Jie Ding , Zhenyuan Teng , Xiaozhi Su , Kosaku Kato , Yuhang Liu , Ting Xiao , Wei Liu , Lingyue Liu , Qiao Zhang , Xinyi Ren , Jincheng Zhang , Zhaoyang Chen , Ohno Teruhisa , Akira Yamakata , Hongbin Yang , Yanqiang Huang , Bin Liu , Yueming Zhai.Chem.（翟月明、刘彬、杨鸿斌）

Abstract：

        By breaking structural symmetry of the single atomic active site, the photocatalytic water oxidation pathway is tuned for highly selective oxidation of CH4to CH3OH in an aqueous solution. The water oxidation ability and its influence on photocatalytic oxidation of CH4over symmetrically coordinated cobalt single atom (Co-4N) on carbon nitride (SC-Co1/PCN) and asymmetrically coordinated cobalt single atom (Co-C2N2) on carbon nitride (AC-Co1/PCNKOH) photocatalysts are systematically investigated. A super selectivity of 87.22% for photocatalytic oxidation of CH4to CH3OH is realized on AC-Co1/PCNKOH, which is only 45% on SC-Co1/PCN. Moreover, a CH4conversion of 2.42% and a CH3OH yield of 2.11% are achieved over AC-Co1/PCNKOH(200 mg). Combining multiplein-situcharacterizations and time-dependent density functional theory calculations, it is revealed that AC-Co1/PCNKOHpossesses a desired electronic configuration for single-electron transfer water oxidation reaction during photocatalysis, leading to a notably promoted selectivity for CH4oxidation to CH3OH under illumination.

        论文链接：https://www.sciencedirect.com/science/article/pii/S2451929423000815