期刊
CHEMICAL SOCIETY REVIEWS
卷 42, 期 6, 页码 2262-2280出版社
ROYAL SOC CHEMISTRY
DOI: 10.1039/c2cs35287g
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资金
- Italian MIUR [PRIN 20085ZXFEE, PRIN 20085M27SS, FIRB RBAP11C58Y NanoSolar]
- University of Padova [PRAT CPDA104105/10]
- Fondazione Cariparo (Nanomode progetti di eccellenza)
Among molecular water oxidation catalysts (WOCs), those featuring a reactive set of four multi-redox transition metals can leverage an extraordinary interplay of electronic and structural properties. These are of particular interest, owing to their close structural, and possibly functional, relationship to the oxygen evolving complex of natural photosynthesis. In this review, special attention is given to two classes of tetrametallic molecular WOCs: (i) M4O4 cubane-type structures stabilized by simple organic ligands, and (ii) systems in which a tetranuclear metal core is stabilized by coordination of two polyoxometalate (POM) ligands. Recent work in this rapidly evolving field is reviewed, with particular emphasis on photocatalytic aspects. Special attention is given to studies addressing the mechanistic complexity of these systems, sometimes overlooked in the rush for oxygen evolving performance. The complementary role of molecular WOCs and their relationship with bulk oxides and heterogeneous catalysis are discussed.
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