CO₂ conversion reactions, including hydrogenation to C₁ chemicals and CO₂ reforming of CH₄ (dry reforming), have attracted significant attention due to rising global energy demand and climate change concerns. Continuous advances in heterogeneous catalysis show that CO₂ hydrogenation over monometallic catalysts is strongly structure-sensitive; however, establishing clear structure–performance relationships in bimetallic systems remains challenging because their architectures and mechanisms are inherently more complex. Here, we construct TiO₂-supported Ni–Ru bimetallic catalysts with precisely controlled alloyed and non-alloyed configurations, confirmed by advanced microscopy characterizations. In situ experiments reveal that Ni–Ru interfaces act as an “H-atom valve,” regulating H₂ spillover and enabling complete switching of CO₂ hydrogenation selectivity during reaction. Extending this concept to CO₂ reforming of CH₄, where Ni catalysts commonly suffer from rapid CO₂ dissociation to CO followed by CO disproportionation that forms Ni–C species and initiates coke deposition, we demonstrate that rationally designed Ni–Cu bimetallic catalysts suppress this pathway and mitigate deactivation. Together, these results provide fundamental insights into bimetallic nano-catalysis and establish structure-controlled hydrogen and carbon management as a general strategy for tuning activity, selectivity, and stability across key carbon-conversion processes.
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