Zhou Ming, Guo Jidong, Guo Li-ping, Bai Jing
Faculty of Chemistry, Northeast Normal University, Changchun, 130024, PR China.
Anal Chem. 2008 Jun 15;80(12):4642-50. doi: 10.1021/ac702496k. Epub 2008 May 14.
In this paper, we report a novel all-carbon two-dimensionally ordered nanocomposite electrode system on the basis of the consideration of host-guest chemistry, which utilizes synergistic interactions between a nanostructured matrix of ordered mesoporous carbon (OMC) and an excellent electron acceptor of nanosized fullerene (C 60) to facilitate heterogeneous electron-transfer processes. The integration of OMC-C 60 by covalent interaction, especially its electrochemical applications for electrocatalysis, has not been explored thus far. Such integration may even appear to be counterintuitive because OMC and C 60 provide opposite electrochemical benefits in terms of facilitating heterogeneous electron-transfer processes. Nevertheless, the present work demonstrates the integration of OMC and C 60 can provide a remarkable synergistic augmentation of the current. To illuminate the concept, eight kinds of inorganic and organic electroactive compounds were employed to study the electrochemical response at an OMC-C 60 modified glassy carbon (OMC-C 60/GC) electrode for the first time, which shows more favorable electron-transfer kinetics than OMC/GC, carbon nanotube modified GC, C 60/GC, and GC electrodes. Such electrocatalytic behavior at OMC-C 60/GC electrode could be attributed to the unique physicochemical properties of OMC and C 60, especially the unusual host-guest synergy of OMC-C 60, which induced a substantial decrease in the overvoltage for NADH oxidation compared with GC electrode. The ability of OMC-C 60 to promote electron transfer not only suggests a new platform for the development of dehydrogenase-based bioelectrochemical devices but also indicates a potential of OMC-C 60 to be of a wide range of sensing applications because the electrocatalysis of different electroactive compounds at the OMC-C 60/GC electrode in this work should be a good model for constructing a novel and promising electrochemical sensing platform for further electrochemical detection of other biomolecules.
在本文中,基于主客体化学的考虑,我们报道了一种新型的全碳二维有序纳米复合电极系统,该系统利用有序介孔碳(OMC)的纳米结构基质与纳米尺寸富勒烯(C60)这种优异电子受体之间的协同相互作用来促进异相电子转移过程。通过共价相互作用实现的OMC - C60整合,尤其是其在电催化方面的电化学应用,迄今为止尚未得到探索。这种整合甚至可能看似违反直觉,因为就促进异相电子转移过程而言,OMC和C60提供了相反的电化学益处。然而,目前的工作表明OMC和C60的整合能够显著增强电流。为阐明这一概念,首次使用了八种无机和有机电活性化合物来研究在OMC - C60修饰玻碳(OMC - C60/GC)电极上的电化学响应,该电极显示出比OMC/GC、碳纳米管修饰的GC、C60/GC和GC电极更有利的电子转移动力学。OMC - C60/GC电极上的这种电催化行为可归因于OMC和C60独特的物理化学性质,尤其是OMC - C60非同寻常的主客体协同作用,与GC电极相比,这导致NADH氧化的过电位大幅降低。OMC - C60促进电子转移的能力不仅为基于脱氢酶的生物电化学装置的开发提供了一个新平台,还表明OMC - C60具有广泛传感应用的潜力,因为在这项工作中,不同电活性化合物在OMC - C60/GC电极上的电催化作用应该是构建用于进一步电化学检测其他生物分子的新型且有前景的电化学传感平台的良好模型。