Configurational-entropy driven formation of single-phase high entropy carbide nanoparticles for efficient hydrogen evolution

IF 11 1区材料科学 Q1 MATERIALS SCIENCE, MULTIDISCIPLINARY

Rare Metals Pub Date : 2025-07-25 DOI:10.1007/s12598-025-03468-8

Lei Feng, Yu-Ying Meng, Yi-Zhong Chen, Ze-Kai Zhu, Yi-Ming Zou, Wen-Biao Zhang, Chun-Yan Xiang, Er-Kang Liu, Deng-Jie Chen, Yi Tang, Damien Voiry, Qing-Sheng Gao

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引用次数: 0

Abstract

Single-phase high-entropy carbides (HECs) are emerging as promising electrocatalysts for the hydrogen evolution reaction (HER) due to their widely tunable electronic configurations and the synergistic effects of multimetallic sites. However, their controllable synthesis and mechanistic understanding remain significant challenges due to the thermodynamic immiscibility of the multi-metallic elements within the carbide structure. In this study, we demonstrate the first successful synthesis of single-phase HECs based on Mo and W systems through an innovative high-entropy design strategy. Guided by comprehensive thermodynamic predictions, the single-phase solid solution formation temperatures were determined for the HEC-n (n = 2–9) series of high-entropy carbides. We achieved the configurational-entropy driven formation of HEC nanoparticles containing 4–9 transition metal elements via an ultra-fast joule heating process (i.e., (TiZrHfVNbTaCrWMo)C). Through rapid synthesis and screening, we obtained (VNbCrWMo)C nanoparticles exhibiting the best HER activities and exceptional long-term stability over 168 h due to high-entropy composition design and synthesis strategies, outperforming unary, binary, ternary, quaternary carbides and carbides with more than six metallic elements. Theoretical calculations and X-ray photoelectron spectroscopy analysis reveal that the (VNbCrWMo)C high-entropy carbide achieves enhanced HER activity through multi-metallic synergy, where constituent elements cooperatively redistribute electron density at catalytic sites. This work provides a new pathway for the rational design of advanced metal carbide electrocatalysts, highlighting the potential of high-entropy effects in tailoring material properties for energy conversion applications.

Graphical abstract

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构型熵驱动形成的单相高熵碳化物纳米颗粒的高效析氢

单相高熵碳化物（HECs）由于其广泛可调的电子构型和多金属位的协同效应而成为析氢反应（HER）的电催化剂。然而，由于碳化物结构中多金属元素的热力学不混溶性，它们的可控合成和机理理解仍然是一个重大挑战。在这项研究中，我们通过一种创新的高熵设计策略，首次成功地合成了基于Mo和W体系的单相HECs。在综合热力学预测的指导下，确定了HEC-n （n = 2-9）系列高熵碳化物的单相固溶体形成温度。我们通过超高速焦耳加热过程（即（TiZrHfVNbTaCrWMo）C）实现了包含4-9个过渡金属元素的HEC纳米粒子的构型熵驱动形成。通过快速合成和筛选，我们获得的（VNbCrWMo）C纳米颗粒表现出最佳的HER活性，并且由于高熵的组成设计和合成策略，在168 h内具有优异的长期稳定性，优于一元、二元、三元、四元碳化物和含6个以上金属元素的碳化物。理论计算和x射线光电子能谱分析表明，（VNbCrWMo）C高熵碳化物通过多金属协同作用实现了HER活性的增强，其中组成元素在催化位点协同重新分配电子密度。这项工作为合理设计先进的金属碳化物电催化剂提供了新的途径，突出了高熵效应在调整能量转换应用中的材料特性方面的潜力。图形抽象

本文章由计算机程序翻译，如有差异，请以英文原文为准。

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来源期刊

Rare Metals 工程技术-材料科学：综合

CiteScore

12.10

自引率

12.50%

发文量

2919

审稿时长

2.7 months

期刊介绍： Rare Metals is a monthly peer-reviewed journal published by the Nonferrous Metals Society of China. It serves as a platform for engineers and scientists to communicate and disseminate original research articles in the field of rare metals. The journal focuses on a wide range of topics including metallurgy, processing, and determination of rare metals. Additionally, it showcases the application of rare metals in advanced materials such as superconductors, semiconductors, composites, and ceramics.