Institute of Physics Rosario, IFIR, National Scientific and Technical Research Council, CONICET, and National University of Rosario, UNR, S2000EKF Rosario, Santa Fe, Argentina.
Institute of Catalysis and Petrochemistry, ICP, Spanish National Research Council, CSIC, 28049 Madrid, Spain.
J Chem Phys. 2023 Jul 21;159(3). doi: 10.1063/5.0153745.
The facet-dependent adsorption of CO on oxidized and reduced CeO2 single crystal surfaces is reviewed, with emphasis on the effect of CO coverage and the ability of state-of-the-art quantum-mechanical methods to provide reliable energies and an accurate description of the IR vibrational frequency of CO. Comparison with detailed, high-resolution experimental infrared reflection absorption spectroscopy data obtained for single crystal samples allows the assignment of the different CO vibrational bands observed on all three low-index ceria surfaces. Good agreement is achieved with the hybrid density functional theory approach with the HSE06 functional and with saturation coverage. It is shown that CO is very sensitive to the structure of cerium oxide surfaces and to the presence of oxygen vacancies. The combined theoretical-experimental approach offers new opportunities for a better characterization of ceria nanoparticles and for unraveling changes occurring during reactions involving CO at higher pressures.
氧化还原 CeO2 单晶表面 CO 的面依赖性吸附综述，重点介绍 CO 覆盖度的影响以及最先进的量子力学方法提供可靠能量和 CO 红外振动频率精确描述的能力。与针对单晶样品获得的详细、高分辨率实验红外反射吸收光谱数据进行比较，允许对在所有三种低指数氧化铈表面上观察到的不同 CO 振动带进行分配。与具有 HSE06 函数和饱和覆盖度的杂化密度泛函理论方法达成了很好的一致性。结果表明，CO 对氧化铈表面的结构和氧空位的存在非常敏感。理论与实验相结合的方法为更好地表征氧化铈纳米粒子以及在涉及更高压力下 CO 的反应中发生的变化提供了新的机会。
