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.
The lack of performance of graphene-based electrocatalysts for oxygen reduction (ORR) is a major concern for fuel cells which can be mastered using nanocomposites. This work is highlighted by the optimization of nitrogen(N)-doped graphene/carbon nanotubes (CNTs) nanocomposite's ORR performance examined by galvanostatic measurements in realistically approached glucose half-cells. Obtained results mark an essential step for the development of nanocarbon-based cathodes, as we specifically evaluate the electrode performance under real fuel cell conditions. The 2D simulations exclusively represent an important approach for understanding the catalytic efficiency of the nanocomposite with unique structure. The kinetics features extracted from simulations are consistent with the experimentally determined kinetics. The morphology analysis reveals a 3D porous structure. The results demonstrate that the incorporation of CNTs implements mesoscale channels for improved mass transport and leads to efficient 4-electron transfer and enhanced overall catalytic activity in pH-neutral media. The nanocomposite shows increased specific surface area of 142 m g, positively shifted ORR onset potential of 67 mV and higher open circuit potential of 268 mV versus Ag/AgCl compared to N-graphene (11 m g, -17, 220 mV). The findings are supported by 2D simulations giving qualitative evidence to the significant role of CNTs for achieving better accessibility of pores, i.e. enabling improved transfer of oxygen and OH, and providing more reaction sites in the nanocomposite. The nanocomposite demonstrates better ORR performance than constituent components regarding potential application in miniaturized single-compartment glucose-based fuel cells.
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