Remarkably enhanced dynamic oxygen migration on graphene oxide supported by copper substrate.
Remarkably enhanced dynamic oxygen migration on graphene oxide supported by copper substrate.
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DOI：
10.1039/d2nh00041e
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发表时间：
2021-09
影响因子：
9.7
通讯作者：
Zihan Yan;W. Yang;Hao Yang;Cheng Ji;S. Zeng;Xiuyun Zhang;Liang Zhao;Y. Tu
中科院分区：
文献类型：
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作者：
Zihan Yan;W. Yang;Hao Yang;Cheng Ji;S. Zeng;Xiuyun Zhang;Liang Zhao;Y. Tu
氧化石墨烯（GO）的动态共价性质是广泛的科学领域和技术应用的基本兴趣。获得用于可逆地断裂/重整GO上的氧官能团的共价键的可行的动态反应仍然是一个挑战，尽管这些反应可以通过光子或机械途径诱导，或者通过吸附的水介导。在这里，使用密度泛函理论计算，我们证明了显着增强的动态氧迁移沿着由铜衬底（GO@铜）支撑的GO的基面，与相邻的环氧和羟基之间的C-O键断裂反应和质子转移。与GO上的反应相比，GO@铜上的氧迁移的能垒急剧降低到小于或相当于热涨落，同时GO与铜衬底之间的晶体匹配诱导了GO@铜上新的氧迁移路径。这项工作揭示了金属衬底增强的动态性能的GO的理解，并证明了调整各种潜在应用的二维界面氧基团的活性的策略。
The dynamic covalent properties of graphene oxide (GO) are of fundamental interest to a broad range of scientific areas and technological applications. It remains a challenge to access feasible dynamic reactions for reversibly breaking/reforming the covalent bonds of oxygen functional groups on GO, although these reactions can be induced by photonic or mechanical routes, or mediated by adsorbed water. Here, using density functional theory calculations, we demonstrate the remarkably enhanced dynamic oxygen migration along the basal plane of GO supported by copper substrate (GO@copper), with C-O bond breaking reactions and proton transfer between neighboring epoxy and hydroxyl groups. Compared to reactions on GO, the energy barriers of oxygen migrations on GO@copper are sharply reduced to be less than or comparable to thermal fluctuations, and meanwhile the crystallographic match between GO and copper substrate induces new oxygen migration paths on GO@copper. This work sheds light on understanding of the metal substrate-enhanced dynamic properties of GO, and evidences the strategy to tune the activity of two-dimensional-interfacial oxygen groups for various potential applications.