Selective Catalytic Production of Urea: Unravelling the Pairwise Competition on p‐d Alloy Catalysts

ABSTRACT Constructing asymmetric structures facilitates electrocatalytic urea synthesis by enabling targeted reactant activation. However, accurate mechanistic understanding is complicated by intricate pairwise competitions among initial adsorption, C‐N coupling, and parasitic hydrogenation. Herein, by decoding these competitive routes on indium‐based coinage metals (In ₄ M ₉ , M = Au, Ag, and Cu), we systematically uncover an intrinsic activity sequence of Ag > Cu > Au. To rationally evaluate these disparate pathways, we deduce two quantifiable stage‐specific descriptors: the Anchoring Affinity ( S _anchor ) for assessing robust reactant capture against proton attack, and the Coupling Propensity ( S _couple ) for evaluating C‐N combination likelihood over fatal hydrogenation. A desired catalytic zone is defined from seven alloy systems under the quantitative criteria of S _anchor < 0 and −0.3 < S _couple < −0.12. Strikingly, In ₄ Ag ₉ falls precisely into this desired zone, driving urea synthesis with a minimal limiting energy of only 0.31 eV. Electronic analyses reveal that In ₄ Ag ₉ affords an appropriate NO activation, maintaining an ideal thermodynamic balance between NO reduction and C‐N coupling. Ultimately, this work unravels the atomic‐level pairwise mechanisms and provides straightforward, quantifiable descriptors as a powerful compass to guide targeted catalyst design.