Scalable nanomanufacturing of holey graphene via chemical etching: an investigation into process mechanisms
Scalable nanomanufacturing of holey graphene via chemical etching: an investigation into process mechanisms
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通过化学蚀刻进行多孔石墨烯的可扩展纳米制造：工艺机制的研究
DOI：
10.1039/d1nr08437b
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发表时间：
2022
期刊：
影响因子：
6.7
通讯作者：
Nian, Qiong
中科院分区：
文献类型：
--
作者：
Bi, Kun;Wang, Dini;Dai, Rui;Liu, Lei;Wang, Yan;Lu, Yongfeng;Liao, Yiliang;Ding, Ling;Zhuang, Houlong;Nian, Qiong
具有面内纳米孔的石墨烯，即多孔石墨烯，由于其快速的质量传输和提高的电化学活性，在电化学应用中显示出巨大的潜力。多孔石墨烯的可缩放纳米制造通常基于使用过氧化氢的化学蚀刻以在石墨烯的基面上形成贯穿厚度的纳米孔。在这项研究中，我们探讨了纳米孔形成的基本机制下过氧化物蚀刻通过综合实验和计算的努力。研究结果表明，氧化石墨烯刻蚀过程中纳米孔的生长是通过还原-氧化-还原三阶段过程实现的。首先，它表明，空位缺陷是通过部分还原基预处理形成的。其次，过氧化氢优先与氧化石墨烯片上缺陷区域的边缘位点反应，导致形成各种含氧官能团。第三，缺陷周围的碳原子通过还原与相邻碳原子一起沿着被去除。通过加深对工艺机制的理解，我们进一步展示了一种改进的纳米制造策略，其中引入具有高缺陷密度的氧化石墨烯进行过氧化物蚀刻，从而增强纳米孔的形成。
Graphene with in-plane nanoholes, named holey graphene, shows great potential in electrochemical applications due to its fast mass transport and improved electrochemical activity. Scalable nanomanufacturing of holey graphene is generally based on chemical etching using hydrogen peroxide to form through-the-thickness nanoholes on the basal plane of graphene. In this study, we probe into the fundamental mechanisms of nanohole formation under peroxide etching via an integrated experimental and computational effort. The research results show that the growth of nanoholes during the etching of graphene oxide is achieved by a three-stage reduction–oxidation–reduction procedure. First, it is demonstrated that vacancy defects are formed via a partial reduction-based pretreatment. Second, hydrogen peroxide reacts preferentially with the edge-sites of defect areas on graphene oxide sheets, leading to the formation of various oxygen-containing functional groups. Third, the carbon atoms around the defects are removed along with the neighboring carbon atoms via reduction. By advancing the understanding of process mechanisms, we further demonstrate an improved nanomanufacturing strategy, in which graphene oxide with a high density of defects is introduced for peroxide etching, leading to enhanced nanohole formation.