9 Search Results

The design of oxygen evolution reaction (OER) electrocatalysts demands a delicate balance between activity and stability. Here, in this study, we present a rational design approach that leverages catalyst-support interactions to enhance both the intrinsic activity and durability of Ir-based catalysts. Our study reveals that while Mo doping energetically promotes the formation of high-valent Ir species, enhancing intrinsic catalytic activity, it also leads to a reduction in electrical conductivity. These findings emphasize that supporting doping can introduce both beneficial and limiting effects, highlighting the need for a carefully balanced design strategy to optimize the overall OER performance. Simultaneously, in situmore » analytical techniques and comparative evaluation reveal the crucial role of oxide supports in stabilizing the catalyst. These findings highlight the pivotal role of interface engineering in maintaining catalyst integrity and the need for support materials that balance dopant-driven electronic promotion with structural and electrochemical robustness. These interconnected degradation pathways highlight the need to move beyond a catalyst-centric view and instead adopt a system-level understanding of the stability. Our approach offers a strong foundation for the rational design and evaluation of high-performance OER electrocatalysts for electrochemical energy applications.« less

Successful development of catalysts for electrochemical formic acid oxidation (FAO) requires finding an optimal balance between catalytic performance (activity, stability, and selectivity) and catalyst cost. While platinum is one of the most active catalyst materials for FAO, it suffers from performance loss at low overpotentials due to poisoning with CO, which is one of the intermediates formed in the so-called indirect path of FAO. In this work, we explored the synergistic effects of the supporting material and annealing temperature on the performance of Pt thin films for FAO in acidic media. Compared to the as-prepared Pt films, the annealed filmsmore » show up to 5-fold and 15-fold improvement for FAO on Pt@Ni and Pt@Cr, respectively. In conclusion, while the most active Pt@Ni thin film shows the lowest stability, the most active Pt@Cr thin film is also the most stable, challenging conventional trade-offs in electrocatalysis and providing a promising candidate for FAO nanocatalyst synthesis.« less

The feasible commercialization of alkaline, phosphoric acid and polymer electrolyte membrane fuel cells depends on the development of oxygen reduction reaction (ORR) electrocatalysts with improved activity, stability, and selectivity. The rational design of surfaces to ensure these improved ORR catalytic requirements relies on the so-called "descriptors" (e.g., the role of covalent and noncovalent interactions on platinum surface active sites for ORR). Here, we demonstrate that through the molecular adsorption of melamine onto the Pt(111) surface [Pt(111)-M_ad], the activity can be improved by a factor of 20 compared to bare Pt(111) for the ORR in a strongly adsorbing sulfuric acid solution.more » Additionally, the M_ad moieties act as "surface-blocking bodies," selectively hindering the adsorption of (bi)sulfate anions (well-known poisoning spectator of the Pt(111) active sites) while the ORR is unhindered. This modified surface is further demonstrated to exhibit improved chemical stability relative to Pt(111) patterned with cyanide species (CN_ad), previously shown by our group to have a similar ORR activity increase compared to bare Pt(111) in a sulfuric acid electrolyte, with Pt(111)-M_ad retaining a greater than ninefold higher ORR activity relative to bare Pt(111) after extensive potential cycling as compared to a greater than threefold higher activity retained on a CN_ad-covered Pt(111) surface. We suggest that the higher stability of the Pt(111)-M_ad interface stems from melamine's ability to form intermolecular hydrogen bonds, which effectively turns the melamine molecules into larger macromolecular entities with multiple anchoring sites and thus more difficult to remove.« less

Perovskite oxides are an important class of oxygen evolution reaction (OER) catalysts in alkaline media, despite the elusive nature of their active sites. In this work, we demonstrate that the origin of the OER activity in a La_1-xSrxCoO₃ model perovskite arises from a thin surface layer of Co hydr(oxy)oxide (CoO_xH_y) that interacts with trace-level Fe species present in the electrolyte, creating dynamically stable active sites. Generation of the hydr(oxy)oxide layer is a consequence of a surface evolution process driven by the A-site dissolution and O-vacancy creation. In turn, this imparts a 10-fold improvement in stability against Co dissolution and amore » 3-fold increase in the activity-stability factor for CoO_xH_y/ LSCO when compared to nanoscale Co-hydr(oxy)oxides clusters. Our results suggest new design rules for active and stable perovskite oxide-based OER materials.« less

The poor activity and stability of electrode materials for the oxygen evolution reaction are the main bottlenecks in the water-splitting reaction for H₂ production. In this work, by studying the activity–stability trends for the oxygen evolution reaction on conductive M¹O_xH_y, Fe–M¹O_xH_y and Fe–M¹M²O_xH_y hydr(oxy)oxide clusters (M¹ = Ni, Co, Fe; M² = Mn, Co, Cu), we show that balancing the rates of Fe dissolution and redeposition over a MO_xH_y host establishes dynamically stable Fe active sites. Together with tuning the Fe content of the electrolyte, the strong interaction of Fe with the MO_xH_y host is the key to controlling themore » average number of Fe active sites present at the solid/liquid interface. We suggest that the Fe–M adsorption energy can therefore serve as a reaction descriptor that unifies oxygen evolution reaction catalysis on 3d transition-metal hydr(oxy)oxides in alkaline media. Thus, the introduction of dynamically stable active sites extends the design rules for creating active and stable interfaces.« less

By combining idealized experiments with realistic quantum mechanical simulations of an interface, we investigate electroreduction reactions of HF, water and methanesulfonic acid on the single crystal (111) facets of Au, Pt, Ir and Cu in a variety of aprotic electrolytes.

The formation of solid electrolyte interphase on graphite anodes plays a key role in the efficiency of Li-ion batteries. However, to date, fundamental understanding of the formation of LiF as one of the main solid electrolyte interphase components in hexafluorophosphate-based electrolytes remains elusive. In this paper, we present experimental and theoretical evidence that LiF formation is an electrocatalytic process that is controlled by the electrochemical transformation of HF impurity to LiF and H₂. Although the kinetics of HF dissociation and the concomitant production of LiF and H₂ is dependent on the structure and nature of surface atoms, the underlying electrochemistrymore » is the same. The morphology, and thus the role, of the LiF formed is strongly dependent on the nature of the substrate and HF inventory, leading to either complete or partial passivation of the interface. Finally, our finding is of general importance and may lead to new opportunities for the improvement of existing, and design of new, Li-ion technologies.« less