Unveiling the High Catalytic Activity of a Dinuclear Iron Complex for the Oxygen Evolution Reaction.

The dinuclear iron complex [(HO)-Fe-(ppq)-O-(ppq)-Fe-Cl] (Fe(ppq), ppq = 2-(pyrid-2'-yl)-8-(1″,10″-phenanthrolin-2″-yl)-quinoline) demonstrates a catalytic activity about one order of magnitude higher than the mononuclear iron complex [Cl-Fe(dpa)-Cl] (Fe(dpa), dpa = ,-di(1,10-phenanthrolin-2-yl)--isopentylamine) for the oxygen evolution reaction (OER). However, the mechanism behind such an unusually high activity has remained largely unclear. To solve this puzzle, a decomposition-and-reaction mechanism is proposed for the OER with the dinuclear Fe(ppq) complex as the initial state of the catalytic agent. In this mechanism, the high-valent dinuclear iron complex first dissociates into two mononuclear moieties, and the oxidized mononuclear iron complexes directly catalyze the formation of an O-O bond through a nitrate attack pathway with nitrate functioning as a cocatalyst. Density functional theory calculations reveal that it is the electron-deficient microenvironment around the iron center that gives rise to the remarkable catalytic activity observed experimentally. Therefore, the outstanding performance of the Fe(ppq) catalyst can be ascribed to the high reactivity of its mononuclear moieties in a high oxidation state, which is concomitant with the structural stability of the low-valent dinuclear complex. The theoretical insights provided by this study could be useful for the optimization and design of novel iron-based water oxidation catalysts.