Mechanochemical Molecular Motion Using Noncovalent Interactions on Graphene and Its Application to Tailoring the Adsorption Energetics
Mechanochemical Molecular Motion Using Noncovalent Interactions on Graphene and Its Application to Tailoring the Adsorption Energetics
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DOI：
10.1021/acsmaterialslett.2c01021
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发表时间：
2023-01
影响因子：
11.4
通讯作者：
Sayanti Banerjee;A. Rappe
中科院分区：
文献类型：
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作者：
Sayanti Banerjee;A. Rappe
在此，我们提出了一种新的方式来驱动和控制定向分子运动的石墨烯通过修改的非共价相互作用（NCIs）。我们发现，分子与石墨烯非共价相互作用选择性地扩散远离山（负曲率）区域的山谷（正曲率）地区。这与先前报道的石墨烯上共价连接的分子从谷到山的分子迁移形成对比。为了推广这一概念，我们研究了一系列NCI，包括π-π，C-H-π，孤对−π，卤素−π，阳离子−π和阴离子−π，并发现了相同的稳健趋势。我们进一步证明，这种非共价键合的分子的定向运动可以被利用来创建弯曲的石墨烯上的可调化学吸附能的结合位点。作为一个概念验证的演示，我们考虑了强电子受体tetracyanoquinodimethane（TCNQ）的运动，并显示出一个显着的化学吸附能的变化，可以达到一组吸附物作为一个后果的NCI驱动的分子迁移的TCNQ。因此，我们建议，NCI驱动的分子迁移可以提供一个额外的可控尺寸，以克服使用二维材料的多相催化的基本限制。
Herein we propose a new way to drive and control directional molecular motion on graphene by modifying the noncovalent interactions (NCIs). We show that molecules noncovalently interacting with graphene selectively diffuse away from the mountain (negative curvature) regions to the valley (positive curvature) regions. This is in contrast to previously reported molecular migration from the valley to the mountain of covalently attached molecules on graphene. To generalize the concept, we investigate a series of NCIs, including π–π, C–H––π, lone pair−π, halogen−π, cation−π, and anion−π, and find the same robust trend. We further demonstrate that such directional motion of noncovalently bonded molecules can be exploited to create binding sites with tunable chemisorption energy on curved graphene. As a proof-of-concept demonstration, we consider the motion of strong electron acceptor tetracyanoquinodimethane (TCNQ) and show that a noticeable change in chemisorption energy can be attained for a set of adsorbates as a consequence of NCI-driven molecular migration of TCNQ. Thus, we propose that NCI-driven molecular migration can provide an additional controllable dimension to overcome the fundamental limitations of heterogeneous catalysis using 2D materials.