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Carbon nanomaterials doped with N and B could activate nearby carbon atoms to promote charge polarization through the synergistic coupling effect between N and B atoms, thus facilitating adsorption of O2 and weakening O−O bond to enhance oxygen reduction reaction. Herein, a simple and controllable self‐assembly strategy is applied to synthesize porous B, N co‐doped carbon‐based catalysts (BCN‐P), which employs the macrocyclic molecule cucurbit[7]uril (CB7) as nitrogen source, and 3D aromatic‐like closo‐[B12H12]2− as boron source. In addition, polystyrene microspheres are added to help introduce porous structure to expose more active sites. Benefitting from porous structures and the synergistic coupling effect between N and B atoms, BCN‐P has a high onset potential (Eonset=0.846 V) and half‐wave potential (E1/2=0.74 V) in alkaline media. The zinc‐air battery assembled with BCN‐P shows high operating voltage (1.42 V), peak power density (128.7 mW cm−2) and stable charge/discharge cycles, which is even comparable with Pt/C. [ABSTRACT FROM AUTHOR]

The strong metal-support interactions between metal and its support have been considered as an effective way to improve the electrocatalytic activity in heterogeneous catalysis, which can modulate metal d -band's energy level and, consequently, affect the adsorption/desorption of the intermediates on the metal nanoparticle's surface. In this paper, we use a self-assembly strategy for construction nano-sized Ru nanoparticles (NPs) anchored on B, N co-doping carbon nanorod carrier (Ru/BCN) as HER catalyst by using unique boron cluster-organic framework as precursor and self-sacrificing templates. This supramolecular framework forming with cucurbit [6]uril as the host and closo -[B 12 H 12 ]2- as the guest can feature unique hexagonal nanorod morphology to confine the Ru NPs into framework through weak reductivity of closo -[B 12 H 12 ]2-. After pyrolysis, the strong metal-support interactions between B, N co-doping carbon support (BCN) and Ru NPs have been found due to the synergistic coupling effect of co-dopants B and N, which can increase electron transfer between the metal nanoparticle and support. The overpotentials of 33 mV and 40 mV are required for as-prepared catalyst Ru/BCN to achieve a current density of 10 mA cm−2 in alkaline and acidic conditions, respectively, which are approximately one third of those of Ru/CN. These findings demonstrate that our synthetic way offers a potential route for fabricating co-doping carbon with B and N atoms to support Ru NPs with enhanced HER performance in pH-independent conditions. • Ru/BCN was synthesized by a unique boron cluster-organic framework (BOFs). • Ru NPs was in situ confined into BOFs through weak reductivity of closo -[B 12 H 12 ]2-. • The synergistic coupling effect of B and N aids to increase the metal-support interaction. • Ru/BCN exhibits excellent catalytic activities in alkaline and acidic solutions. [ABSTRACT FROM AUTHOR]