Amorphous MnO2 Lamellae Encapsulated Covalent Triazine Polymer-Derived Multi-Heteroatoms-Doped Carbon for ORR/OER Bifunctional Electrocatalysis.

The intelligent construction of non-noble metal materials that exhibit reversible oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) with bifunctional electrocatalytic performance is greatly coveted in the realm of zinc-air batteries (ZABs). Herein, a crafted structure-amorphous MnO2 lamellae encapsulated covalent triazine polymer-derived N, S, P co-doped carbon sphere (A-MnO2/NSPC) is designed using a self-doped pyrolysis coupled with an in situ encapsulation strategy. The customized A-MnO2/NSPC-2 demonstrates a superior bifunctional electrocatalytic performance, confirmed by a small ΔE index of 0.64 V for ORR/OER. Experimental investigations, along with density functional theory calculations validate that predesigned amorphous MnO2 surface defects and abundant heteroatom catalytic active sites collectively enhance the oxygen electrocatalytic performance. Impressively, the A-MnO2/NSPC-based rechargeable liquid ZABs show a large open-circuit potential of 1.54 V, an ultrahigh peak power density of 181 mW cm-2, an enormous capacity of 816 mAh g-1, and a remarkable stability for more than 1720 discharging/charging cycles. Additionally, the assembled flexible all-solid-state ZABs also demonstrate outstanding cycle stability, surpassing 140 discharging/charging cycles. Therefore, this highly operable synthetic strategy offers substantial understanding in the development of magnificent bifunctional electrocatalysts for various sustainable energy conversions and beyond.

Boosting Bifunctional Catalysis by Integrating Active Faceted Intermetallic Nanocrystals and Strained Pt-Ir Functional Shells.

PtIr-based nanostructures are fascinating materials for application in bifunctional oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) catalysis. However, the fabrication of PtIr nanocatalysts with clear geometric features and structural configurations, which are crucial for enhancing the bifunctionality, remains challenging. Herein, PtCo@PtIr nanoparticles are precisely designed and fabricated with a quasi-octahedral PtCo nanocrystal as a highly atomically ordered core and an ultrathin PtIr atomic layer as a compressively strained shell. Owing to their geometric and core-shell features, the PtCo@PtIr nanoparticles deliver approximately six and eight times higher mass and specific activities, respectively, as an ORR catalyst than a commercial Pt/C catalyst. The half-wave potential of PtCo@PtIr exhibits a negligible decrease by 9 mV after 10 000 cycles, indicating extraordinary ORR durability because of the ordered arrangement of Pt and Co atoms. When evaluated using the ORR-OER dual reaction upon the introduction of Ir, PtCo@PtIr exhibits a small ORR-OER overpotential gap of 679 mV, demonstrating its great potential as a bifunctional electrocatalyst for fabricating fuel cells. The findings pave the way for designing precise intermetallic core-shell nanocrystals as highly functional catalysts.

Defect Electrocatalysts and Alkaline Electrolyte Membranes in Solid-State Zinc-Air Batteries: Recent Advances, Challenges, and Future Perspectives.

Rechargeable zinc-air batteries (ZABs) have attracted much attention due to their promising capability for offering high energy density while maintaining a long operational lifetime. One of the biggest challenges in developing all-solid-state ZABs is to design suitable bifunctional air-electrodes, which can efficiently catalyze the key oxygen reduction reaction (ORR)/oxygen evolution reaction (OER) electrochemical processes. The other one is to develop robust electrolyte membranes with high ionic conductivity and superb water retention capability. In this review, an in-depth discussion of the challenges, mechanisms, and design strategies for the defect electrocatalyst and the electrolyte membrane in all-solid-state ZABs will be offered. In particular, the crucial defect engineering strategies to tune the ORR/OER catalysts are summarized, including direct controllable strategies: 1) atomically dispersed metal sites control, 2) vacancy defects control, and 3) lattice-strain control, and the indirect strategies: 4) crystallographic structure control and 5) metal-carbon support interaction control. Moreover, the most recent progress in designing electrolyte membranes, including polyvinyl alcohol-based membranes and gel polymer electrolyte membranes, is presented. Finally, the perspectives are proposed for rational design and fabrication of the desired air electrode and electrolyte membrane to improve the performance and prolong the lifetime of all-solid-state ZABs.