Atomic-Scale Asymmetric Rh-Mo Site for CO2 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.