Freiburg Materials Research Center (FMF), University of Freiburg, Stefan-Meier-Strasse 21, 79104 Freiburg, Germany.
Nanoscale. 2017 May 18;9(19):6436-6447. doi: 10.1039/c7nr01391d.
The limited performance of platinum-based electrocatalysts for glucose electrooxidation is a major concern for glucose fuel cells, since glucose electrooxidation is characterized by slow reaction kinetics and low diffusion coefficient. Here, the presented graphene-supported platinum-based hierarchical nanostructures attain highly enhanced electrocatalytic activity towards glucose oxidation. Platinum nanoparticles electrodeposited on graphene support retain mechanical stability and act as junctions allowing a reliable, smooth and dense growth of platinum nanowires with extremely small diameters (>10 nm) on graphene. The electrode's surface roughness was increased by factors up to 4000 to the geometrical surface area enabling maximized exploitation of the electrocatalytic activity of platinum and efficient electron transfer between nanowires and the substrate. The unique three-dimensional geometry of these hierarchical nanostructures has a significant impact on their catalytic performance offering short diffusional paths for slow glucose species, thus, mass transport limitations are optimized leading to lower polarization losses. This was examined by galvanostatic measurements of the operation as anodes in glucose half-cells under conditions corresponding to implantable glucose fuel cells. The presented hierarchical nanostructures show remarkably enhanced catalytic performance for glucose electrooxidation, i.e. a negatively shifted open circuit potential of -580 mV vs. Ag/AgCl, hence, representing appropriate electrocatalysts for use as anodes in glucose fuel cells. In combination with a non-metal N-doped graphene cathode, a cell potential of 0.65 V was achieved at a galvanostatic load of 17.5 μA cm which noticeably surpasses the performance of state of the art catalysts for the aforementioned operation conditions.
基于铂的电催化剂在葡萄糖电氧化方面的性能有限,这是葡萄糖燃料电池的一个主要关注点,因为葡萄糖电氧化的反应动力学缓慢,扩散系数低。在这里,所提出的基于石墨烯的铂基分级纳米结构在葡萄糖氧化方面表现出了高度增强的电催化活性。在石墨烯载体上电沉积的铂纳米颗粒保持机械稳定性,并作为连接点,允许在石墨烯上可靠、平滑和致密地生长具有极细直径(>10nm)的铂纳米线。电极的表面粗糙度增加了高达 4000 倍,相对于几何表面积,从而最大限度地利用了铂的电催化活性和纳米线与基底之间的有效电子转移。这些分级纳米结构的独特的三维几何形状对其催化性能有重大影响,为缓慢的葡萄糖物种提供了较短的扩散路径,因此,优化了质量传输限制,从而降低了极化损失。这通过在与可植入葡萄糖燃料电池相对应的条件下作为阳极在葡萄糖半电池中的恒电流测量进行了检查。所提出的分级纳米结构在葡萄糖电氧化方面表现出显著增强的催化性能,即开路电位负移至-580mV 相对于 Ag/AgCl,因此,代表了适合用作葡萄糖燃料电池阳极的合适电催化剂。与非金属 N 掺杂石墨烯阴极结合,在 17.5μA cm 的恒电流负载下实现了 0.65V 的电池电势,明显超过了上述操作条件下的最先进催化剂的性能。