that reactivity that was not observed for molecular analogues can be introduced through molecule-electrode derivatization.