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Supported gold clusters as effective and reusable photocatalysts for the abatement of endocrine-disrupting chemicals under visible light
Journal of Catalysis ( IF 7.3 ) Pub Date : 2017-08-20 , DOI: 10.1016/j.jcat.2017.07.027
Fei Xu , Jinfan Chen , Sergii Kalytchuk , Ling Chu , Yiru Shao , Dexin Kong , Kung-Hui Chu , Patrick H.-L. Sit , Wey Yang Teoh

Photocatalysts based on glutathione-protected Au clusters (1.5 ± 0.4 nm) were synthesized and assessed for the visible-light degradation of ten different endocrine-disrupting chemicals (EDCs) and related compounds. In its as-prepared form, the Au clusters undergo rapid photocharge recombination resulting in no appreciable photocatalytic activity. Coupling with non-activated TiO2 acceptor was necessary to achieve efficient interfacial charge separation that allowed the photocharges on the Au clusters to be effectively harvested for surface redox reactions. Under visible light excitation, the Au cluster undergoes ligand-to-metal charge transfer and resulting in the accumulation of photohole on the glutathione ligand (i.e., the HOMO state). The transfer of photoholes to the hydrogen-bonded EDCs is identified as the main oxidation pathway. The hole transfer oxidation, which was probably complemented by superoxide radicals attack, was necessary since the low HOMO level of the Au clusters (+1.21 V vs. RHE, pH 0) disallowed the production of hydroxyl radicals (+2.68 V vs. RHE, pH 0). As such, the photocatalytic degradation rates of EDCs are in accordance with the trend of Langmuir adsorption capacities. Lastly, we demonstrated the high reusability of the Au cluster/TiO2 photocatalyst, retaining 96% of the initial activity even after 5 repeated cycles or equivalent to 25 h of continuous irradiation.



中文翻译:

支持的金团簇可作为有效和可重复使用的光催化剂,用于在可见光下减少破坏内分泌的化学物质

合成了基于谷胱甘肽保护的金簇(1.5±0.4 nm)的光催化剂,并评估了十种不同的破坏内分泌的化学物质(EDC)和相关化合物的可见光降解率。以其制备的形式,Au簇经历快速的光电荷复合,导致没有明显的光催化活性。与未活化的TiO 2偶联受体对于实现有效的界面电荷分离是必不可少的,该界面分离可以有效收集Au团簇上的光电荷以进行表面氧化还原反应。在可见光激发下,Au团簇经历了配体到金属的电荷转移,并导致光空穴在谷胱甘肽配体上积累(即,HOMO状态)。光孔向氢键合的EDC的转移被确定为主要的氧化途径。空穴转移氧化很可能是由超氧化物自由基的攻击所补充,因为Au簇的低HOMO水平(+1.21 V vs. RHE,pH 0)不允许产生羟基自由基(+2.68 V vs. 2)。RHE,pH 0)。因此,EDC的光催化降解速率与Langmuir吸附能力的趋势一致。最后,我们证明了Au团簇/ TiO 2光催化剂的高度可重复使用性,即使经过5次重复循环或相当于25 h连续照射,仍可保持96%的初始活性。

更新日期:2017-08-20
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