上海大学谭启涛团队近日研究了一种用于光催化和与富勒烯组装的含氮石墨碗烯。相关论文于2025年6月16日发表在《德国应用化学》杂志上。

以钯催化脱氢环胺化反应为关键步骤，在六邻六苯并冠（p-HBC）的碗烯位通过五边形环化反应合成了含氮石墨烯巴克波（3N-HBC）。碗的外围结合了三个吡咯环，使其具有强烈的富电子特性，在循环伏安法（CV）中显示出三种可逆氧化，因此在逐渐加入氧化剂后，可以逐渐氧化为阳离子自由基和高电荷物种。有趣的是，阳离子自由基也是由酸产生的，无论是在空气还是惰性气氛下，酸都可以被光显著加速。 

3N-HBC表现出有趣的特性，这些特性源于其富含电子的特性和独特的弯曲几何形状。3N-HBC被证明是一种在蓝色LED照射下在1.0 mol%催化负载下将2-异氰联苯转化为菲啶衍生物的优良有机光催化剂。此外，3N-HBC的供电子性质和弯曲的π表面使其能够在溶液和固体状态下与富勒烯（C60和C70）结合。这项工作还表明，通过在碗区域引入少量含有小尺寸杂原子的五边形，纳米石墨烯片可以弯曲成π碗状。

附：英文原文

Title: A Nitrogen-Containing Graphenic Buckybowl for Photocatalysis and Assembly with Fullerenes

Author: Huiling Liu, Jimin Guo, Tiantian Che, Changhua Ding, Bin Xu, Qitao Tan

Issue&Volume: 2025-06-16

Abstract: A nitrogen-containing graphenic buckybowl (3N-HBC) has been synthesized through pentagonal cyclization at the bay positions of hexa-peri-hexabenzocoronene (p-HBC) using a Pd-catalyzed dehydrogenative cycloamination as a key step. The incorporation of three pyrrole rings to the periphery of the bowl endows it with strong electron-rich character, showing three reversible oxidations in cyclic voltammetry (CV), and thus could be progressively oxidized into cationic radical and high-charged species upon gradual addition of the oxidant. Interestingly, the cationic radical was also generated by acids, which could be significantly accelerated by light, whether under an air or inert atmosphere. 3N-HBC exhibits interesting properties that arise from its electron-rich character and the unique curved geometry. 3N-HBC proved to be a superior organic photocatalyst for the conversion of 2-isocyanobiphenyl to phenanthridine derivatives at 1.0 mol% catalytic loading under blue LEDs irradiation. Furthermore, the electron-donating nature and curved π-surface of 3N-HBC enable its association with fullerenes (C60 and C70) in solution and solid states. This work also demonstrates that nanographene sheets can be bent to π-bowls through introduction of few pentagons containing small-sized heteroatom to their bay regions.

DOI: 10.1002/anie.202506862

Source: https://onlinelibrary.wiley.com/doi/10.1002/anie.202506862