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Abstract To reduce the costs of proton exchange membrane fuel cells, the amount of Pt necessary to drive efficient oxygen reduction reaction (ORR) should be minimized. Particle nanostructuring, (nano‐)alloying, and metal‐doping can yield higher activities per Pt mass through tailoring catalysts owning a high number of active sites and precise electronic properties. In this work, the atom‐precise [NBnMe3]2[Co8Pt4C2(CO)24] (Co8Pt4) cluster is encapsulated and activated in a zeolitic imidazolate framework (ZIF)‐8, which unlocks the access to defined, bare Pt−Co nanoclusters, Co8±xPt4±yNC@ZIF‐8, for the fabrication of highly active ORR catalysts. Upon controlled C‐interfacing and ZIF‐8‐digestion, Co‐doped Pt NPs (Pt27Co1) with a homogenous and narrow size distribution of (1.1±0.4) nm are produced on Vulcan® carbon. Restructuring of the Pt27Co1/C catalyst throughout the ORR measurement was monitored via high‐angle annular dark field‐scanning transmission electron microscopy and X‐ray photoelectron spectroscopy. The measured ORR mass activity of (0.42±0.07) A mgPt−1 and the specific activity of (0.67±0.06) mA cmECSA−2 compare favourably with the catalyst obtained by direct C‐interfacing the pristine Co8Pt4 cluster and with state‐of‐the‐art Pt/C reference catalysts. Our results demonstrate the potential of ZIF‐8‐mediated Pt−Co NP synthesis toward devising ORR catalysts with high Pt‐mass activity.

Abstract Graphite electrodes are widely used in commercial metal‐ion batteries as anodes. Electrochemical impedance spectroscopy serves as one of the primary non‐destructive techniques to obtain key information about various batteries during their operation. However, interpretation of the impedance response of graphite electrodes in contact with common organic electrolytes can be complicated. It is especially challenging, particularly when utilizing the 2‐electrode configuration that is common in battery research. In this work, we elaborate on a physical impedance model capable of accurately describing the impedance spectra of a graphite|electrolyte|metallic Li system in a coin‐cell assembly during two initial charge/discharge cycles. We analyze the dependencies of the model parameters for graphite and metallic lithium as a function of the state of charge to verify the model. Additionally, we suggest that the double layer capacitance values obtained during specific intercalation stages could help to determine if the area‐normalized values align with the expected range. The data and the procedure necessary for calibration are provided.