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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >A comparison between artificial and natural water oxidation
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A comparison between artificial and natural water oxidation

机译：人造水与天然水氧化的比较

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Two artificial water oxidation catalysts, the blue dimer and the Llobet catalyst, have been studied using hybrid DFT methods. The results are compared to those for water oxidation in the natural photosystem II enzyme. Studies on the latter system have now reached a high level of understanding, at present much higher than the one for the artificial systems. A recent high resolution X-ray structural investigation of PSII has confirmed the main features of the structure of the oxygen evolving complex (OEC) suggested by previous DFT cluster studies. The O-O bond formation mechanism suggested is of direct coupling (DC) type between an oxygen radical and a bridging oxo ligand. A similar DC mechanism is found for the Llobet catalyst, while an acid-base (AB) mechanism is preferred for the blue dimer. All of them require at least one oxygen radical. Full energy diagrams, including both redox and chemical steps, have been constructed illustrating similarities and differences to the natural system. Unlike previous DFT studies, the results of the present study suggest that the blue dimer is rate-limited by the initial redox steps, and the Llobet catalyst by O_2 release. The results could be useful for further improvement of the artificial systems.
机译：使用混合DFT方法研究了两种人造水氧化催化剂，蓝色二聚体和Llobet催化剂。将结果与天然光系统II酶中水氧化的结果进行比较。现在，对后一种系统的研究已经达到了很高的理解水平，目前远远高于人工系统。最近对PSII进行的高分辨率X射线结构研究已经证实了先前DFT簇研究表明的析氧复合物（OEC）结构的主要特征。所提出的O-O键形成机理是氧自由基与架桥氧代配体之间的直接偶联（DC）型。对于Llobet催化剂，发现了类似的DC机理，而对于蓝色二聚体，优选酸碱（AB）机理。它们全部都需要至少一个氧自由基。已构建完整的能量图，包括氧化还原步骤和化学步骤，它们说明了与自然系统的相似之处和不同之处。与以前的DFT研究不同，本研究的结果表明，蓝色二聚体受初始氧化还原步骤的速率限制，而Llobet催化剂受O_2释放的速率限制。结果对于进一步改进人工系统可能是有用的。

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