Scalable Synthesis of Crystalline One-Dimensional Carbon Nanothreads through Modest-Pressure Polymerization of Furan
Scalable Synthesis of Crystalline One-Dimensional Carbon Nanothreads through Modest-Pressure Polymerization of Furan
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DOI：
10.1021/acsnano.0c10400
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发表时间：
2021-01-20
期刊：
影响因子：
17.1
通讯作者：
Elacqua, Elizabeth
中科院分区：
文献类型：
--
作者：
Huss, Steven;Wu, Sikai;Elacqua, Elizabeth
碳纳米线是一维的富含sp（3）的聚合物，由于亚纳米宽度和金刚石样芯，联合收割机结合了高拉伸强度和柔性。这些扩展的碳固体是通过压力诱导的sp（2）分子（如苯）聚合而形成的。尽管已经报道了碳纳米线的一些实例，但是合成它们需要高起始压力（>= 17 GPa），这排除了可扩展性并限制了范围。在本文中，我们报告了基于分子呋喃的碳纳米线的可扩展合成，其可以通过环境温度压力诱导聚合来实现，由于其相对于其他分子前体的芳香性降低，起始反应压力仅为10 GPa。当缓慢压缩至15 GPa并逐渐减压至1.5 GPa时，原位观察到尖锐的6倍衍射图案，表明由液体呋喃形成的有序结晶材料。反应产物的单晶X射线衍射（XRD）显示出从4.75到4.9埃的三个不同的d-间距，其尺寸，角间距和各向异性程度与我们对呋喃纳米线晶体的原子模拟一致。通过粉末XRD、拉曼/IR光谱和质谱获得聚合的进一步证据。计算的振动模式的IR光谱的比较提供了临时识别的光谱特征的特定的纳米线结构，即顺，反，和顺/反配置。质谱表明分子量至少为6 kDa是可能的。因此，呋喃为可扩展的碳纳米线提供了一个战略入口。
Carbon nanothreads, which are one-dimensional sp(3)-rich polymers, combine high tensile strength with flexibility owing to subnanometer widths and diamond-like cores. These extended carbon solids are constructed through pressure-induced polymerization of sp(2) molecules such as benzene. Whereas a few examples of carbon nanothreads have been reported, the need for high onset pressures (>= 17 GPa) to synthesize them precludes scalability and limits scope. Herein, we report the scalable synthesis of carbon nanothreads based on molecular furan, which can be achieved through ambient temperature pressure-induced polymerization with an onset reaction pressure of only 10 GPa due to its lessened aromaticity relative to other molecular precursors. When slowly compressed to 15 GPa and gradually decompressed to 1.5 GPa, a sharp 6-fold diffraction pattern is observed in situ, indicating a well-ordered crystalline material formed from liquid furan. Single-crystal X-ray diffraction (XRD) of the reaction product exhibits three distinct d-spacings from 4.75 to 4.9 angstrom, whose size, angular spacing, and degree of anisotropy are consistent with our atomistic simulations for crystals of furan nanothreads. Further evidence for polymerization was obtained by powder XRD, Raman/IR spectroscopy, and mass spectrometry. Comparison of the IR spectra with computed vibrational modes provides provisional identification of spectral features characteristic of specific nanothread structures, namely syn, anti, and syn/anti configurations. Mass spectrometry suggests that molecular weights of at least 6 kDa are possible. Furan therefore presents a strategic entry toward scalable carbon nanothreads.