高温高压下的富勒烯

宋静; 王霖

doi:10.11858/gywlxb.20261069

高温高压下的富勒烯

doi: 10.11858/gywlxb.20261069

宋静^{1, 2,},
王霖^2,*, ,

1.
燕山大学理学院, 河北省微结构材料物理重点实验室, 河北秦皇岛　066004
2.
燕山大学材料科学与工程学院, 亚稳材料全国重点实验室, 高压科学中心, 河北秦皇岛　066004

基金项目: 国家自然科学基金（52288102，52090020）；河北省创新能力提升计划项目-高水平人才团队建设专项（225A1102D）

详细信息

作者简介:
宋　静（2000－），女，博士研究生，主要从事高压物理实验研究. E-mail：songjing0006@163.com

通讯作者:
王　霖（1977－），男，博士，教授，主要从事材料结构与性能的高压调控研究. E-mail：linwang@ysu.edu.cn

中图分类号: O521.2
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出版历程
- 收稿日期: 2026-04-01
- 修回日期: 2026-05-10
- 网络出版日期: 2026-05-20
- 刊出日期: 2026-09-05

Fullerenes under High Temperature and High Pressure

SONG Jing^{1, 2
,},
WANG Lin^{2,*
, ,}

1.
Key Laboratory for Microstructural Material Physics of Hebei Province, School of Science, Yanshan University, Qinhuangdao 066004, Hebei, China
2.
Center for High Pressure Science, State Key Laboratory of Metastable Materials Science and Technology, School of Materials Science and Engineering, Yanshan University, Qinhuangdao 066004, Hebei, China

摘要

摘要: 富勒烯（以 C₆₀/C₇₀ 为代表）作为典型分子晶体碳同素异形体，在高温高压（high temperature and high pressure，HTHP）条件下可经历由取向有序化、分子间初始成键到低维聚合、多维交联乃至笼结构塌缩与无定形化的一系列连续结构演化过程，是连接“分子晶体碳”与“高密度共价碳网络”的重要桥梁。围绕富勒烯在压强-温度协同调控下的相变与聚合行为，系统梳理了其面心立方→简单立方取向转变、二聚（典型[2+2]环加成）到一维链状聚合、二维层状聚合（四方/菱方等）以及可能的三维结构的形成机制与结构特征，并讨论了不同加载路径和动力学因素对相区边界与产物有序度的影响。同时，对C₇₀在分子各向异性驱动下更易出现的多路径竞争与无序化趋势进行对比总结，进一步评述金属富勒烯以及溶剂化富勒烯等体系中客体分子对高温高压下富勒烯聚合路径以及物理性质的调控作用。最后，结合富勒烯衍生 sp³富集超硬无定形碳及相关新型碳结构的研究进展，展望了通过前驱体工程与多维度调控策略实现可设计高压碳材料的潜在研究方向。
- 富勒烯 /
- 高温高压 /
- 聚合 /
- 超硬材料 /
- 新型碳材料
Abstract: Fullerenes, represented by C₆₀ and C₇₀, are typical molecular-crystal carbon allotropes. Under high-temperature and high-pressure (HTHP) conditions, they can undergo a continuous sequence of structural evolution, including orientational ordering, initial intermolecular bonding, low-dimensional polymerization, multidimensional cross-linking, cage collapse, and amorphization. Therefore, fullerenes serve as an important bridge between molecular-crystal carbon and high-density covalent carbon networks. This review focuses on the phase transitions and polymerization behavior of fullerenes under combined pressure-temperature control. The structural features and formation mechanisms of the fcc to sc orientational transition, dimerization, typically through [2+2] cycloaddition, one-dimensional chain polymerization, two-dimensional layered polymerization, including tetragonal and rhombohedral phases, and possible three-dimensional structures are systematically summarized. The effects of different loading paths and kinetic factors on phase boundaries and product ordering are also discussed. In addition, the multi-pathway competition and disordering tendency of C₇₀ driven by molecular anisotropy are comparatively reviewed. The regulatory roles of guest species in metallofullerenes and solvated fullerenes on the polymerization pathways and physical properties of fullerenes under HTHP conditions are further discussed. Finally, based on recent progress in fullerene-derived sp³-rich superhard amorphous carbon and related novel carbon structures, potential research directions for the controllable synthesis of high-pressure carbon materials through precursor engineering and multidimensional regulation strategies are proposed.
- fullerene /
- high-temperature and high-pressure /
- polymerization /
- ultrahard materials /
- novel carbon materials

HTML全文

图 1 C₆₀的压强-温度相图^{[4, 8]}

Figure 1. Pressure-temperature phase diagram of C₆₀^{[4, 8]}

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图 2 理论计算获得的C₆₀不同压强-温度下的结构总结^[47]

Figure 2. Summary of C₆₀ structures at different pressures and temperatures obtained from theoretical calculations^[47]

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图 3 C₆₀[2+2]环加成形成聚合物^[28]

Figure 3. Formation of polymers by [2+2] cycloaddition of pristine C₆₀^[28]

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图 4 晶体模型中C₆₀二聚体和单体在(001)面上的随机分布^[54]

Figure 4. Random distribution of C₆₀ dimers and isolated monomers in the (001) plane of a model crystal^[54]

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图 5 对于不同的聚合物结构，沿着单体晶格立方相<110>方向的高分子链的示意图^[58]

Figure 5. Schematic diagrams of the polymer chains running along <110> cubic directions of the parent monomer lattice, for the different polymer structures^[58]

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图 6 三维C₆₀聚合物的晶体结构^[64]

Figure 6. Crystal structure of the 3D C₆₀ polymer^[64]

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图 7 C₇₀的结构相图^[74]

Figure 7. Structural phase diagram of C₇₀^[74]

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图 8 富勒烯-立方烷杂分子晶体的结构^[50]

Figure 8. Structures of fullerene-cubane heteromolecular crystals^[50]

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图 9 不同压强条件下C₆₀·m-xylene的结构模拟^[6]

Figure 9. Simulated structures of C₆₀·m-xylene under different compression and decompression conditions^[6]

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图 10 将Sc₂C₂@C₈₂加压至20 GPa时在金刚石砧面留下的刻痕^[92]

Figure 10. Grooves on the surface of the diamond anvil resulting from trenching of the Sc₂C₂@C₈₂ sample at a shear pressure of 20 GPa^[92]

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图 11 部分I_h-C₈₀系EMFs的固态结构和电荷载流子迁移率^[93]

Figure 11. Solid-state structures and charge-carrier mobilities of some I_h-C₈₀ EMFs^[93]

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