First-Principle Investigations of the Interaction between CO and O2 with Group 11 Atoms on a Defect-Free MgO(001) Surface.
First-Principle Investigations of the Interaction between CO and O2 with Group 11 Atoms on a Defect-Free MgO(001) Surface.
复制标题
DOI：
10.1021/acs.jpca.8b00647
复制
发表时间：
2018-02
期刊：
影响因子：
--
通讯作者：
K. Töpfer;J. Tremblay
中科院分区：
文献类型：
--
作者：
K. Töpfer;J. Tremblay
在这一贡献中，我们用周期点电荷嵌入的密度泛函理论研究了CO和O2与沉积在无缺陷氧化镁表面上的第11族金属原子的相互作用。我们首次从单原子催化的角度对CO和O2在金属氧化物表面沉积的金属原子上的吸附和共吸附进行了横向研究。各种分析工具揭示了金属原子与衬底的结合情况，以及两个分子在不同金属中心的情况。我们的分析表明，协同电子效应增强了CO在三个金属中心与O2共吸附时的稳定性。我们的结果还解释了热条件下11族金属原子对CO氧化缺乏催化活性，这是OC-O2键活化和表面扩散的竞争，导致金属原子聚集。此外，研究还表明，CO和O2在Au/Mg(001)上的共吸附为单原子光催化奠定了基础。
In this contribution, we investigate the interaction between CO and O2 with metal atoms of group 11 deposited on a defect-free magnesium oxide surface using density functional theory with periodic point charge embedding. We present the first transversal study of the adsorption and coadsorption of CO and O2 on coinage metal adatoms deposited on metal oxide surfaces from the perspective of single-atom catalysis. Various analysis tools shed light on the binding situation of the metal atoms to the substrate as well as on the situation of the two molecules on the different metal centers. Our analysis demonstrates that cooperative electronic effects enhance the stability of CO upon coadsorption with O2 for all three metal centers. Our results also explain the lack of catalytic activity of group 11 metal atoms with respect to CO oxidation under thermal conditions as a competition between OC-O2 bond activation and surface diffusion, leading to metal atom agglomeration. Additionally, it is shown how coadsorption of CO and O2 on Au/Mg(001) could pave the way to single-atom photocatalysis.