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Hydrogenative coupling of CO2 to ethanol presents a sustainable pathway for carbon neutralization, yet the fundamental active sites and reaction pathway/mechanism remain unclear. Here, we investigate CO2 hydrogenative coupling over Cu/CeO2−x catalysts, achieving an optimal CO2 conversion of ~ 5% and ethanol selectivity of ~ 95% under 30 atm, H2/CO2 = 3, at 240 °C, and gas hourly space velocity (GHSV) = 120 mL·gcat−1·h−1. We revealed that both Cu(I) and oxygen vacancies (Ov) serve as active sites, with turnover frequencies (TOFs) of 0.23 h−1 per Ov site and 3.97 h−1 per Cu(I) site, respectively. We also concluded that neither Cu(I) nor Ov can function independently; both Cu(I) and Ov are required for CO2 activation and ethanol formation. Operando Fourier-transform infrared (FTIR) spectroscopy and density functional theory (DFT) calculations identify CH2OH* and CH2* as key intermediates in the C–C coupling step. These findings establish a mechanistic framework for CO2 hydrogenative coupling and provide valuable insights for designing more efficient catalysts for ethanol synthesis from CO2 conversion.
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