Selective conversion of syngas to value-added higher alcohols (containing two or more carbon atoms), particularly to a specific alcohol, is of great interest but remains challenging. Here we show that atomically intimate assembly of FeO_x-Rh-ZrO₂ dual interfaces by selectively architecting highly dispersed FeO_x on ultrafine raft-like Rh clusters supported on tetragonal zirconia enables highly efficient tandem conversion of syngas to ethanol. The ethanol selectivity in oxygenates reached ~90% at CO conversion up to 51%, along with a markedly high space-time yield of ethanol of 668.2 mg g_cat⁻¹ h⁻¹. In situ spectroscopic characterization and theoretical calculations reveal that Rh-ZrO₂ interface promotes dissociative CO activation into CH_x through a formate pathway, while the adjacent Rh-FeO_x interface accelerates subsequent C–C coupling via nondissociative CO insertion. Consequently, these dual interfaces in atomic-scale proximity with complementary functionalities synergistically boost the exclusive formation of ethanol with exceptional productivity in a tandem manner.

将合成气选择性转化为高附加值的高级醇（包含两个或多个碳原子），特别是转化为特定的醇，这非常有趣，但仍然具有挑战性。在这里，我们展示了 FeO _{x-Rh-ZrO 2} 双界面的原子紧密组装，方法是在四方氧化锆支撑的超细筏状 Rh 簇上选择性地构建高度分散的 FeO_x，从而实现合成气向乙醇的高效串联转化。在 CO 转化率高达 51% 时，含氧化合物中的乙醇选择性达到 ~90%，同时乙醇的时空产率达到 668.2 mg g ^{cat-1 h-1}。原位光谱表征和理论计算表明，Rh-ZrO₂ 界面通过甲酸盐途径促进解离 CO 活化到 CH_x，而相邻的 Rh-FeO_x 界面通过非解离 CO 插入加速随后的 C-C 耦合。因此，这些原子级接近的双界面具有互补功能，协同促进乙醇的独家形成，并以串联方式提供卓越的生产率。