Guo Shuyue, Yan Hailong, Wu Fei, Zhao Lijun, Yu Ping, Liu Huibiao, Li Yuliang, Mao Lanqun
Beijing National Laboratory for Molecular Sciences, Key Laboratory of Analytical Chemistry for Living Biosystems, Key Laboratory of Organic Solids, Institute of Chemistry, The Chinese Academy of Sciences , Beijing 100190, China.
University of Chinese Academy of Sciences , Beijing 100049, China.
Anal Chem. 2017 Dec 5;89(23):13008-13015. doi: 10.1021/acs.analchem.7b04115. Epub 2017 Nov 21.
Graphdiyne (GDY) is recently synthesized two-dimensional carbon allotrope with hexagonal rings cross-linked by diacetylene through introducing butadiyne linkages (-C≡C-C≡C-) to form 18-C hexagons and is emerging to be fundamentally interesting and particularly useful in various research fields. In this study, we for the first time find that GDY can be used as an electrode material with reactivity tunable by electronic states and surface chemistry of GDY. To demonstrate this, GDY is oxidized into graphdiyne oxide (GDYO) that is then chemically and electrochemically reduced into chemically reduced GDYO (cr-GDYO) and electrochemically reduced GDYO (er-GDYO), respectively. Electrode reactivity of GDY and its derivatives (i.e., GDYO, cr-GDYO, and er-GDYO) is studied with hexaammineruthenium chloride ([Ru(NH)]Cl) and potassium ferricyanide (KFe(CN)) as redox probes. We find that electron transfer kinetics of the redox probes employed here at GDYs depends on the density of electronic state (DOS) and the synergetic effects of the surface chemistry as well as the hydrophilicity of the materials, and that the electron transfer kinetics at cr-GDYO and er-GDYO are faster than those at GDY and GDYO, and quite comparable with those at carbon nanotubes and graphene and its derivatives (i.e., GO, cr-GO, and er-GO). These properties, combined with the unique electronic and chemical structures of GDY, essentially enable GDY as a new kind of electrode material for fundamental studies on carbon electrochemistry and various electroanalytical applications.
石墨炔（GDY）是最近合成的一种二维碳同素异形体，它通过引入丁二炔键（-C≡C-C≡C-）使六边形环由二乙炔交联形成18碳六边形，并且在各个研究领域中逐渐展现出重要的基础研究价值和特别的实用性。在本研究中，我们首次发现GDY可作为一种电极材料，其反应活性可通过GDY的电子态和表面化学进行调节。为了证明这一点，将GDY氧化成氧化石墨炔（GDYO），然后分别将其化学还原和电化学还原为化学还原氧化石墨炔（cr-GDYO）和电化学还原氧化石墨炔（er-GDYO）。以六氨合钌（III）氯化物（[Ru(NH₃)₆]Cl₃）和铁氰化钾（K₃Fe(CN)₆）作为氧化还原探针，研究了GDY及其衍生物（即GDYO、cr-GDYO和er-GDYO）的电极反应活性。我们发现，此处使用的氧化还原探针在GDY上的电子转移动力学取决于电子态密度（DOS）、表面化学的协同效应以及材料的亲水性，并且cr-GDYO和er-GDYO上的电子转移动力学比GDY和GDYO上的更快，与碳纳米管、石墨烯及其衍生物（即GO、cr-GO和er-GO）上的相当。这些特性，结合GDY独特的电子和化学结构，从本质上使GDY成为一种新型电极材料，可用于碳电化学的基础研究和各种电分析应用。
