Visible-light-driven methane conversion with oxygen enabled by atomically precise nickel catalyst

Abstract

It remains an extreme challenge to activate thermodynamically unfavorable, chemically inert methane molecules under mild conditions. Herein, we report a molecular-like nickel-thiolate hexameric cluster [Ni6(PET)12; PET = SC2H4Ph] catalyst that resembles a double crown, comprising of a hexagonal Ni6 kernel encapsulated by an exterior shell of 12 thiolates capable of efficient conversion of methane plus O2 to methanol and formic acid under visible light irradiation. Exclusive photocatalysis by Ni6(PET)12 is related to its suitable molecular orbital gap, energy alignment, and the unique atomic-packing structure able to harvest solar energy to activate O2 with the subsequent accomplishment of H-atom abstraction from sluggish methane. This work is a major step toward promising practical applications of atomically precise metal catalysts in arduous bond cleavages and construction of low-carbon alkanes, with the potential to further facilitate fossil energy conversions.