Elemental Core Level Shift in High Entropy Alloy Nanoparticles via X-ray Photoelectron Spectroscopy Analysis and First-Principles Calculation.
Elemental Core Level Shift in High Entropy Alloy Nanoparticles via X-ray Photoelectron Spectroscopy Analysis and First-Principles Calculation.
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DOI：
10.1021/acsnano.0c09470
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发表时间：
2020-12
期刊：
影响因子：
17.1
通讯作者：
Xiang Xu;Yang Guo;B. Bloom;Jianjun Wei;Haoyang Li;Hailong Li;Yankun Du;Zheng Zeng;Liqing Li
中科院分区：
文献类型：
--
作者：
Xiang Xu;Yang Guo;B. Bloom;Jianjun Wei;Haoyang Li;Hailong Li;Yankun Du;Zheng Zeng;Liqing Li
高熵合金纳米粒子（HEA-NPs）正在扩大其在许多领域的影响力。为了探索此类多元素系统中的电子结构，通过碳热冲击和原位还原方法在两种不同的碳基底上合成了 HEA-NP。通过X射线光电子能谱（XPS）分析和第一原理电子结构计算，研究了五元金属HEA-NPs组分之间的表观核能级能量偏移（负或正）与电子密度变化之间的关系。研究发现，Cu 显示出负的核心能级偏移，而 Fe、Co、Mg、Cr 和 Mn 显示出正的核心能级偏移。虽然实验显示 Ni 具有明显的正核心能级偏移，但电子结构计算表明，这是由费米能级的偏移引起的，并且 Ni 中的电子密度重新分布的行为比其他元素更像 Cu。研究结果表明，纳米粒子中的电子密度重新分布是从电负性较小的元素到电负性较多的元素发生的。这项工作应该指导 HEA-NP 的设计，以扩大其在机械结构、医学、催化和能量存储/转换方面的潜在应用。
High entropy alloy nanoparticles (HEA-NPs) are expanding their influence in many fields. To explore the electronic structures in such multielemental systems, HEA-NPs were synthesized on two different carbon substrates through carbothermal shock and in situ reduction methods. The relationship between the apparent core level energy shifts (negative or positive) and the electron density changes among the components of quinary-metal HEA-NPs was investigated by X-ray photoelectron spectroscopy (XPS) analysis and first-principles electronic structure calculations. It was found that Cu displays a negative core level shift while Fe, Co, Mg, Cr, and Mn display a positive core level shift. While experiments show an apparent positive core level shift for Ni, electronic structure calculations reveal that this arises from shifts in the Fermi level and that the electron density redistribution in Ni behaves more like Cu than the other elements. The findings show that the electron density redistribution in the NPs occurs from less electronegative elements to more electronegative ones. This work should guide the design of HEA-NPs to expand their potential applications in mechanical structures, medicine, catalysis, and energy storage/conversion.