Engineering ORR Electrocatalysts from Co8Pt4 Carbonyl Clusters via ZIF‐8 Templating

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 (R) 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 cm(ECSA)(-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.