Aliev Ali E, Guo Yongzhe, Fonseca Alexandre F, Razal Joselito M, Wang Zhong, Galvão Douglas S, Bolding Claire M, Chapman-Wilson Nathaniel E, Desyatkin Victor G, Leisen Johannes E, Ribeiro Junior Luiz A, Kanegae Guilherme B, Lynch Peter, Zhang Jizhen, Judicpa Mia A, Parra Aaron M, Zhang Mengmeng, Gao Enlai, Hu Lifang, Rodionov Valentin O, Baughman Ray H
Alan G. MacDiarmid NanoTech Institute, University of Texas at Dallas, Richardson, TX 75080.
School of Civil Engineering, Wuhan University, Wuhan 430072, Hubei, China.
Proc Natl Acad Sci U S A. 2025 Feb 4;122(5):e2413194122. doi: 10.1073/pnas.2413194122. Epub 2025 Jan 28.
The highest sheet symmetry form of graphyne, with one triple bond between each neighboring hexagon in graphene, irreversibly transforms exothermically at ambient pressure and low temperatures into a nongraphitic, planar-sheet, zero-bandgap phase consisting of intrasheet-bonded sp carbons. The synthesis of this sp carbon phase is demonstrated, and other carbon phases are described for possible future synthesis from graphyne without breaking graphyne bonds. While measurements and theory indicate that the reacting graphyne becomes nonplanar because of sheet wrinkling produced by dimensional mismatch between reacted and nonreacted sheet regions, sheet planarity is regained when the reaction is complete. Although the observed elimination of triple bonds to make parallel planar sp carbon sheets likely requires ordered transformation within each sheet, diffraction data for reacted multisheet stacks indicate that the relative lateral positions of neighboring sheets are disordered, as predicted, since no crystalline diffraction peak (other than for the intersheet spacing) is observed.
石墨炔的最高片层对称形式，即在石墨烯中每个相邻六边形之间有一个三键，在常压和低温下会不可逆地放热转变为一种由片内键合的sp碳组成的非石墨化、平面片层、零带隙相。文中展示了这种sp碳相的合成，并描述了其他碳相，以便未来有可能在不破坏石墨炔键的情况下由石墨炔合成。虽然测量和理论表明，由于反应区和未反应区片层尺寸不匹配产生的片层褶皱，反应中的石墨炔会变得非平面，但反应完成时片层会恢复平面性。尽管观察到消除三键以形成平行平面的sp碳片层可能需要在每个片层内进行有序转变，但反应后的多片层堆叠的衍射数据表明，相邻片层的相对横向位置是无序的，正如所预测的那样，因为未观察到晶体衍射峰（除了片层间距的衍射峰）。
