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A highly selective and durable electrocatalyst for carbon dioxide (CO2) conversion to formate is developed, consisting of tin (Sn) nanosheets decorated with bismuth (Bi) nanoparticles. Owing to the formation of active sites through favorable orbital interactions at the Sn‐Bi interface, the Bi‐Sn bimetallic catalyst converts CO2 to formate with a remarkably high Faradaic efficiency (96%) and production rate (0.74 mmol h−1 cm−2) at −1.1 V versus reversible hydrogen electrode. Additionally, the catalyst maintains its initial efficiency over an unprecedented 100 h of operation. Density functional theory reveals that the addition of Bi nanoparticles upshifts the electron states of Sn away from the Fermi level, allowing the HCOO* intermediate to favorably adsorb onto the Bi‐Sn interface compared to a pure Sn surface. This effectively facilitates the flow of electrons to promote selective and durable conversion of CO2 to formate. This study provides sub‐atomic level insights and a general methodology for bimetallic catalyst developments and surface engineering for highly selective CO2 electroreduction.

A thin-film, flexible, and rechargeable zinc-air battery having high energy density is reported particularly for emerging portable and wearable electronic applications. This freeform battery design is the first demonstrated by sandwiching a porous-gelled polymer electrolyte with a freestanding zinc film and a bifunctional catalytic electrode film. The flexibility of both the electrode films and polymer electrolyte membrane gives great freedom in tailoring the battery geometry and performance.

Developing high-safety Li-metal anodes (LMAs) are extremely important for the application of high-energy Li-metal batteries. The recently state-of-the-art technologies, strategies and perspectives for developing LMAs are comprehensively summarized in this review.

Rational construction of atomic‐scale interfaces in multiphase nanocomposites is an intriguing and challenging approach to developing advanced catalysts for both oxygen reduction (ORR) and evolution reactions (OER). Herein, a hybrid of interpenetrating metallic Co and spinel Co3O4 “Janus” nanoparticles stitched in porous graphitized shells (Co/Co3O4@PGS) is synthesized via ionic exchange and redox between Co2+ and 2D metal–organic‐framework nanosheets. This strategy is proven to effectively establish highways for the transfer of electrons and reactants within the hybrid through interfacial engineering. Specifically, the phase interpenetration of mixed Co species and encapsulating porous graphitized shells provides an optimal charge/mass transport environment. Furthermore, the defect‐rich interfaces act as atomic‐traps to achieve exceptional adsorption capability for oxygen reactants. Finally, robust coupling between Co and N through intimate covalent bonds prohibits the detachment of nanoparticles. As a result, Co/Co3O4@PGS outperforms state‐of‐the‐art noble‐metal catalysts with a positive half‐wave potential of 0.89 V for ORR and a low potential of 1.58 V at 10 mA cm−2 for OER. In a practical demonstration, ultrastable cyclability with a record lifetime of over 800 h at 10 mA cm−2 is achieved by Zn–air batteries with Co/Co3O4@PGS within the rechargeable air electrode.

Transition metal atoms with corresponding nitrogen coordination are widely proposed as catalytic centers for the oxygen reduction reaction (ORR) in metal–nitrogen–carbon (M–N–C) catalysts. Here, an effective strategy that can tailor Fe–N–C catalysts to simultaneously enrich the number of active sites while boosting their intrinsic activity and utilization is reported. This is achieved by edge engineering of FeN4 sites via a simple ammonium chloride salt‐assisted approach, where a high fraction of FeN4 sites are preferentially generated and hosted in a graphene‐like porous scaffold. Theoretical calculations reveal that the FeN4 moieties with adjacent pore defects are likely to be more active than the nondefective configuration. Coupled with the facilitated accessibility of active sites, this prepared catalyst, when applied in a practical H2–air proton exchange membrane fuel cell, delivers a remarkable peak power density of 0.43 W cm−2, ranking it as one of the most active M–N–C catalysts reported to date. This work provides a new avenue for boosting ORR activity by edge manipulation of FeN4 sites.

Rechargeable zinc–air batteries (ZnABs) are attracting great interest due to their high theoretical specific energy, safety, and economic viability. However, their performance and large‐scale practical applications are largely limited by poor durability and high overpotential on the air‐cathode due to the slow kinetics of the oxygen reduction and evolution reactions (ORR/OER). Therefore, it is highly desired to exploit an ideal bifunctional catalyst to endow the obtained ZnABs with excellent ORR/OER catalytic performances. Herein, a new nonprecious‐metal bifunctional catalyst of urchin‐like NiCo2S4 microsphere synergized with sulfur‐doped graphene nanosheets (S‐GNS/NiCo2S4) is controllably designed and synthesized by simply tailoring the structure and electronic arrangement, which endow the as‐prepared catalyst with excellent electroactivity and long‐term durability toward ORR and OER. Importantly, ZnABs constructed by this outstanding catalyst exhibit high power density, small charge/discharge voltage gap, and excellent cycle stability, notably outperforming the more costly commercial Pt/C + Ir/C mixture catalyst. These excellent electrocatalytic performances together with the simplicity of the synthetic method, make the urchin‐like NiCo2S4 microsphere/S‐GNS hybrid nanostructure exhibit great promise as a superior air‐cathode catalyst for high‐performance rechargeable ZnABs.

Pt‐based electrocatalysts are considered as one of the most promising choices to facilitate the oxygen reduction reaction (ORR), and the key factor enabling their success is to reduce the required amount of platinum. Herein, we focus on illuminating both the theoretical mechanisms which enable enhanced and sustained ORR activity and the practical methods to achieve them in catalysts. The various multi‐step pathways of ORR are firstly reviewed and the rate‐determining steps based on the reaction intermediates and their binding energies are analyzed. We then explain the critical aspects of Pt‐based electrocatalysts to tune oxygen reduction properties from the viewpoints of active sites exposure and altering the surface electronic structure, and further summarize representative research progress towards practically achieving these activity enhancements with a focus on platinum size reduction, shape control and core Pt elimination methods. We finally outline the remaining challenges and provide our perspectives with regard to further enhancing their activities.