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.

This work draws attention to the optimal hierarchical nanostructure morphology and the morphological characteristics that lead to a rational design of heterogeneous nanocatalysts, especially for reactions that exhibit sluggish kinetics. A simplified methanol oxidation on two types of hierarchical nanostructures, external and internal, is reported. A complex system of asymmetric geometries was simplified by mapping 3 D geometries into 2 D models by using a mass transport approach. The macropore size was the most comprehensive characteristic to evaluate the specific activity and current density of hierarchical nanostructures. The optimal current densities for both types of nanostructures were achieved in macropore size ranges of 3.2–4.5 and 1.9–3.2 μm, respectively. The optimal mass activity of the internal nanostructures was achieved in the porosity range of 40–50 %, whereas that of the external hierarchical nanostructures was achieved at high porosity values. In comparison to internal hierarchical nanostructures, external hierarchical nanostructures tend to be cost‐effective catalysts that have a high catalytic activity.

Efficiency, selectivity and sensitivity are important issues in catalytic applications, such as fuel cells and electrochemical sensors. This paper discusses the catalytic activity of porous layers in heterogeneous reactions based on the impact of pore morphology on pore accessibility in liquids. We present three-dimensional simulations to discuss some critical geometrical characteristics that influence the overall catalytic activity of porous catalyst. Sensitivity is proportional to the overall catalytic activity of the surface area. However, selectivity depends on pore accessibility. Simulation results demonstrate that at constant k 0 , porous layers with small pores and large numbers of pores are selective to the species with high diffusion coefficient because of high pore accessibility. In contrast, porous electrodes with low number of large pores and a large top surface area are selective to the species with low diffusion coefficient because of low pore accessibility. Additionally, pore accessibility influences the diffusional resistance, which has an impact on the local pH-value. High diffusional resistance in the porous layer leads to an accumulation of reaction products and a modification in the concentration of buffer molecules, which change local pH-value and therefore the catalytic behavior.