Zhou Si, Pei Wei, Du Qiuying, Zhao Jijun
Key Laboratory of Materials Modification by Laser, Ion and Electron Beams (Dalian University of Technology), Ministry of Education, Dalian 116024, China.
Phys Chem Chem Phys. 2019 May 28;21(20):10587-10593. doi: 10.1039/c9cp01517e. Epub 2019 May 10.
Gold clusters are known for their unique catalytic properties, among which, endohedral gold clusters doped with heteroatoms have remarkable stabilities, with electronic structures tunable by both cluster size and doping element. Thus, it is intriguing and imperative to understand the principles for modulating the catalytic behaviors of these novel clusters. Here, we exploit experimentally produced M@Au (M = transition metal) cage clusters for catalysis of CO oxidation. The doping effects of 3d, 4d and 5d transition metals (V, Cr, Mn, Nb, Mo, Ta, W and Re) on the catalytic properties were systematically explored by first-principles calculations. Among the considered M@Au clusters, Cr@Au and Mn@Au provide a suitable binding strength with reaction intermediates and are highly active for CO oxidation with reaction barriers of 0.41 eV under the Langmuir-Hinshelwood mechanism. More importantly, we establish a distinct relationship between catalytic activity and the M-Au bond order and the d orbital center of the M@Au clusters, which would help tailor their catalytic performance with atomistic precision and enable utilization of these stable gold cages for catalysis of various chemical processes.
金团簇因其独特的催化性能而闻名，其中，掺杂杂原子的内包金团簇具有显著的稳定性，其电子结构可通过团簇尺寸和掺杂元素进行调节。因此，了解调控这些新型团簇催化行为的原理既有趣又势在必行。在此，我们利用实验制备的M@Au（M = 过渡金属）笼状团簇催化CO氧化反应。通过第一性原理计算系统地研究了3d、4d和5d过渡金属（V、Cr、Mn、Nb、Mo、Ta、W和Re）对催化性能的掺杂效应。在所考虑的M@Au团簇中，Cr@Au和Mn@Au与反应中间体具有合适的结合强度，并且在Langmuir-Hinshelwood机制下对CO氧化反应具有高活性，反应势垒为0.41 eV。更重要的是，我们建立了催化活性与M@Au团簇的M-Au键级和d轨道中心之间的明确关系，这将有助于以原子精度调整其催化性能，并使这些稳定的金笼能够用于催化各种化学过程。
