Abstract Ceria has been shown to catalyze the dephosphorylation of phosphate monoesters at ambient temperature. As a step toward understanding the reaction mechanism on ceria, first-principles density functional theory calculations in the GGA-PW91+U approach have been carried out to study the adsorption of phosphoric acid and two model phosphate monoesters, methyl phosphate and para-nitrophenyl phosphate, on CeO2(111). General patterns are found in terms of energetic, structural, electronic, and vibrational properties upon adsorption. For the parent molecules, bonding of the phosphorous atom directly to a surface lattice oxygen atom (Olatt) is the only stable molecular adsorption state. Common entities that reduce Ce4+ to Ce3+ (e.g., co-adsorbed H atom, surface and subsurface oxygen vacancy) mildly perturb the P-Olatt bonding, but Ce3+ by itself has only a negligible effect. Deprotonation is exothermic for all three phosphate species on CeO2(111), much more so if they are adsorbed in an oxygen vacancy via a phosphoryl O than on a stoichiometric surface. Infrared spectra have been simulated for the adsorbed states of the model phosphates for comparison with future experiments.

中文翻译：

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磷酸和模型磷酸单酯在 CeO2(111) 上吸附的理论分析

摘要 氧化铈已被证明可在环境温度下催化磷酸单酯的去磷酸化。作为了解二氧化铈反应机理的一步，在 GGA-PW91+U 方法中进行了第一性原理密度泛函理论计算，以研究磷酸和两种模型磷酸单酯，磷酸甲酯和对硝基苯基磷酸酯的吸附, 在 CeO2(111) 上。在吸附时的能量、结构、电子和振动特性方面发现了一般模式。对于母体分子，磷原子直接与表面晶格氧原子（Olatt）键合是唯一稳定的分子吸附状态。将 Ce4+ 还原为 Ce3+ 的常见实体（例如，共吸附的 H 原子、表面和亚表面氧空位）会轻微扰乱 P-Olatt 键合，但 Ce3+ 本身的影响微乎其微。CeO2(111) 上的所有三种磷酸盐物质的去质子化都是放热的，如果它们通过磷酰基 O 吸附在氧空位中而不是化学计量表面上，则放热更多。红外光谱已经模拟了模型磷酸盐的吸附状态，以便与未来的实验进行比较。