Abstract
The efficient conversion of methane to valuable C(2) liquid oxygenates still remains silent. Here we show a new catalytic system of C-C coupling towards the C(2) liquid oxygenates with high selectivity and productivity by the selective anchoring zero-valent ruthenium atoms from individual ones to two and three atoms in the electron-rich 18-carbon cavity of graphdiyne. Theoretical calculations demonstrate that Ru(3)-GDY supplies neighboring robust active sites to promote efficient C-C coupling to C(2) liquid oxygenates, due to the p-d coupling resonance that guarantees the distributed charge among Ru(3) sites resulting in active region to accelerate the methane oxidation. Our results show Ru atoms in GDY enable the highly efficient and selective activation of CH(4) to the key ·CH(3) and ·CH(2)OH intermediates, which allows the selective C-C coupling to gain C(2) liquid oxygenates and shows the high selectivity (67%) and yields (7.25 mmol g(cat)(-1) h(-1)) towards C(2) liquid oxygenates.