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The advancement of cost-effective, high-performance catalysts for both electrochemical oxygen reduction reactions (ORRs) and oxygen evolution reactions (OERs) is crucial for the widespread implementation of metal–air batteries. In this research, we fabricated leaf-like N-doped carbon frames embedded with Co nanoparticles by pyrolyzing a ZIF-L/carbon nanofiber (ZIF-L/CNF) composite. Consequently, the optimized ZIF-L/CNF-700 catalyst exhibit exceptional catalytic activities in both ORRs and OERs, comparable to the benchmark 20 wt% Pt/C and RuO2. Addressing the issue of diminished cycle performance in the Zn–air battery cycle process, further detailed investigations into the post-electrolytic composition reveal that both the carbon framework and Co nanoparticles undergo partial oxidation during both OERs and ORRs. Owing to the varying local pH on the catalyst surface due to the consumption and generation of OH− by OERs and ORRs, after OERs, the product is reduced-size Co particles, while after ORRs, the product is outer-layer Co(OH)2-enveloping Co particles. [ABSTRACT FROM AUTHOR]

Electrochemical carbon dioxide reduction (eCO2R) in neutral electrolytes represents a viable solution for alleviating energy and carbon losses associated with carbonate formation, but limited by suboptimal C2+ selectivity and productivity owing to the higher C−C coupling kinetic barrier in such media. To address the issue, here Cu2O nanocubes are encapsulated within metalloporphyrin frameworks to create a benign microenvironment for C−C coupling, with the best catalyst of Cu2O@Cu−TCPP(Co) demonstrating a maximal C2H4 and C2+ FE of 54 ± 2% and 69 ± 4%, respectively, at 500 mA cm−2 in 1 M KCl. Comprehensive structural and spectrometric characterizations utilizing in situ attenuated total reflectance surface‐enhanced infrared absorption spectroscopy (ATR−SEIRAS), in situ X‐ray absorption spectroscopy (XAS), operando Raman, and high‐resolution transmission electron microscopy (HR−TEM) unveil that the high CO2 adsorption endowed by the metal‐organic framework (MOF) overlayer, high CO concentration yield by metalloporphyrins, high local pH rendered by spatial confinement, as well as the highly dispersed Cu crystallites exposing (200) facets synergistically contribute to the asymmetric C−C coupling of *CO and *COH intermediates in favor of C2+ production. Orchestrating the active moieties in a concerted fashion, this study offers a paradigm for the design of eCO2R catalysts in neutral electrolytes. [ABSTRACT FROM AUTHOR]

Electrocatalytic conversion of carbon dioxide into high‐value multicarbon (C2+) chemical feedstocks offers a promising avenue to liberate the chemical industry from fossil‐resource dependence and eventually close the anthropogenic carbon cycle but is severely impeded by the lack of high‐performance catalysts. To break the linear scaling relationship of intermediate binding and minimize the kinetic barrier of CO2 reduction reactions, ternary Cu–Au/Ag nanoframes were fabricated to decouple the functions of CO generation and C−C coupling, whereby the former is promoted by the alloyed Ag/Au substrate and the latter is facilitated by the highly strained and positively charged Cu domains. Thus, C2H4 production in an H‐cell and a flow cell occurred with high Faradic efficiencies of 69±5 and 77±2 %, respectively, as well as good electrocatalytic stability and material durability. In situ IR and DFT calculations unveiled two competing pathways for C2H4 generation, of which direct CO dimerization is energetically favored. [ABSTRACT FROM AUTHOR]