Molecular-Level Engineering of Organic-Modified Cu(100) for Tailored Selectivity in CO ₂ Electroreduction

Interfacial molecular engineering offers a powerful yet underexplored strategy to modulate the electronic structure and catalytic selectivity of metal-based electrocatalysts. Herein, first-principles calculations reveal how multifunctional organic modifiers, i.e., 2-aminoacetaldehyde and glycine, regulate the electronic properties of Cu(100) and steer reaction pathways during CO 2 electroreduction. Upon adsorption, these molecules form hydrogen bonds with CO 2 through −NH 2 or protonated −NH 3 + groups, stabilizing the adsorbed CO 2 intermediate, while simultaneously redistributing the electronic density of the Cu surface, thereby promoting electron transfer to CO 2 and enhancing its activation. The cooperative interaction between −NH 2 and auxiliary groups (−CHO or −COOH) establishes directional hydrogen bond that selectively stabilize key intermediates and lower the C–C coupling barriers. The 2-aminoacetaldehyde further facilitates synergistic dual-site coordination, strengthening interfacial coupling and shifting product selectivity from methane to methanol. Moreover, molecular modification steers distinct C–C coupling pathways: 2-aminoacetaldehyde favors *CHO–*CHO dimerization with ultralow barriers (0.08–0.15 eV), whereas protonated −NH 3 + in glycine promotes *CO–*CHO coupling. Concurrently, the competing hydrogen evolution reaction (HER) is effectively suppressed. Overall, this work establishes a unified mechanistic framework linking interfacial configuration to electronic modulation and catalytic selectivity, providing a rational strategy for designing molecularly engineered Cu-based CO 2 electroreduction catalysts.