Mechanochemical Molecular Migration on Graphene
Mechanochemical Molecular Migration on Graphene
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DOI：
10.1021/jacs.1c13193
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发表时间：
2022-04-27
影响因子：
15
通讯作者：
Rappe, Andrew M.
中科院分区：
文献类型：
--
作者：
Banerjee, Sayan;Rappe, Andrew M.
在这项研究中，我们提出，可以利用石墨烯的曲率进行定向分子运动，并通过密度泛函理论计算提供原子的见解曲率依赖的分子迁移。我们首先揭示了实验观察到的芳香族分子与p-掺杂的功能化石墨烯上的供电子和吸电子基团的不同迁移趋势的起源。接下来，我们证明了迁移的动力学障碍取决于曲率的量和性质，即正曲率与负曲率。我们发现，分子迁移的褶皱/波纹石墨烯片优先发生从山谷（正曲率）的山（负曲率）地区。为了理解这种曲率依赖的分子运动和迁移动力学势垒趋势的起源，我们开发了一个基于石墨烯前沿轨道取向的描述符。最后，基于这些发现，我们预测时空变化的曲率可以驱动石墨烯上的定向分子运动，从而进一步提出，努力应该集中在探索其他二维材料作为执行受控分子运动的活性平台。
In this study, we propose that the curvature of graphene can be exploited to perform directional molecular motion and provide atomistic insights into the curvature-dependent molecular migration through density functional theory calculations. We first reveal the origin of the different migration trends observed experimentally for aromatic molecules with electron-donating and -withdrawing groups on p-doped functionalized graphene. Next, we show that the kinetic barrier for migration depends on the amount and nature of the curvature, that is, positive versus negative curvature. We find that the molecular migration on a wrinkled/rippled graphene sheet preferentially happens from the valley (positive curvature) to the mountain (negative curvature) regions. To understand the origin of such curvature-dependent molecular motion and migrational kinetic barrier trends, we develop a descriptor based on the frontier orbital orientation of graphene. Finally, based on these findings, we predict that time- and space-varying curvature can drive directional molecular motion on graphene and thus further propose that efforts should focus on exploring other two-dimensional materials as active platforms for performing controlled molecular motion.