Reaction Network of CO₂ Hydrogenation into C1-2 Oxygenates and Its BEP Relationships

Despite many efforts to steer CO₂ hydrogenation for the synthesis of valuable chemicals, its mechanistic intricacies remain poorly understood, complicating industrial applications. In this work, we apply a novel ansatz to construct simplified catalytic reaction networks of CO₂ hydrogenation on Cu and Pd and account for the realistic active sites on catalyst nanoparticles. Moreover, we present Brønsted-Evans-Polanyi relationships tailored to transition state characteristics, enabling further machine learning-driven exploration of CO₂ hydrogenation on transition metal-based catalysts and deepening our understanding of the underlying reaction mechanism. By assessing the kinetic viability of various reaction pathways, we highlight the outstanding properties of Cu in the catalysis of various hydrogenation and C–C coupling steps in the CO₂ hydrogenation network. Our theoretical framework addresses the intrinsic complexities of CO₂ hydrogenation, advancing our understanding of its mechanism and guiding rational catalyst design studies.