The synthesis of ethanol (EtOH) via hydrogenation of dimethyl oxalate (DMO) from syngas has gained wide attention, but its practical application is still limited by the poor selectivity on conventional Cu-based catalysts. This work developed an efficient Fe2C catalyst confined in the ordered mesoporous carbon (Fe/CMK-3) for the hydrogenation of DMO to EtOH. The formation of epsilon-carbide phase was favored by moderate carbonization process via stepwise methanol dissociation in a confined redox microenvironment. The lower energy barriers of the epsilon-carbide phase for C═O activation enhanced the intrinsic activity of Fe/CMK-3 in the deep hydrogenation of MA to EtOH, which was the rate-determining step of DMO hydrogenation. In addition, the confined effect of ordered mesoporous carbon allowed a high dispersion of the iron carbonates, which further boosted the EtOH production. On this catalyst, a high EtOH yield of 97.6%, an unprecedent space time yield of 1004 gEtOH kgcat–1 h–1, and a durability of 120 h were successfully achieved, which could provide an alternative route for the industrial production of ethanol from syngas conversion.
