Atomic-Scale Asymmetric Rh–Mo Site for CO ₂ Hydrogenation to Methanol at Near-Ambient Temperature

CO₂ hydrogenation to methanol offers a promising route for greenhouse gas mitigation and sustainable nonpetroleum carbon utilization. Rhodium (Rh), known for its high surface energy, excels in CO₂ activation. However, its strong reducibility often leads to deep hydrogenation of CO₂ to CH₄, rather than stabilizing key C-O intermediates. Herein, we report a catalyst comprising Rh atoms embedded in a MoC lattice, constructed through an ultralow Rh loading that regulates matrix phase formation. This design results in atomic-scale asymmetric Rh-Mo coordination environments, which enhance CO₂ molecular bending and facilitate C=O bond cleavage. Electron transfer modulation from neighboring Mo atoms stabilizes Rh in the Rhδ+ state, thereby improving the adsorption of C-O intermediates and promoting methanol formation. Notably, the catalyst delivers exceptional methanol selectivity of up to 95% at 110 °C, along with long-term operational stability. A high methanol formation rate of 1,287 μmol gRh⁻¹ s⁻¹ is also attained, highlighting the superior atomic utilization of Rh. This work presents an atomic-level design strategy for tailoring local coordination and electronic structure, driving efficient CO₂ hydrogenation under mild conditions.