Atomic-layer-deposited ZnO tailors Niδ⁻–ZnOδ⁺ interfaces to switch CO2 hydrogenation selectivity from CH4 to CO

Regulating product selectivity in CO 2 thermocatalytic hydrogenation remains challenging, particularly for shifting inherent preferences toward C 1 products. Here, we demonstrate that atomic layer deposition (ALD) of ZnO on nickel vanadate precursor (NiVO) enables a dramatic shift from methane (CH 4 ) to carbon monoxide (CO). The optimized NiVO-10ZnO-R400 (10 ALD cycles) achieves 88.1 % CO selectivity at 350°C and 0.1 MPa, surging from 1.3 % over unmodified NiVO-R400. Crucially, ALD-engineered Ni-ZnO interfaces exhibit superior CO production and stability (>200 h) compared to impregnation-synthesized counterparts, attributed to sufficient Ni-ZnO contact. Multimodal characterization and theoretical calculations reveal that ZnO-to-Ni electron transfer generates an electron-rich Ni surface, weakening CO 2 /CO adsorption and lowering surface H concentration. This suppresses the CO→CH 4 step in the CO 2 hydrogenation pathway (CO 2 →CO→CH 4 ), thereby redirecting product selectivity toward CO rather than CH 4 . Our work provides a precise interface-engineering strategy to manipulate reaction pathways for CO 2 utilization.