Binary catalytic systems constructed by porphyrin cobalts(II) with confining nano-region and Zn(OAc)2 for oxygenation of cycloalkanes with O2 in relay mode

•A novel and effective relay oxygenation mode with confining regions was presented.•Relay oxygenation in binary system favored selective C-H bonds oxygenation with O2.•Disordered free radical diffusion was suppressed by confining catalytic regions.•Oxygenation intermediate R-OOH was used as additional oxidant to oxidize substrate.•Concurrently increased conversion and selectivity in C-H bonds oxygenation with O2.