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Composition engineering of high-entropy diboride nanoparticles for efficient catalytic degradation of antibiotics

高熵二硼化物纳米颗粒的组分设计与催化降解抗生 素研究

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Abstract

Exploiting functional characteristics of high-entropy boride materials is critical for extending their potential applications in harsh environments. Herein we develop high-entropy diboride (HEB2) nanoparticles with efficient catalytic performance by engineering their compositions. Based on the theoretical analysis of the lattice size difference and mixing enthalpy of HEB2 and the self-propagating combustion mode of the system, six different compositional HEB2 nanoparticles are synthesized via a facile, rapid, and low-cost combustion synthesis method. By engineering their compositions, we achieve the efficient catalytic ability of HEB2 nanoparticles in persulfate activation towards antibiotics removal, namely the highest tetracycline removal efficiency of 93.5%. Further investigations of the adsorption energy and the charge density difference of various adsorption sites via density functional theory confirm that the outstanding catalytic ability mainly originates from the Ti constituent rather than the high-entropy effect. In addition, a potential catalytic mechanism of HEB2 towards persulfate activation for antibiotics degradation is proposed based on the detected reactive oxygen species and the computational reaction energy barrier. This study not only provides theoretical basis for their component design in the efficient catalytic degradation of antibiotics, but also shows a promising application of HEB2 for removal of emerging contaminants from environmental water matrices.

摘要

开发高熵硼化物材料的功能特性对于拓宽其在极端环境中的潜 在应用至关重要. 为此, 本文通过调控材料的组分开发出具有高效催化 性能的高熵二硼化物(HEB2)纳米颗粒: 首先基于对HEB2的尺寸差异因 子、混合焓以及体系自蔓延燃烧模式的理论分析, 我们采用一种简 便、快速、低成本的燃烧合成方法合成了6种不同组分的HEB2纳米颗 粒; 然后, 通过对材料的组分进行调控实现了HEB2纳米颗粒活化过硫酸 盐降解抗生素的高效催化能力(四环素的最高去除效率可达93.5%). 不 同吸附位点的吸附能和差分电荷密度的第一性原理计算结果进一步证 实了HEB2优异的催化性能主要归因于Ti组元, 而非高熵效应. 此外, 基 于检测到的活性氧和计算的反应能垒, 我们提出了HEB2活化过硫酸盐 降解抗生素的潜在催化机理. 本研究不仅为HEB2高效催化降解抗生素 的组分设计提供了理论依据, 而且显示出HEB2在去除自然水体中新污 染物方面的潜在应用前景.

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Acknowledgements

This work was supported by the National Key Research and Development Program of China (2021YFA0715801), the National Natural Science Foundation of China (52122204, 51972116, and 52072381), and Guangzhou Basic and Applied Basic Research Foundation (202201010632).

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  1. These authors contributed equally to this work.

Authors and Affiliations

  1. School of Materials Science and Engineering, South China University of Technology, Guangzhou, 510641, China

    Renwang Yu  (余仁旺), Yiwen Liu  (刘译文) & Yanhui Chu  (褚衍辉)

  2. College of Environmental Science and Engineering, Nankai University, Tianjin, 300350, China

    Xiaohong Sun  (孙晓红) & Heng Dong  (董恒)

  3. Tianjin Key Laboratory of Functional Crystal Materials, Institute of Functional Crystal, College of Material Science and Engineering, Tianjin University of Technology, Tianjin, 300384, China

    Gang He  (贺刚)

  4. Key Laboratory of Cryogenics, Technical Institute of Physics and Chemistry, Chinese Academy of Sciences, Beijing, 100190, China

    Shuxiang Deng  (邓书香) & Jiangtao Li  (李江涛)

Authors
  1. Renwang Yu  (余仁旺)
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  2. Yiwen Liu  (刘译文)
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  8. Yanhui Chu  (褚衍辉)
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Contributions

Chu Y conceived and designed this work. He G, Yu R, Li J, and Deng S performed the synthesis and characterization. Sun X and Dong H performed the test experiments. Liu Y performed the first-principles calculations. All authors analyzed the data. Chu Y, Yu R, Liu Y, and Dong H wrote the manuscript. All authors commented on the manuscript.

Corresponding authors

Correspondence to Gang He  (贺刚), Heng Dong  (董恒) or Yanhui Chu  (褚衍辉).

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The authors declare that they have no conflict of interest.

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Supplementary information

Supporting data are available in the online version of the paper.

Renwang Yu is currently a Master student at South China University of Technology, Guangzhou, China. His research interests focus on combustion synthesis of high-entropy diboride ceramic nanopowders.

Yiwen Liu is currently a Master student at South China University of Technology, Guangzhou, China. Her research interests focus on the oxidation of high-entropy non-oxide ceramics by first-principles calculations.

Gang He is an associate professor at Tianjin University of Technology, Tianjin, China. He received his PhD degree in materials science from the University of Chinese Academy of Sciences in 2015. From Jul. 2015 to Dec. 2021, He was a research associate at the Technical Institute of Physics and Chemistry, Chinese Academy of Sciences. His current research interests include non-oxide ceramic powders, transparent ceramics, and combustion synthesis technology.

Heng Dong is an associate professor at Nankai University, Tianjin, China. She received her PhD degree in environmental engineering from Nankai University in 2013. From Sep. 2019 to Sep. 2020, she worked at the University of California, Berkeley as a visiting scholar. Her current research focuses on advanced oxidation process for water/ wastewater treatment.

Yanhui Chu is currently a professor at South China University of Technology, Guangzhou, China. He received his PhD degree from Northwestern Polytechnical University in 2016. From Jan. 2014 to Sep. 2015, he was as a visiting scholar at Harvard University. His current research interest mainly focuses on the design, modeling and fabrication of high-entropy ceramics.

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Yu, R., Liu, Y., Sun, X. et al. Composition engineering of high-entropy diboride nanoparticles for efficient catalytic degradation of antibiotics. Sci. China Mater. 66, 3582–3591 (2023). https://doi.org/10.1007/s40843-023-2496-5

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  • DOI: https://doi.org/10.1007/s40843-023-2496-5

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