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Fine control over the physicochemical structures of carbon electrocatalysts is important for improving the sluggish oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) in rechargeable Zn–air batteries. Covalent organic frameworks (COFs) are considered good candidate carbon materials because their structures can be precisely controlled. However, it remains a challenge to impart bifunctional electrocatalytic activities for both the ORR and OER to COFs. Herein, a pyridine‐linked triazine covalent organic framework (PTCOF) with well‐defined active sites and pores is readily prepared under mild conditions, and its electronic structure is modulated by incorporating Co nanoparticles (CoNP‐PTCOF) to induce bifunctional electrocatalytic activities for the ORR and OER. The CoNP‐PTCOF exhibits lower overpotentials for both ORR and OER with outstanding stability. Computational simulations find that the p‐band center of CoNP‐PTCOF down‐shifted by charge transfer, compared to pristine PTCOF, facilitate the adsorption and desorption of oxygen intermediates on the pyridinic carbon active sites during the reactions. The Zn–air battery assembled with bifunctional CoNP‐PTCOF exhibits a small voltage gap of 0.83 V and superior durability for 720 cycles as compared with a battery containing commercial Pt/C and RuO2. This strategy for modulating COF electrocatalytic activities can be extended for designing diverse carbon electrocatalysts. [ABSTRACT FROM AUTHOR]

Precise control over doping of photocatalysts is required to modulate their photocatalytic activity in visible light-driven reactions. Here, a single precursor-employing bottom-up approach is developed to produce different heteroatom-doped graphene quantum dots (GQDs) with unique photocatalytic activities. The solvothermal reaction of a norepinephrine precursor with redox active and condensable moieties effectively produces both nitrogen/sulfur codoped GQDs (NS-GQDs) and nitrogen-doped GQDs (N-GQDs) by simply varying solvents (from dimethyl sulfoxide to water) under microwave irradiation. As-prepared NS-GQDs and N-GQDs show similar lateral sizes (3-4 nm) and heights (1-2 nm), but they include different dopant types and doping constitution and content, which lead to changes in photocatalytic activity in aerobic oxidative coupling reactions of various amines. NS-GQDs exhibit much higher photocatalytic activity in reactions under visible light than N-GQDs and oxygen-doped GQDs (O-GQDs). The mechanism responsible for the outstanding photocatalytic activity of NS-GQDs in visible light-driven oxidative coupling reactions of amines is also fully investigated. [ABSTRACT FROM AUTHOR]