单原子铂稳定在氮掺杂石墨烯上：一氧化碳氧化很容易通过三分子埃利-里德尔机理发生。

Single Pt atom stabilized on nitrogen doped graphene: CO oxidation readily occurs via the tri-molecular Eley-Rideal mechanism.

作者信息

Zhang Xilin, Lu Zhansheng, Xu Guoliang, Wang Tianxing, Ma Dongwei, Yang Zongxian, Yang Lin

机构信息

College of Physics and Electronic Engineering, Henan Normal University, Xinxiang, 453007, China.

出版信息

Phys Chem Chem Phys. 2015 Aug 14;17(30):20006-13. doi: 10.1039/c5cp01922b.

DOI:10.1039/c5cp01922b

PMID:26172523

Abstract

Single-atom catalysts, especially with single Pt atoms, have attracted more and more attention due to their high catalytic activity for CO oxidation. The outstanding stability and catalytic activity of a single Pt atom supported on nitrogen doped graphene (Pt/NG) are revealed using first-principles calculations. We find that the stability of a Pt atom on the NG can be promoted by picking an appropriate doping configuration. The exceptionally stable Pt/NG catalyst exhibits excellent catalytic activity for CO oxidation via a new tri-molecular Eley-Rideal mechanism (2CO + O2 → OCO-OCO → 2CO2) with an energy barrier of 0.16 eV for the rate-limiting step of OCO-OCO dissociation, which is more preferable than the other two normal Langmuir-Hinshelwood and Eley-Rideal mechanisms.

摘要

单原子催化剂，尤其是含单个铂原子的催化剂，因其对一氧化碳氧化具有高催化活性而受到越来越多的关注。通过第一性原理计算揭示了负载在氮掺杂石墨烯（Pt/NG）上的单个铂原子具有出色的稳定性和催化活性。我们发现，通过选择合适的掺杂构型可以提高铂原子在NG上的稳定性。这种异常稳定的Pt/NG催化剂通过一种新的三分子埃利-里德机理（2CO + O2 → OCO-OCO → 2CO2）对CO氧化表现出优异的催化活性，OCO-OCO解离的速率限制步骤的能垒为0.16 eV，这比另外两种常见的朗缪尔-欣谢尔伍德和埃利-里德机理更具优势。