Local electronic modulation by single-atom Cu for CO₂ hydrogenation to light olefins

Despite significant progress in bifunctional catalysts for CO₂ hydrogenation, simultaneously achieving high CO₂ conversion and excellent light olefins selectivity remains challenging due to the unclear role of H₂ activation pathways. Herein, we establish a local electronic modulation strategy that enables precise control of H₂ activation by constructing isolated Cu–O–Zr interfacial sites within ZnZrO_x. The introduction of single-atom Cu serves as an atomic-level model to realize this modulation, where the Cu–O–Zr interface reduces the H₂ dissociation barrier to 0.85 eV and promotes methanol-mediated olefin formation while suppressing side reactions. When integrated with SAPO-34, the Cu single-atoms (SAs) doped ZnZrO_x catalyst achieves a 50 % increase in light olefins yield compared to its Cu-free counterpart, effectively overcoming the conventional activity–selectivity trade-off. Combined DFT and in situ spectroscopic analyses reveal that the moderate hydrogenation capability of Cu_SAs–H intermediates selectively channels reaction pathways toward olefins production, in sharp contrast to the overactive Cu–H species derived from metallic Cu⁰ nanoparticles (Cu NPs). This work establishes local electronic modulation as a powerful and generalizable strategy to tune hydrogen activation at the atomic level, offering mechanistic insights into selective CO₂ hydrogenation and beyond.