Understanding synergistic catalysis on Pt–Cu diatomic sites via operando X-ray absorption spectroscopy in sulfur redox reactions

IF 42.9 Q1 ELECTROCHEMISTRY eScience Pub Date : 2024-10-01 DOI:10.1016/j.esci.2023.100222
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Abstract

Sulfur redox reactions render lithium–sulfur (Li–S) batteries with an energy density of > 500 ​Wh ​kg−1 but suffer a low practical capacity and fast capacity fade due to sluggish sulfur redox reaction (SRR) kinetics, which lies in the complex reaction process that involves a series of reaction intermediates and proceeds via a cascade reaction. Here, we present a Pt–Cu dual-atom catalyst (Pt/Cu-NG) as an electrocatalyst for sulfur redox reactions. Pt/Cu-NG enabled the rapid conversion of soluble polysulfide intermediates into insoluble Li2S2/Li2S, and consequently, it prevented the accumulation and shuttling of lithium polysulfides, thus outperforming the corresponding single-atom catalysts (SACs) with individual Pt or Cu sites. Operando X-ray absorption spectroscopy and density functional theory calculations revealed that a synergistic effect between the paired Pt and Cu atoms modifies the electronic structure of the Pt site through d-orbital interactions, resulting in an optimal moderate interaction of the metal atom with the different sulfide species. This optimal interaction enhanced charge transfer kinetics and promoted sulfur redox reactions. Our work thus provides important insights on the atomic scale into the synergistic effects operative in dual-atom catalysts and will thus pave the way to electrocatalysts with enhanced efficiency for high-performance Li–S batteries.

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通过 X 射线吸收光谱了解硫氧化还原反应中 Pt-Cu 二原子位点的协同催化作用
硫氧化还原反应可使锂硫(Li-S)电池的能量密度达到 > 500 Wh kg-1,但由于硫氧化还原反应动力学缓慢,实际容量低且容量衰减快,这主要是因为反应过程复杂,涉及一系列反应中间体,并通过级联反应进行。在此,我们提出了一种铂铜双原子催化剂(Pt/Cu-NG)作为硫氧化还原反应的电催化剂。Pt/Cu-NG 能够将可溶性多硫化物中间产物快速转化为不溶性 Li2S2/Li2S,从而防止了多硫化锂的积累和穿梭,因此性能优于具有单独 Pt 或 Cu 位点的相应单原子催化剂 (SAC)。操作X射线吸收光谱和密度泛函理论计算显示,成对的铂原子和铜原子之间的协同效应通过d-轨道相互作用改变了铂位点的电子结构,从而使金属原子与不同的硫化物产生了最佳的适度相互作用。这种最佳相互作用增强了电荷转移动力学,促进了硫氧化还原反应。因此,我们的工作提供了在原子尺度上了解双原子催化剂协同效应的重要视角,从而为高性能锂-S 电池的高效电催化剂铺平了道路。
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