Cross‐Interface Quasi‐Tandem Catalysis Over Amorphous Oxide‐Metal Junctions Steers CO ₂ Electroreduction Toward C ₃ Products

ABSTRACT The selective electroreduction of CO 2 to n ‐propanol is fundamentally constrained by sluggish C 1 ─C 2 coupling and the instability of key oxygenated intermediates. Here, we propose a quasi‐tandem catalytic strategy enabled by defect‐rich amorphous ZrO 2 , where the amorphous oxide‐metal interfacial environment promotes *CO generation, stabilization of oxygenated C 2 intermediates (*OCCOH), and subsequent C─C coupling toward n ‐propanol formation. The resulting catalyst, composed of amorphous ZrO 2 , Cu, and Ag, delivers a Faradaic efficiency of 23.2% ± 1.6% and a partial current density of 50.6 mA cm −2 for n ‐propanol, representing more than 2.5‐ and 3.5‐fold enhancements, respectively, compared to its crystalline ZrO 2 analogue. Density functional theory (DFT) calculations reveal that the amorphous ZrO 2 ─Cu interface, not only enhances the formation of *COH, but also significantly lowers the energy barriers for *CO‐COH coupling and *CO‐*OCCOH coupling toward n ‐propanol generation. These findings establish amorphous oxide‐metal interfacial engineering as an effective strategy for quasi‐tandem catalysis, enabling cooperative multistep C─C coupling pathways toward selective C 3 electrosynthesis from CO 2 .