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Catalytic conversion of biomass-derived synthesis gas to ethanol and other C₂⁺ oxygenates has received considerable attention recently due to the strong demands for alternative, renewable energy sources. Combining experimental measurements with first-principles-based kinetic modeling, we investigated the reaction kinetics of ethanol synthesis from CO hydrogenation over SiO₂ -supported Rh/Mn alloy catalysts. We find that an Mn promoter can exist in a binary alloy with Rh and play a critical role in lowering the CO insertion reaction (CO+CH_x (x=1–3)) barriers thus improving the selectivity toward ethanol and other C₂⁺ oxygenates, although the barrier toward methane formation is unaffected. The postulation of supported Rh/Mn alloy nanoparticle being the active phase is supported by our experimental characterization using X-ray photoelectron spectroscopy, transmission electron microscopy, and X-ray …