Platinum group metal-free (PGM-free) metal-nitrogen-carbon catalysts have emerged as a promising alternative to their costly platinum (Pt)-based counterparts in polymer electrolyte fuel cells (PEFCs) but still face some major challenges, including (i) the identification of the most relevant catalytic site for the oxygen reduction reaction (ORR) and (ii) demonstration of competitive PEFC performance under automotive-application conditions in the hydrogen (H)-air fuel cell. Herein, we demonstrate H-air performance gains achieved with an iron-nitrogen-carbon catalyst synthesized with two nitrogen precursors that developed hierarchical porosity. Current densities recorded in the kinetic region of cathode operation, at fuel cell voltages greater than ~0.75 V, were the same as those obtained with a Pt cathode at a loading of 0.1 milligram of Pt per centimeter squared. The proposed catalytic active site, carbon-embedded nitrogen-coordinated iron (FeN), was directly visualized with aberration-corrected scanning transmission electron microscopy, and the contributions of these active sites associated with specific lattice-level carbon structures were explored computationally.

A general synthetic strategy for yolk-shell nanocrystal@ZIF-8 nanostructures has been developed. The yolk-shell nanostructures possess the functions of nanoparticle cores, microporous shells, and a cavity in between, which offer great potential in heterogeneous catalysis. The synthetic strategy involved first coating the nanocrystal cores with a layer of Cu(2)O as the sacrificial template and then a layer of polycrystalline ZIF-8. The clean Cu(2)O surface assists in the formation of the ZIF-8 coating layer and is etched off spontaneously and simultaneously during this process. The yolk-shell nanostructures were characterized by transmission electron microscopy, scanning electron microscopy, X-ray diffraction, and nitrogen adsorption. To study the catalytic behavior, hydrogenations of ethylene, cyclohexene, and cyclooctene as model reactions were carried out over the Pd@ZIF-8 catalysts. The microporous ZIF-8 shell provides excellent molecular-size selectivity. The results show high activity for the ethylene and cyclohexene hydrogenations but not in the cyclooctene hydrogenation. Different activation energies for cyclohexene hydrogenation were obtained for nanostructures with and without the cavity in between the core and the shell. This demonstrates the importance of controlling the cavity because of its influence on the catalysis.

Significant mass-transport resistances in polymer-electrolyte-fuel-cell catalyst layers (CLs) impose a lower limit on Pt-loading levels, hindering widespread fuel-cell commercialization. The origin of this resistance remains unclear. Minimization of CL mass-transport resistance is imperative to achieve better CL design and performance. In this paper, an operando method based on H 2 limiting current is used to characterize and quantify CL resistance in traditional porous Pt/carbon-based electrodes. CL sub-resistances are isolated using continuum multiscale modeling and experiments, investigating the effects of reactant molecular weight, pressure, and ionomer to carbon weight ratio. The results expose CL resistance including both interfacial and transport components, although the majority of the CL resistance is ascribed to a local resistance close to the Pt reaction sites, which includes interfacial resistance and local transport resistance. Variations in temperature, humidity, and primary particle loading (Pt:C ratio) highlight the impact of operating conditions and CL design parameters on CL sub-resistances. The observed trends guide optimization of CL design to achieve novel low-loaded fuel-cell electrodes.