摘要
Copper complexes inspired by O_(2)-activating enzymes have been widely investigated as molecular water oxidation catalysts,capable of facile and reversible O─O bond formation and cleavage under mild conditions.In this study,two copper phenanthroline complexes,namely,Cu(phen)and Cu(dophen),exhibit high turnover frequencies(TOFs)of 74±13 and(5.66±0.29)×10^(3)s^(−1)for water oxidation,respectively.Moreover,amino acid-functionalized carbon dots(CDs)were used to support the adhesion of the[Cu]complexes onto the electrode,significantly enhancing the TOFs of(2.80±0.12)×10^(3)and(4.11±0.24)×10^(4)s^(−1),respectively,exceeding the activity of photosystem Ⅱ in nature.Remarkably,the amino acid-functionalized CDs provide a secondary sphere that mimics the catalytic microenvironment of the copper centre,which promotes proton-coupled electron transfer and O─O bond formation.Finally,the photovoltaic-electrolysis(PVE)system was established using CDs-supported Cu catalysts and commercial silicon solar panels,achieving a high solar-to-hydrogen efficiency of 11.59%under the illumination of AM 1.5 G.This represents the most efficient solar-driven water splitting system based on copper-based catalysts to date,introducing the biomimetic secondary sphere to a“proton-rocking”process for water oxidation catalysis and application of the PVE system.
基金
supported by the National Natural Science Foundation of China(No.52273187)
National Key R&D Program of China(2021YFA1500800)
Guangdong Basic and Applied Basic Research Foundation(2022A1515110372,2023A1515011306,2023A1515240077)
Guangdong-Hong Kong Joint Laboratory for Preparation and Application of Ordered Structural Materials of Guangdong Province(2023B1212120011)。
