The development of high-performance and low-cost oxygen reduction and evolution catalysts that can be easily integrated into existing devices is crucial for the wide deployment of energy storage systems that utilize O₂-H₂O chemistries, such as regenerative fuel cells and metal-air batteries. Herein, we report an NH₃-activated N-doped hierarchical carbon (NHC) catalyst synthesized via a scalable route, and demonstrate its device integration. The NHC catalyst exhibited good performance for both the oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER), as demonstrated by means of electrochemical studies and evaluation when integrated into the oxygen electrode of a regenerative fuel cell. The activities observed for both the ORR and the OER were comparable to those achieved by state-of-the-art Pt and Ir catalysts in alkaline environments. We have further identified the critical role of carbon defects as active sites for electrochemical activity through density functional theory calculations and high-resolution TEM visualization. This work highlights the potential of NHC to replace commercial precious metals in regenerative fuel cells and possibly metal-air batteries for cost-effective storage of intermittent renewable energy.

Highly active and low-cost catalysts for electrochemical reactions such as the hydrogen evolution reaction (HER) are crucial for the development of efficient energy conversion and storage technologies. Theoretical simulations have been instrumental in revealing the correlations between the electronic structure of materials and their catalytic activity, and guide the prediction and development of improved catalysts. However, difficulties in accurately engineering the desired atomic sites lead to challenges in making direct comparisons between experimental and theoretical results. In MoS₂, the Mo-edge has been demonstrated to be active for HER whereas the S-edge is inert. Using a computational descriptor-based approach, we predict that by incorporating transition metal atoms (Fe, Co, Ni, or Cu) the S-edge site should also become HER active. Vertically standing, edge-terminated MoS₂ nanofilms provide a well-defined model system for verifying these predictions. The transition metal doped MoS₂ nanofilms show an increase in exchange current densities by at least two-fold, in agreement with the theoretical calculations. This work opens up further opportunities for improving electrochemical catalysts by incorporating promoters into particular atomic sites, and for using well-defined systems in order to understand the origin of the promotion effects.