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Calcium manganese oxides as oxygen evolution catalysts: O_2 formation pathways indicated by ~(18)O-labelling studies

机译:钙锰氧化物作为氧气释放催化剂:〜(18)O-标记研究表明O_2的形成途径

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Oxygen evolution catalysed by calcium manganese and manganese-only oxides was studied in ~(18)O-enriched water. Using membrane-inlet mass spectrometry, we monitored the formation of the different O_2 isotopologues ~(16)O_2, ~(16)O~(18)O and ~(18)O_2 in such reactions simultaneously with good time resolution. From the analysis of the data, we conclude that entirely different pathways of dioxygen formation catalysis exist for reactions involving hydrogen peroxide (H_2O_2), hydrogen persulfate (HSO_5~-) or single-electron oxidants such as Ce~(IV) and [Ru ~(III)(bipy)_3]~(3+). Like the studied oxide catalysts, the active sites of manganese catalase and the oxygen-evolving complex (OEC) of photosystem II (PSII) consist of μ-oxido manganese or μ-oxido calcium manganese sites. The studied processes show very similar ~(18)O-labelling behaviour to the natural enzymes and are therefore interesting model systems for in vivo oxygen formation by manganese metalloenzymes such as PSII. Clearly labelled: Oxygen formed in reactions catalysed by (calcium) manganese oxides showed distinct ~(18)O-labelling patterns depending on the oxidation agent used. The results allow parallels to be drawn to manganese metalloenzymes involved in O-O bond formation in vivo.
机译:研究了〜(18)O富集水中钙锰和仅锰氧化物催化的氧气逸出。使用膜入口质谱法,我们以良好的时间分辨率同时监测了这些反应中不同的O_2同位素〜(16)O_2,〜(16)O〜(18)O和〜(18)O_2的形成。通过对数据的分析,我们得出结论,涉及过氧化氢(H_2O_2),过硫酸氢盐(HSO_5〜-)或单电子氧化剂(例如Ce〜(IV)和[Ru〜]的反应)存在完全不同的双氧形成催化途径。 (III)(bipy)_3]〜(3+)。与所研究的氧化物催化剂一样,锰过氧化氢酶的活性位点和光系统II(PSII)的析氧复合物(OEC)由μ-氧化锰或μ-氧化钙锰位点组成。所研究的过程显示出与天然酶非常相似的〜(18)O标记行为,因此是通过锰金属酶(如PSII)在体内形成氧气的有趣模型系统。清晰地标记:由(钙)锰氧化物催化的反应中形成的氧气根据所使用的氧化剂表现出不同的〜(18)O-标记模式。结果使得与体内参与O-O键形成的锰金属酶相似。

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