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Heimann et al. Nature 306, 164 (1983)
Bottom-up method: 2 to 44 carbon atoms in 50 years!
Hale Waihona Puke Baidu
Why carbyne?
Last missing allotrope of carbon? Ideal 1D quantum wire: Structurally and electronically a 1D system 1D semiconductor for nanoelectronic devices
碳的同素异形体的发现之旅 及其拉曼光谱表征
Outline
• 拉曼光谱的基础知识和常见的问题-补充
• 碳的同素异形体的发现之旅
传统碳的同素异形体：石墨、金刚石，无定形碳 富勒烯 碳纳米管 石墨烯（GO、 rGO、以及石墨插层化合物） 碳链
• 几种拉曼光谱应用
• Summary
carbon chain@DWCNT Shi et al. Nature Mater. CsI chain@DWCNT Senga et al. Nature Mater.
碳的同素异形体的拉曼峰位
Casari et al. Nanoscale 2016
Raman spectra of polyynes
1/N
The longer the polyyne, the lower the Raman frequency. So it is possible to estimate the length of polyyne by its Raman frequency.
拉曼光谱的类型
• • • • • • • • • 共焦显微拉曼光谱 透射拉曼光谱 偏振拉曼光谱 共振拉曼光谱 傅里叶变化拉曼光谱 表面增强拉曼光谱（SERS） 针尖增强拉曼光谱（TERS） 受激拉曼增益光谱 拉曼联用系统…
• 变温，变压，磁场…
Lapin et al. Faraday Discussions, 2015
Gaussian, Lorentzian
几个常见问题
拉曼光谱分峰的原则：尊重物理规律，少而精
ID/IG计算中使用强度还是峰面积（目的）： 缺陷的多种类型，不同的官能团… 掺杂、复合碳材料的拉曼： 峰位移动、峰宽变化 GO还原为rGO的拉曼光谱的强度变化： 还原的方法决定
Allotropes of Carbon
The discovery of fullerenes
Sir Harold Kroto
Richard E. Smalley
Robert F. Curl Jr.
The Nobel Prize in Chemistry 1996: "for their discovery of fullerenes" Curl, Kroto, Smalley. Nobel Lecture, 1996
Type of carbon chains
Fantini et al. Phys. Rev. B 73, 193408 (2006) Jin et al., Phys. Rev. Lett. 102, 205501 (2009) Casillas et al., Carbon, 66, 436 (2014)
拉曼光谱定义和特点
• 瑞利/拉曼散射：弹性/非弹性散射(~10-7—10-11) • Raman shift = 107/ λ laser – 107/ λ outgoing
拉曼光谱的作用
• 如何处理拉曼数据？（提问的艺术） 分峰拟合（峰位及其移动、峰宽、峰强…）
Adapted from HORIBA
• Fusion of short polyynes into longer ones. One of my goals is to use carbon nanotubes as nanoreactors for bulk LLCC synthesis.
Zhao et al. Phys. Rev. Lett. 90, 187401 (2003) Zhao et al. J. Phys. Chem. C, 115, 13166 (2011)
Theoretically the strongest carbon material (strength, elastic modulus, and stiffness)
Tunable band gap simply by its length (5 - 1.8 eV) But: Carbyne is very reactive and unstable Needs termination or stabilizing environment Even existance of carbyne is controversial!
Hirsch A. Nature Mater. 9, 871 (2010)
Motivation: History of Carbyne
In 1950s, carbyne was found in some meteorites—the mineral from the space.
Structure and even their existence have not been finally proven!
Januszewski et al. Chem. Soc. Rev. 43, 3184 (2014)
Stabilizing carbon chains
Wesley et al. Nature Chem. 2, 967 (2010) Zhao et al. Phys. Rev. Lett. 90, 187401 (2003) Zhao et al. J. Phys. Chem. C 115, 13166 (2011)
Two methods used to stabilize the polyyne: Chemical ending groups or protected by carbon nanotubes
Synthesis of long polyynes inside CNTs
• Arc-discharge in a hydrogen, He or liquid nitrogen environments.
