Hydrogen, a renewable and outstanding energy carrier with zero carbon dioxide emission, is regarded as the best alternative to fossil fuels. The most preferred route to large-scale production of hydrogen is by water electrolysis from the intermittent sources (e.g., wind, solar, hydro, and tidal energy). However, the efficiency of water electrolysis is very much dependent on the activity of electrocatalysts. Thus, designing high-effective, stable, and cheap materials for hydrogen evolution reaction (HER) could have a substantial impact on renewable energy technologies. Recently, single-atom catalysts (SACs) have emerged as a new frontier in catalysis science, because SACs have maximum atom-utilization efficiency and excellent catalytic reaction activity. Various synthesis methods and analytical techniques have been adopted to prepare and characterize these SACs. In this review, we discuss recent progress on SACs synthesis, characterization methods, and their catalytic applications. Particularly, we highlight their unique electrochemical characteristics toward HER. Finally, the current key challenges in SACs for HER are pointed out and some potential directions are proposed as well.

Rechargeable zinc-air batteries (ZABs) are currently receiving extensive attention because of their extremely high theoretical specific energy density, low manufacturing costs, and environmental friendliness. Exploring bifunctional catalysts with high activity and stability to overcome sluggish kinetics of oxygen reduction reaction and oxygen evolution reaction is critical for the development of rechargeable ZABs. Atomically dispersed metal-nitrogen-carbon (M-N-C) catalysts possessing prominent advantages of high metal atom utilization and electrocatalytic activity are promising candidates to promote oxygen electrocatalysis. In this work, general principles for designing atomically dispersed M-N-C are reviewed. Then, strategies aiming at enhancing the bifunctional catalytic activity and stability are presented. Finally, the challenges and perspectives of M-N-C bifunctional oxygen catalysts for ZABs are outlined. It is expected that this review will provide insights into the targeted optimization of atomically dispersed M-N-C catalysts in rechargeable ZABs.

Nitrogen-doped carbon materials, including nitrogen-doped carbon nanotubes (NCNTs) and nitrogen-doped graphene (NG), have attracted increasing attention for oxygen reduction reaction (ORR) in metal-air batteries and fuel cell applications, due to their optimal properties including excellent electronic conductivity, 4e⁻ transfer and superb mechanical properties. Here, the recent progress of NCNTs- and NG-based catalysts for ORR is reviewed. Firstly, the general preparation routes of these two N-doped carbon-allotropes are introduced briefly, and then a special emphasis is placed on the developments of both NCNTs and NG as promising metal-free catalysts and/or catalyst support materials for ORR. All these efficient ORR electrocatalysts feature a low cost, high durability and excellent performance, and are thus the key factors in accelerating the widespread commercialization of metal-air battery and fuel cell technologies.

Highlights: Three-dimensional (3D) core‐shell heterostructured Ni_xS_y@MnO_xH_y nanorods grown on nickel foam (Ni_xS_y@MnO_xH_y/NF) were successfully fabricated via a simple hydrothermal reaction and a subsequent electrodeposition process. The fabricated Ni_xS_y@MnO_xH_y/NF shows outstanding bifunctional activity and stability for hydrogen evolution reaction and oxygen evolution reaction, as well as overall‐water‐splitting performance. The main origins are the interface engineering of Ni_xS_y@MnO_xH_y, the shell‐protection characteristic of MnO_xH_y, and the 3D open nanorod structure, which remarkably endow the electrocatalyst with high activity and stability. Exploring highly active and stable transition metal-based bifunctional electrocatalysts has recently attracted extensive research interests for achieving high inherent activity, abundant exposed active sites, rapid mass transfer, and strong structure stability for overall water splitting. Herein, an interface engineering coupled with shell-protection strategy was applied to construct three-dimensional (3D) core‐shell Ni_xS_y@MnO_xH_y heterostructure nanorods grown on nickel foam (Ni_xS_y@MnO_xH_y/NF) as a bifunctional electrocatalyst. Ni_xS_y@MnO_xH_y/NF was synthesized via a facile hydrothermal reaction followed by an electrodeposition process. The X-ray absorption fine structure spectra reveal that abundant Mn‐S bonds connect the heterostructure interfaces of Ni_xS_y@MnO_xH_y, leading to a strong electronic interaction, which improves the intrinsic activities of hydrogen evolution reaction and oxygen evolution reaction (OER). Besides, as an efficient protective shell, the MnO_xH_y dramatically inhibits the electrochemical corrosion of the electrocatalyst at high current densities, which remarkably enhances the stability at high potentials. Furthermore, the 3D nanorod structure not only exposes enriched active sites, but also accelerates the electrolyte diffusion and bubble desorption. Therefore, Ni_xS_y@MnO_xH_y/NF exhibits exceptional bifunctional activity and stability for overall water splitting, with low overpotentials of 326 and 356 mV for OER at 100 and 500 mA cm^–2, respectively, along with high stability of 150 h at 100 mA cm^–2. Furthermore, for overall water splitting, it presents a low cell voltage of 1.529 V at 10 mA cm^–2, accompanied by excellent stability at 100 mA cm^–2 for 100 h. This work sheds a light on exploring highly active and stable bifunctional electrocatalysts by the interface engineering coupled with shell-protection strategy.