A "MOFs plus ZIFs" Strategy toward Ultrafine Co Nanodots Confined into Superficial N-Doped Carbon Nanowires for Efficient Oxygen Reduction.

N-doped carbon-confined transition metal nanocatalysts display efficient oxygen reduction reaction (ORR) performance comparable to commercial Pt/C electrocatalysts because of their efficient charge transfer from metal atoms to active N sites. However, the sheathed active sites inside the electrocatalysts and relatively large-size confined metal particles greatly restrict their activity improvement. Here, we develop a facile and efficient "MOFs plus ZIFs" synthesis strategy to successfully construct ultrafine sub-5 nm Co nanodots confined into superficial N-doped carbon nanowires (Co@C@NC) via a well-designed synthesis process. The unique synthesis mechanism is based on low-pressure vapor superassembly of thin zeolitic imidazolate framework (ZIF) coatings on metal-organic framework substrates. During the successive pyrolysis, the preferential formation of the robust N-doped carbon shell from the ZIF-67 shell keeps the core morphology without shrinkage and limits the growth of Co nanodots. Benefiting from this architecture with accessible and rich active N sites on the surface, stable carbon confined architecture, and large surface area, the Co@C@NC exhibits excellent ORR performance, catching up to commercial Pt/C. Density functional theory demonstrates that the confined Co nanodots efficiently enhance the charge density of superficial active N sites by interfacial charge transfer, thus accelerating the ORR process.