时间：2025-09-06
来源： 77779193永利集团
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ABSTRACT
Besides our extended studies on photocatalytic hydrogen evolution by Pt(II)-based molecular catalysts [1], mechanistic studies on single-site water oxidation catalysts (WOCs) of Ru, Fe, Co, and Cu have been advanced [2,3]. Recently, the O-O coupling by a cobalt polyoxomolybdate (CoPOM) was shown to proceed among the preinstalled oxygen atoms in the cluster [4]. We also showed that both CoPOM and cobalt tetraphenylporphyrin (CoTPP) WOCs effectively promote photocatalytic WO when they are physisorbed over the photosensitizing carbon nitrides (C3N4) [5]. Our molecular-based TiO2 photoanode fabricated by chemisorption of Ru-based polypyridyl photosensitizer and WOC (Ru-bda catalyst) were also shown to drive photocatalytic WO at an interface [6].
Another important issue has been to fabricate artificial photosynthetic systems enabling photocatalytic carbon dioxide (CO2) reduction into value-added fuels. By insisting in the use of aqueous reaction platforms, our initial challenge was to gain a sufficiently high CO2 reduction selectivity versus water reduction even in fully aqueous media. A high selectivity in CO2 reduction versus water reduction (SelCO2=90 %) with a high turnover number (TONCO=4000, 12 h) was successfully achieved by us [7-9]. The high selectivity was rationalized by the mismatch in frontier MO association of the metal nucleophile with a 1s(H+) orbital [9]. The lifetime of our water-soluble copper(I) diphosphine-diimine photosensitizer was shown to be drastically elongated by the hydrophobic coverage of alkylammonium ions, leading to demonstrate a new technique to improve the reductive quenching efficiency [10].
Although formate is an attractive alternative to fossil fuels due to its potential application in reversible hydrogen storage, selective catalysts for CO2-to-HCOOH conversion are still limited, especially when photo-driven in aqueous media. Our recent studies successfully unveiled the mechanism of CO2 reduction to formate which undergoes via the M-H attack on CO2, directly ends up with the release of formate [11,12]. Remarkably, the water-soluble [RhIIICp*(dihydroxy-bpy)Cl]+ family was found to be the first example showing the water-induced switching in selectivity for the CO2-to-HCOOH conversion [12].
Keywords: Water Oxidation Catalysis; Hydrogen Evolution Catalysis; CO2 Reduction Catalysis
REFERENCES
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