@article{Herrero2025, 
author = {Joaquin Herrero and Peilei He and Fan Yang and Jiaping Weng and Nicole J. LiBretto and Daniela S. Mainardi and Jeffrey T. Miller and Yue Wu and Yang Xiao},
title = {Synergy of Cu(I) and oxygen vacancies in CO2 hydrogenative coupling to ethanol on Cu/CeO2−x catalysts},
year = {2025},
journal = {Nano Research},
volume = {18},
number = {8},
pages = {94907518},
keywords = {oxygen vacancy, synergistic effect, CO2 hydrogenation, CO2 to ethanol, Cu/CeO2 catalysts},
url = {https://www.sciopen.com/article/10.26599/NR.2025.94907518},
doi = {10.26599/NR.2025.94907518},
abstract = {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.}
}