Water splitting, in which water molecules can be transformed into hydrogen and oxygen, is an appealing energy conversion and transformation strategy to address the environmental and energy crisis. The oxygen evolution reaction (OER) is dynamically slow, which limits energy conversion efficiency during the water-splitting process and requires high-efficiency water oxidation catalysts (WOCs) to overcome the OER energy barrier. It is generally accepted that multinuclear WOCs possess superior OER performances, as demonstrated by the CaMn4 O5 cluster in photosystem II (PSII), which can catalyze the OER efficiently with a very low overpotential. Inspired by the CaMn4 O5 cluster in PSII, some multinuclear WOCs were synthesized that could catalyze water oxidation. In addition, some mononuclear molecular WOCs also show high water oxidation activity. However, it cannot be excluded that the high activity arises from the formation of dimeric species. Recently, some mononuclear heterogeneous WOCs showed a high water oxidation activity, which testified that mononuclear active sites with suitable coordination surroundings could also catalyze water oxidation efficiently. This Review focuses on recent progress in the development of mono-/multinuclear homo- and heterogeneous catalysts for water oxidation. The active sites and possible catalytic mechanisms for water oxidation on the mono-/multinuclear WOCs are provided.
Keywords: electrochemistry; heterogeneous catalysis; homogeneous catalysis; transition metals; water splitting.
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