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用于增强碱性溶液中析氧反应催化性能的辉铜矿CuS纳米晶体的表面重构

Surface Reconstruction of Covellite CuS Nanocrystals for Enhanced OER Catalytic Performance in Alkaline Solution.

作者信息

Zhu Jiamin, Zi Shengjie, Zhang Nan, Hu Yang, An Li, Xi Pinxian

机构信息

State Key Laboratory of Applied Organic Chemistry, Frontiers Science Center for Rare Isotopes, College of Chemistry and Chemical Engineering, Lanzhou University, Lanzhou, 730000, P. R. China.

出版信息

Small. 2023 Sep;19(37):e2301762. doi: 10.1002/smll.202301762. Epub 2023 May 7.

Abstract

Oxygen evolution reaction (OER) is one of the important half-reactions in energy conversion equipment such as water-spitting devices, rechargeable metal-air batteries, and so on. It is beneficial to develop efficient and low-cost catalysts that understand the reaction mechanism of OER and analyze the reconstruction phenomenon of transition metal sulfide. Interestingly, copper sulfide and cuprous sulfide with the same components possess different reconstruction behaviors due to their different metal ion valence states and different atomic arrangement modes. Because of a unique atomic arrangement sequence and certain cationic defects, the reconstruction phenomenon of CuS nanomaterials are that S is firstly oxidized to SO and then Cu is converted into CuO via Cu(OH) . In addition, the specific "modified hourglass structure" of CuS with excellent conductivity is easier to produce intermediates. Compared with Cu S, CuS exhibits excellent OER activity with a lower overpotential of 192 mV at 10 mA cm and remarkable electrochemical stability in 1.0 m KOH for 120 h. Herein, this study elucidates the reconstruction modes of CuS and Cu S in the OER process and reveals that CuS has a stronger CuS bond and a faster electronic transmission efficiency due to "modified hourglass structure," resulting in faster reconstruction of CuS than Cu S.

摘要

析氧反应(OER)是诸如析水装置、可充电金属空气电池等能量转换设备中的重要半反应之一。开发能够理解OER反应机理并分析过渡金属硫化物重构现象的高效低成本催化剂具有重要意义。有趣的是,具有相同成分的硫化铜和硫化亚铜由于其不同的金属离子价态和不同的原子排列方式而具有不同的重构行为。由于独特的原子排列顺序和一定的阳离子缺陷,CuS纳米材料的重构现象是S首先被氧化为SO ,然后Cu 通过Cu(OH) 转化为CuO。此外,具有优异导电性的CuS的特定“修饰沙漏结构”更容易产生中间体。与Cu S相比,CuS在10 mA cm 时具有192 mV的较低过电位,表现出优异的OER活性,并且在1.0 m KOH中120小时具有显著的电化学稳定性。在此,本研究阐明了OER过程中CuS和Cu S的重构模式,并揭示由于“修饰沙漏结构”,CuS具有更强的CuS键和更快的电子传输效率,导致CuS的重构比Cu S更快。

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