Hierarchical CuS@ZnIn 2 S 4 Hollow Double-Shelled p-n Heterojunction Octahedra Decorated with Fullerene C 60 for Remarkable Selectivity and Activity of CO 2 Photoreduction into CH 4 .

In this work, a hollow double-shelled architecture, based on n-type ZnIn 2 S 4 nanosheet-coated p-type CuS hollow octahedra (CuS@ZnIn 2 S 4 HDSOs), is designed and fabricated as a p-n heterojunction photocatalyst for selective CO 2 photoreduction into CH 4 . The resulting hybrids provide rich active sites and effective charge migration/separation to drive CO 2 photoreduction, and meanwhile, CO detachment is delayed to increase the possibility of eight-electron reactions for CH 4 production. As expected, the optimized CuS@ZnIn 2 S 4 HDSOs manifest a CH 4 yield of 28.0 μmol g -1 h -1 and a boosted CH 4 selectivity up to 94.5%. The decorated C 60 both possesses high electron affinity and improves catalyst stability and CO 2 adsorption ability. Thus, the C 60 -decorated CuS@ZnIn 2 S 4 HDSOs exhibit the highest CH 4 evolution rate of 43.6 μmol g -1 h -1 and 96.5% selectivity. This work provides a rational strategy for designing and fabricating efficient heteroarchitectures for CO 2 photoreduction.