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过渡金属硼化物的结构与性质

陶强 马帅领 崔田 朱品文

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过渡金属硼化物的结构与性质

陶强, 马帅领, 崔田, 朱品文

Structures and properties of functional transition metal borides

Tao Qiang, Ma Shuai-Ling, Cui Tian, Zhu Pin-Wen
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  • 过渡金属硼化物(TMBs)是一类具有强耐磨性、抗腐蚀性、耐高温、高硬度的多功能材料.过渡金属与硼原子间电荷转移量的多样性决定了过渡金属硼化物中化学键的成键方式和成键强弱,最终导致过渡金属硼化物丰富的结构以及潜在的多功能特性.过渡金属硼化物的制备、晶体结构和力学性能一直是该领域的研究热点.硼原子间的强共价键决定了过渡金属硼化物的合成需要高能量;晶体结构中化学键的强弱与过渡金属硼化物的硬度性质息息相关;多种化学键成键方式使过渡金属硼化物展现出了丰富的多功能性质.本文主要从过渡金属硼化物的合成、结构、硬度性质和多功能性质四个方面,以不同硼原子亚结构单元为出发点,总结和分析了过渡金属硼化物的研究现状.我们认为,利用高温高压制备TMBs,诱导过渡金属与硼原子之间的电子转移,构造(准)三维的化学键,是设计制备新型多功能硬质过渡金属硼化物的有效方法.
    Transition metal borides (TMBs) are hard or potential superhard materials due to abrasion resistant, corrosion preventive, oxidation resistance and high hardness. However, few TMBs are superhard materials, so, discussing the strength of TMBs to understand hardness mechanism is necessary. Moreover, there are superconductors, magnetic materials, and catalysts in TMBs. But uncovering more functions in TMBs is important for finding a new kind of functional hard or superhard material. While, high energy is necessary to synthesize TMBs due to strong BB covalent bonds and high melting of transition metal. Thus high temperature or extreme condition is necessary for synthesizing single crystal or bulk sample with high density, which is important for testing physical properties. Various ways of hybridizing boron atoms and high content of valence electron of transition metal are used to induce a large number of structures and potential new properties in TMBs. Boron atoms can form different substructures with different content of boron in TMBs, such as one-dimensional, two-dimensional and three-dimensional (3D) structures. These different boron atom substructures can affect the stability of structure and physical properties, especially hardness, because of the strong covalent bonds between boron atoms. Thus the structure and hardness of TMBs have always received much attention. The multiple electron transfer between transition metal and boron induces diverse chemical bonds in TMBs. All of covalent bonds, ionic bonds, and metal bonds in TMBs determine the mechanic performances, electricitic and magnetic properties, and chemical activity of TMBs. In this work, synthesis method, stability of structure, hardness, and functional properties of TMBs are discussed. The using of high pressure and high temperature is an effective method to prepare TMBs, because under high pressure and high temperature the electrons can transfer between transition-metal atoms and boron atoms in TMBs. There are not only stable TMBs which are even under very high pressure, but also many metastable structures in TMBs. Hardness values of TMBs are discussed by different content of boron, the high boron content or even 3D boron structure is not superhard material. Because insufficient electron transfer can form the distorted BB covalent bond which is weaker than directional covalent bonds like CC in diamond. Thus electron transfer is significant in TMBs for designing hard or even superhard materials. Besides high hardness, there are superconductor, magnetic material, and catalyzers in TMBs, but there are many potential properties of TMBs which are unknown. Further study to uncover the new properties of TMBs is significant for finding a new kind of functional hard material.
      通信作者: 朱品文, zhupw@jlu.edu.cn
    • 基金项目: 国家自然科学基金(批准号:51032001,51172091,41572357)资助的课题.
      Corresponding author: Zhu Pin-Wen, zhupw@jlu.edu.cn
    • Funds: Project supported by the National Natural Science Foundation of China (Grant Nos. 51032001, 51172091, 41572357).
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  • 收稿日期:  2016-10-18
  • 修回日期:  2016-11-25
  • 刊出日期:  2017-02-05

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