Baskaran Sambath, Xu Cong-Qiao, Jiang Ya-Fei, Wang Yang-Gang, Li Jun
Department of Chemistry, Southern University of Science and Technology, Shenzhen, 518055, China.
Department of Chemistry and Key Laboratory of Organic Optoelectronics & Molecular Engineering of Ministry of Education, Tsinghua University, Beijing, 100084, China.
Chemphyschem. 2021 Feb 16;22(4):378-385. doi: 10.1002/cphc.202000950. Epub 2021 Jan 27.
Single-atom catalysts (SACs) have attracted extensive attention owing to their high catalytic activity. The development of efficient SACs is crucial for applications in heterogeneous catalysis. In this article, the geometric configuration, electronic structure, stabilitiy and catalytic performance of phosphorene (Pn) supported single metal atoms (M=Ru, Rh, Pd, Ir, Pt, and Au) have been systematically investigated using density functional theory calculations and ab initio molecular dynamics simulations. The single atoms are found to occupy the hollow site of phosphorene. Among the catalysts studied, Ru-decorated phosphorene is determined to be a potential catalyst by evaluating adsorption energies of gaseous molecules. Various mechanisms including the Eley-Rideal (ER), Langmuir-Hinshelwood (LH) and trimolecular Eley-Rideal (TER) mechanisms are considered to validate the most favourable reaction pathway. Our results reveal that Ru-Pn exhibits outstanding catalytic activity toward CO oxidation reaction via TER mechanism with the corresponding rate-determining energy barrier of 0.44 eV, making it a very promising SAC for CO oxidation under mild conditions. Overall, this work may provide a new avenue for the design and fabrication of two-dimensional materials supported SACs for low-temperature CO oxidation.
单原子催化剂（SACs）因其高催化活性而受到广泛关注。高效单原子催化剂的开发对于多相催化应用至关重要。在本文中，利用密度泛函理论计算和从头算分子动力学模拟，系统研究了磷烯（Pn）负载的单金属原子（M = Ru、Rh、Pd、Ir、Pt和Au）的几何构型、电子结构、稳定性和催化性能。发现单原子占据磷烯的中空位点。通过评估气态分子的吸附能，在所研究的催化剂中，Ru修饰的磷烯被确定为一种潜在的催化剂。考虑了包括埃里-里德（ER）、朗缪尔-欣谢尔伍德（LH）和三分子埃里-里德（TER）机制在内的各种机制，以验证最有利的反应途径。我们的结果表明，Ru-Pn通过TER机制对CO氧化反应表现出优异的催化活性，相应的速率决定能垒为0.44 eV，使其成为温和条件下CO氧化非常有前景的单原子催化剂。总体而言，这项工作可能为设计和制备用于低温CO氧化的二维材料负载单原子催化剂提供一条新途径。
