Thermal stability and oxidation resistance of single-digit boron-doped nanodiamonds

IF 5.3 3区材料科学 Q2 MATERIALS SCIENCE, MULTIDISCIPLINARY

Materials Research Bulletin Pub Date : 2025-06-06 DOI:10.1016/j.materresbull.2025.113604

E.A. Ekimov , A.A. Shiryaev , T.B. Shatalova , K.I. Maslakov , S.G. Lyapin , K.M. Kondrina , Y.V. Grigoriev , S. Stehlik , M.V. Kondrin

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引用次数: 0

Abstract

Single-digit boron-doped nanodiamonds (SD-BND) are potentially promising for use in various applications, including medicine, energy storage, and electronic devices. However, thermal stability and oxidation resistance of SD-BND remains unexplored, hindering their practical application and development of production methods. In this study, we investigate thermal stability in vacuum of SD-BND in comparison with larger BND, both synthesized by pyrolysis of 9-borabicyclo(3.3.1)nonane under high pressures, and with detonation nanodiamonds (DND). In situ X-ray phase analysis shows that the thermal stability of 4.5 nm SD-BND is comparable to that of 4.5 nm DND, since graphitization is observed at 1000 °C in both cases, and inferior to the stability of 30 nm BND. The oxidation resistance of SD-BND was studied in comparison with DND. In contrast to the widely accepted assumption that boron doping increases the oxidative resistance of diamonds, the oxidation of the 4.5 nm SD-BND in air begins ∼100 °C earlier than 4.5 nm DND. Density functional theory (DFT) calculations indicate that the presence of a boron impurity promotes nanodiamond oxidation. As detected by Raman spectroscopy, the boron impurity state remains largely unchanged during heat treatment at 550 °C in air despite the instability of SD-BND in an oxidizing atmosphere. This study delineates field of SD-BND stability upon heating in vacuum and in air, which is important for practical applications.

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一位数掺硼纳米金刚石的热稳定性和抗氧化性

单位数掺硼纳米金刚石（SD-BND）具有潜在的应用前景，包括医学、能源存储和电子设备。然而，SD-BND的热稳定性和抗氧化性仍未得到充分研究，阻碍了其实际应用和生产方法的发展。在这项研究中，我们研究了SD-BND在真空中的热稳定性，并与在高压下由9-硼环壬烷（3.3.1）热解合成的大BND进行了比较，并与爆轰纳米金刚石（DND）进行了比较。原位x射线相分析表明，4.5 nm SD-BND的热稳定性与4.5 nm DND相当，因为在1000°C下两种情况下都观察到石墨化，但不如30 nm BND的稳定性。研究了SD-BND与DND的抗氧化性能。与广泛接受的硼掺杂增加金刚石抗氧化性的假设相反，4.5 nm SD-BND在空气中的氧化比4.5 nm DND早开始~ 100°C。密度泛函理论（DFT）计算表明硼杂质的存在促进了纳米金刚石的氧化。通过拉曼光谱检测，尽管SD-BND在氧化气氛中不稳定，但在550℃空气中热处理时，硼杂质状态基本保持不变。该研究描绘了SD-BND在真空和空气中加热时的稳定性范围，对实际应用具有重要意义。

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

Materials Research Bulletin 工程技术-材料科学：综合

CiteScore

9.80

自引率

5.60%

发文量

372

审稿时长

42 days

期刊介绍： Materials Research Bulletin is an international journal reporting high-impact research on processing-structure-property relationships in functional materials and nanomaterials with interesting electronic, magnetic, optical, thermal, mechanical or catalytic properties. Papers purely on thermodynamics or theoretical calculations (e.g., density functional theory) do not fall within the scope of the journal unless they also demonstrate a clear link to physical properties. Topics covered include functional materials (e.g., dielectrics, pyroelectrics, piezoelectrics, ferroelectrics, relaxors, thermoelectrics, etc.); electrochemistry and solid-state ionics (e.g., photovoltaics, batteries, sensors, and fuel cells); nanomaterials, graphene, and nanocomposites; luminescence and photocatalysis; crystal-structure and defect-structure analysis; novel electronics; non-crystalline solids; flexible electronics; protein-material interactions; and polymeric ion-exchange membranes.