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Enhancement of Solar Fuel Production Schemes by Using a Ru,Rh,Ru Supramolecular Photocatalyst Containing Hydroxide Labile Ligands

机译:使用含氢氧根不稳定配体的Ru,Rh,Ru超分子光催化剂增强太阳能生产方案

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摘要

Polyazine-bridged (RuRhRuII)-Rh-II-Ru-III complexes with two halide ligands, Cl- or Br-, bound to the catalytically active Rh center are efficient single-component photocatalysts for H2O reduction to H-2 fuel, with the coordination environment on Rh impacting photocatalysis. Herein reported is a new, halide-free (RuRhRuII)-Rh-II-Ru-III photocatalyst with OH- ligands bound to Rh, further enhancing the photocatalytic reactivity of the structural motif. H-2 production experiments using the photocatalyst bearing OH- ligands at Rh relative to the analogues bearing halides at Rh in solvents of varying polarity (DMF, CH3CN, and H2O) suggest that ion pairing with halides deactivates photocatalyst function, representing an exciting phenomenon to exploit in the development of catalysts for solar H-2 production schemes.
机译:具有两个卤化物配体Cl-或Br-的聚嗪桥(RuRhRuII)-Rh-II-Ru-III配合物结合到具有催化活性的Rh中心上,是将H2O还原为H-2燃料的有效单组分光催化剂,配体环境对Rh影响的光催化作用。本文报道了一种新的无卤(RuRhRuII)-Rh-II-Ru-III光催化剂,其中OH-配体与Rh结合,进一步增强了结构基序的光催化反应性。在具有不同极性的溶剂(DMF,CH3CN和H2O)中,使用Rh处带有OH-配体的光催化剂相对于Rh处带有卤化物的类似物(DMF,CH3CN和H2O)进行H-2生产实验表明,与卤化物配对的离子会失活光催化剂功能,这代表了一种令人兴奋的现象。开发用于太阳能H-2生产方案的催化剂。

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