用循环伏安法和SECM研究了HOPG和石墨插层化合物的宏观和微观电子传递动力学。

IF 1.9 4区 工程技术 Q3 MICROSCOPY
Rossella Yivlialin, Gregorio Bonazza, Dario Battistel, Gianlorenzo Bussetti, Salvatore Daniele
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引用次数: 0

摘要

高取向热解石墨(HOPG)由于其高度有序的结构,是制备和研究石墨插层化合物最常用的载体材料之一。在硫酸中电化学插层HOPG的实验具有模型性质,因为所得结果不仅适用于其他石墨化合物,也适用于其他层状主体晶格的插层。此外,HOPG/H2SO4系统在电化学生产氧化石墨方面具有诱人的潜力,理想情况下,通过可逆氧化/还原循环,这对工业规模的储能和石墨烯生产很有兴趣。然而,这种电化学插层过程中的氧化/还原循环是不可逆的和拓扑定向的,因此HOPG结构发生了很大的变化。这种变化可能会影响,例如,电化学生产的石墨烯的质量。特别是,电化学插层对HOPG基面等石墨烯片的电导率的影响仍然存在争议。在这项工作中,我们分别使用循环伏安法(CV)和扫描电化学显微镜(SECM)研究了插入1 M H2SO4得到石墨插层化合物前后HOPG表面的宏观和微观电子转移(ET)动力学。采用[Fe(CN)6]3-/4-和[Ru(NH3)6]3+/2+两种氧化还原体系定量评价了HOPG的非均相动力学常数k0。通过原子力显微镜(AFM)研究了样品的形貌,发现在HOPG嵌入过程中广泛形成了水泡和沉淀物。CV和SECM结果表明,在插入后,HOPG的电化学行为发生了明显的变化,ET明显降低。然而,这种影响取决于所使用的氧化还原介质,对[Fe(CN)6]3-/4-体系的影响更为明显,其k0降低了几个数量级。AFM观察到,ET的减少可能与HOPG插入过程中出现的水泡和沉淀有关。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
Macroscopic and microscopic electron transfer kinetics of HOPG and graphite intercalated compound investigated by cyclic voltammetry and SECM.

Highly oriented pyrolytic graphite (HOPG) is one of the most used host materials for obtaining and investigating graphite intercalated compounds, because of the high degree structural order of this polycrystal. Experiments on electrochemically intercalated HOPG in sulphuric acid have a model character, as the results obtained can be usefully generalised, not only with respect to other graphite compounds but also for the intercalation of other layered host lattices. In addition, the HOPG/H2SO4 system has an attractive potential for the possibility of electrochemically producing graphite oxide, ideally, by reversible oxidation/reduction cycles, which is of interest for energy storage and graphene production on an industrial scale. However, the oxidation/reduction cycles in such electrochemical intercalation process are not reversible and topotactic, so that the HOPG structure is considerably altered. This alteration may affect, for instance, the quality of the electrochemically produced graphene. In particular, the impact the electrochemical intercalation has on the conductivity of basal planes of HOPG, and so on graphene sheets, is still debated. In this work, we investigated both the macroscopic and microscopic electron transfer (ET) kinetics of the HOPG surface, before and after the intercalation of 1 M H2SO4 to obtain graphite intercalated compound, by using cyclic voltammetry (CV) and scanning electrochemical microscopy (SECM), respectively. The heterogeneous kinetic constant (k0) of the HOPG was evaluated quantitatively by using the redox systems [Fe(CN)6]3-/4- and [Ru(NH3)6]3+/2+. The morphology of the samples was also investigated by atomic force microscopy (AFM), which revealed a widespread formation of blisters and precipitates during the HOPG intercalation process. The CV and SECM results indicate that, upon intercalation, the electrochemical behaviour of the HOPG changes sensibly and the ET decreases sensibly. However, this effect depends on the redox mediators employed and it results more dramatic for the [Fe(CN)6]3-/4- system, for which a decrease of k0 by orders of magnitude was obtained. The decrease of ET can be correlated to the blisters and precipitates, which occur during the HOPG intercalation, as observed by AFM.

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来源期刊
Journal of microscopy
Journal of microscopy 工程技术-显微镜技术
CiteScore
4.30
自引率
5.00%
发文量
83
审稿时长
1 months
期刊介绍: The Journal of Microscopy is the oldest journal dedicated to the science of microscopy and the only peer-reviewed publication of the Royal Microscopical Society. It publishes papers that report on the very latest developments in microscopy such as advances in microscopy techniques or novel areas of application. The Journal does not seek to publish routine applications of microscopy or specimen preparation even though the submission may otherwise have a high scientific merit. The scope covers research in the physical and biological sciences and covers imaging methods using light, electrons, X-rays and other radiations as well as atomic force and near field techniques. Interdisciplinary research is welcome. Papers pertaining to microscopy are also welcomed on optical theory, spectroscopy, novel specimen preparation and manipulation methods and image recording, processing and analysis including dynamic analysis of living specimens. Publication types include full papers, hot topic fast tracked communications and review articles. Authors considering submitting a review article should contact the editorial office first.
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