Wu, Bo; Lin, Tiejun; Lu, Zhengxing; Yu, Xing; Huang, Min; Yang, Ruoou; Wang, Caiqi; Tian, Chen; Li, Jiong; Sun, Yuhan; Zhong, Liangshu

CHEM

2022, 8, 2451-9294

Wu, Bo; Lin, Tiejun; Lu, Zhengxing; Yu, Xing; Huang, Min; Yang, Ruoou; Wang, Caiqi; Tian, Chen; Li, Jiong; Sun, Yuhan; Zhong, Liangshu

The direct conversion of methane to C-2 oxygenates with high selectivity under mild conditions has attracted wide attention but still remains a great challenge. Herein, we report the conversion of methane to acetic acid (CH3COOH) with ultrahigh selectivity for oxygenated products by the direct coupling of CH4, CO, and H2O2 over ZSM-5-supported Fe binuclear sites under 30 degrees C. The unexpected ultrahigh selectivity toward CH3COOH was attributed to the unique Fe binuclear site structure of [Fe(III)-(mu O)(2)-Fe(III)-(OH)(2)], which was evidenced by advanced spectroscopic techniques and density functional theory (DFT) calculations. It was suggested that the lower energy barriers for the direct coupling of methyl radicals (center dot CH3) and adsorbed CO* and OH* species to form CH3COOH, compared with the oxidation of CH4 by OH* to form CH3OH, benefited the CH3COOH formation.