As a clean and renewable energy carrier, hydrogen (H2) has become an attractive alternative to dwindling fossil fuels. The key to realize hydrogen-based energy systems is to develop efficient and...

The development of nonprecious metal catalysts with both oxygen reduction and evolution reactions (ORR/OER) is very important for Zn–air batteries (ZABs). Herein, a Co5.47N particles and Fe single atoms co‐doped hollow carbon nanofiber self‐supporting membrane (H‐CoFe@NCNF) is synthesized by a coaxial electrospinning strategy combined with pyrolysis. X‐ray absorption fine spectroscopy analyses confirm the state of the cobalt nitride and Fe single atoms. As a result, H‐CoFe@NCNF exhibits a superior bifunctional performance of Eonset = 0.96 V for ORR, and Ej = 10 = 1.68 V for OER. Density functional theory calculations show that H‐CoFe@NCNF has a moderate binding strength to oxygen due to the coexistence of nanoparticle and single atoms. Meanwhile, the Co site is more favorable to the OER, while the Fe site facilitates the ORR, and the proton and charge transfer between N and metal atoms further lower the reaction barriers. The liquid ZAB composed of H‐CoFe@NCNF has a charge–discharge performance of ≈1100 h and a peak power density of 205 mW cm−2. The quasi‐solid‐state ZAB assembled by the self‐supporting membrane of H‐CoFe@NCNF is proven to operate stably in any bending condition.

Electrocatalytic water splitting is one of the most efficient ways of producing green hydrogen energy. The design of stable, active, and efficient electrocatalysts plays a crucial role in water splitting for achieving efficient energy conversion from electrical to hydrogen energy, aimed at solving the lingering energy crisis. In this work, CNT composites modified with CoP-V4P3 composites (CoVO-10-CNT-450P) were formed by carbonising a pencil-like precursor (Co3V2O8-H2O) and growing carbon nanotubes in situ, followed by in situ phosphorylation on the carbon nanotubes. In the HER electrocatalytic process, an overpotential of only 124 mV was exhibited at a current density of 10 mA cm−2. In addition, as an OER catalyst, a low overpotential of 280 mV was attained at a current density of 10 mA cm−2. Moreover, there was no noticeable change in the performance of the catalyst over a 90 h test in a continuous total water splitting experiment. The unique electronic structure and hollow carbon nanotube structure of CoVO-10-CNT-450P effectively increased the catalytic active sites, while also significantly improving the electrocatalytic activity. This work provides theoretical guidance for the design and synthetic route of high-performance non-precious metal electrocatalysts, and actively promotes the commercial application of electrochemical water splitting.