The fundamentals related to the oxygen evolution reaction and catalyst design are summarized and discussed.

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Oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) are the two most important reactions in rechargeable metal‐air battery, a promising technology to meet the energy requirements for various applications. The development of low‐cost, highly efficient and stable bifunctional ORR/OER catalysts is critical for a large‐scale application of this technology. In this review, the authors first introduce the fundamentals of bifunctional ORR/OER electrocatalysis in alkaline electrolyte. Various types of nanostructured materials as bifunctional ORR/OER catalysts including metal oxide, hydroxide and sulfide, functional carbon material, metal, and their composites are then reviewed. The crucial factors that can be used to tune the activity of the catalyst towards ORR/OER are summarized, including (1) phase, morphology, crystal facet, defect, mixed‐metal and strain engineering for metal oxide; (2) heteroatom doping, topological defects, and formation of metal‐N‐C structure for carbon material; (3) alloy effect for metal. These experiences lay the foundation for large scale application of metal‐air battery and can also effectively guide the rational design of catalysts for other electrocatalytic reactions.

The development of highly active, universal, and stable inexpensive electrocatalysts/cocatalysts for hydrogen evolution reaction (HER) by morphology and structure modulations remains a great challenge. Herein, a simple self-template strategy was developed to synthesize hollow Co-based bimetallic sulfide (MxCo3-xS4, M = Zn, Ni, and Cu) polyhedra with superior HER activity and stability. Homogenous bimetallic metal-organic frameworks are transformed to hollow bimetallic sulfides by solvothermal sulfidation and thermal annealing. Electrochemical measurements and density functional theory computations show that the combination of hollow structure and homoincorporation of a second metal significantly enhances the HER activity of Co3S4. Specifically, the homogeneous doping in Co3S4 lattice optimizes the Gibbs free energy for H* adsorption and improves the electrical conductivity. Impressively, hollow Zn0.30Co2.70S4 exhibits electrocatalytic HER activity better than most of the reported nobel-metal-free electrocatalysts over a wide pH range, with overpotentials of 80, 90, and 85 mV at 10 mA cm(-2) and 129, 144, and 136 mV at 100 mA cm(-2) in 0.5 M H2SO4, 0.1 M phosphate buffer, and 1 M KOH, respectively. It also exhibits photocatalytic HER activity comparable to that of Pt cocatalyst when working with organic photosensitizer (Eosin Y) or semiconductors (TiO2 and C3N4). Furthermore, this catalyst shows excellent stability in the electrochemical and photocatalytic reactions. The strategy developed here, i.e., homogeneous doping and self-templated hollow structure, provides a way to synthesize transition metal sulfides for catalysis and energy conversion.