Selective Synthesis of N,N‐Dimethylformamide From CO ₂ Hydrogenation Coupled With Dimethylamine Over a ZnZrO _x Solid‐Solution Catalyst

ABSTRACT N,N‐Dimethylformamide (DMF) is a widely used solvent and versatile organic building block. To reduce carbon emissions and mitigate safety risks in its manufacture, new synthetic strategies are urgently needed. Here, we report a ZnZrO x solid‐solution catalyst that enables the direct synthesis of DMF from CO 2 , H 2 , and dimethylamine (DMA) in a fixed‐bed reactor. Under an optimized gas‐liquid velocity ratio, the catalyst delivers 99% DMF selectivity at 14% single‐pass DMA conversion and exhibits excellent durability, with no measurable deactivation over 1000 h on stream. Mechanistic analysis reveals a synergistic interplay between Zn and Zr sites that promotes the formation of reactive formate intermediates, which couple with DMA to form DMF, while kinetically hindering further hydrogenation of formate to CH 2 O* species. This pathway ensures high DMF selectivity and suppresses trimethylamine (TMA) formation from DMA and CH 2 O*. This dual‐metal‐oxide solid‐solution platform provides a general route to couple CO 2 hydrogenation with amines to access formamides.