The durability and reactivity of catalysts can be effectively and precisely controlled through the careful design and engineering of their surface structures and morphologies. Herein, we develop a novel "adsorption-calcination-reduction" strategy to synthesize spinel transitional metal oxides with a unique necklace-like multishelled hollow structure exploiting sacrificial templates of carbonaceous microspheres, including NiCoO (NCO), CoMnO, and NiMnO. Importantly, benefiting from the unique structures and reduction treatment to offer rich oxygen vacancies, the unique reduced NCO (R-NCO) as a bifunctional electrocatalyst exhibits the dual characteristics of good stability as well as high electrocatalytic activity for both the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER). At 1.61 V cell voltage, a 10 mA cm water splitting current density is obtained from the dual-electrode, alkaline water electrolyzer. Calculations based on density functional theory (DFT) reveal a mechanism for the promotion of the catalytic reactions based on a decrease in the energy barrier for the formation of intermediates resulting from the introduction of oxygen vacancies through the reduction process. This method could prove to be an effective general strategy for the preparation of complex, hollow structures and functionalities.

Metal single‐atom materials with their high atom utilization efficiency and unique electronic structures usually show remarkable catalytic performances in many crucial chemical reactions. Herein, a facile and easily scalable “impregnation‐carbonization‐acidification” strategy for fabricating a class of single‐atom‐anchored (including cobalt and nickel single atoms) monolith as superior binder‐free electrocatalysts for developing high‐performance wearable Zn–air batteries is reported. The as‐prepared single atoms, supported by N‐doped carbon flake arrays grown on carbon nanofibers assembly (M SA@NCF/CNF), demonstrate the dual characteristics of excellent catalytic activity (reversible oxygen overpotential of 0.75 V) and high stability, owing to the greatly improved active sites' accessibility and optimized single‐sites/pore‐structures correlations. Furthermore, wearable Zn–air battery based on Co SA@NCF/CNF air electrode displays superior stability under deformation, satisfactory energy storage capacity, and good practicality to be utilized as an integrated battery system. Theoretical calculations reveal a mechanism for the promotion of the catalytic performances on single atomic sites by lowering the overall oxygen reduction/evolution reaction barriers comparing to metal cluster co‐existing configuration. These findings provide a facile strategy for constructing free‐standing single‐atom materials as well as the engineering of high‐performance binder‐free catalytic electrodes.

Rational design and massive production of bifunctional catalysts with superior oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) activities are essential for developing metal–air batteries and fuel cells. Herein, controllable large‐scale synthesis of sulfur‐doped CaMnO3 nanotubes is demonstrated via an electrospinning technique followed by calcination and sulfurization treatment. The sulfur doping can not only replace oxygen atoms to increase intrinsic electrical conductivity but also introduce abundant oxygen vacancies to provide enough catalytically active sites, which is further demonstrated by density functional theory calculation. The resulting sulfur‐modified CaMnO3 (CMO/S) exhibits better electrocatalytic activity for ORR and OER in alkaline solution with higher stability performance than the pristine CMO. These results highlight the importance of sulfur treatment as a facile yet effective strategy to improve the ORR and OER catalytic activity of the pristine CaMnO3. As a proof‐of‐concept, a rechargeable Zn–air battery using the bifunctional catalyst exhibits a small charge–discharge voltage polarization, and long cycling life. Furthermore, a solid‐state flexible and rechargeable Zn–air battery gives superior discharge–charge performance and remarkable stability. Therefore, the CMO/S nanotubes might be a promising replacement to the Pt‐based electrocatalysts for metal–air batteries and fuel cells.

• Coronavirus pandemic have made facemasks worldwide healthcare essentials • Shortage of masks exposes medical personnel and the public to the risk of infection • Utilisation of sustainable raw materials to develop bio-based masks is needed • Electrospun and compression moulded gluten can be used to develop biobased masks • Gluten masks can be made flame retardant by adding b10 wt% of lanosol.