Pt single-atom materials possess an ideal atom economy but suffer from limited intrinsic activity and side reaction of producing H2O2 in catalyzing the oxygen reduction reaction (ORR); platinum alloys have higher intrinsic activity but weak stability. Here, we demonstrate that anchoring platinum alloys on single-atom Pt-decorated carbon (Pt-SAC) surmounts their inherent deficiencies, thereby enabling a complete four-electron ORR pathway catalysis with high efficiency and durability. Pt3Co@Pt-SAC demonstrates an exceptional mass and specific activities 1 order of magnitude higher than those of commercial Pt/C. They are durable throughout 50000 cycles, showing only a 10 mV decay in half-wave potential. An in situ Raman analysis and theoretical calculations reveal that Pt3Co core nanocrystals modulate electron structures of the adjacent Pt single atoms to facilitate the intermediate absorption for fast kinetics. The superior durability is attributed to the shielding effect of the Pt-SAC coating, which significantly mitigates the dissolution of Pt3Co cores. The hybridizing strategy might promote the development of highly active and durable ORR catalysts.

The use of porous hard carbons (PHCs) as electrode materials in sodium-ion batteries has great potential; however, the exposure of large surface areas to electrolyte flow results in irregular and irreversible solid electrolyte interfaces (SEIs), leading to deteriorated ionic and electronic mobility and inferior initial Coulombic efficiency (ICE). These issues can be addressed through suitable structural modifications of PHC materials. Herein, the integration of high-surface-area PHCs with carbon nanofibers (CNFs) was accomplished by a simple electrospinning technique, which resulted in a uniform and reversible SEI layer. In the meantime, the CNFs’ mesh provided connectivity and conductivity in the as-integrated electrodes, whereas PHCs offered fast diffusion kinetics and high Na+ ion storage capacity. Additionally, PHC integration with CNFs demonstrated an excellent ICE of 77% and a specific capacity of 505 mAh/g at 25 mA/g. Furthermore, the conjugated microstructure also provided flexibility and stability to the electrode (260 mAh/g after 500 cycles). This remarkable synergy may promote the development of free-standing, flexible, and highly porous properties in a single material for advanced energy storage applications.

Electrocatalysts for the oxygen reduction reaction (ORR) play a central role in fuel cells and zinc–air batteries. Bimetal single atoms and nanoparticle hybrids are emerging ORR electrocatalysts, superior to the most exploited unary metal single-atom catalysts (SACs). Here, we report bimetal SAC-based nanofiber networks of Co3Fe7@Co/Fe-SAC for efficient ORR electrocatalysis and zinc–air batteries. A facile and easy-to-scale-up process is developed, and the versatility is validated in three hybrids. Strong electronic interaction is revealed between bimetal single atoms and alloy nanoparticles, leading to improved catalytic performances for ORR. Specifically, the Co3Fe7@Co/Fe-SAC hybrids exhibit a half-wave potential of 0.841 V in a basic electrolyte, comparable to the Pt/C electrocatalyst. Assembled in a zinc–air battery, a Co3Fe7@Co/Fe-SAC hybrid-based cell demonstrates a power density 1.8 times higher than the benchmark Pt/C-IrO2-based one, and it is stable for 150 cycles galvanostatic charge/discharge. The superior device performance is attributed to the appealing intrinsic activity, the carbon shielding effect for anti-leaching, and the hierarchical porous networks for large accessibility of active sites and favorable mass transport. Theoretical calculations suggest that alloy nanoparticles significantly improved the intrinsic catalytic activity of Fe single-atom sites at the expense of slightly lowering the activity of Co single-atom sites. This work presents a versatile process for the mass production of efficient composite electrocatalysts and highlights the power of bimetal single-atom-based hybrids and hierarchically porous structures for ORR device performances.

The development of high-performance non-noble metal-based oxygen electrocatalysts is crucial for the practical application of zinc–air batteries. Most of them suffer from low intrinsic activity and poor stability, failing to meet the needs of practical applications. Here, we report an efficient and durable bifunctional oxygen electrocatalyst of Fe@Fe-SAC composite (SAC stands for single atoms on carbon). A facile and ease-to-scale-up process synthesizes it. Fe single-atom and Fe nanoparticles are anchored on nitrogen-doped porous carbon, with the latter encapsulated by the graphitic shell. It exhibits appealing activity and durability in a basic electrolyte, requiring a half-wave potential of 0.805 V for oxygen reduction reaction (ORR) and an overpotential of only 348 mV to deliver a current density of 10 mA cm−2 for oxygen evolution reaction (OER). Both activities are comparable to the corresponding benchmarking electrocatalyst of Pt/C for ORR and IrO2 for OER. The superior activities are attributed to the strong electronic interaction between metal single-atom and nanoparticles. The favorable stability is ascribed to the physical encapsulation of carbon coatings on nanoparticles. This work presents a feasible scheme for designing and large-scale preparation of high-performance non-noble metal-based bifunctional oxygen electrocatalysts.