Lin I-Hsiang, Lu Yu-Huan, Chen Hsin-Tsung
Department of Chemistry, Chung Yuan Christian University, Chungli District, Taoyuan City, 32023, Taiwan.
J Comput Chem. 2017 Sep 5;38(23):2041-2046. doi: 10.1002/jcc.24851. Epub 2017 Jul 4.
The O activation and CO oxidation on nitrogen-doped C N fullerene are investigated using first-principles calculations. The calculations indicate that the C N fullerene is able to activate O molecules resulting in the formation of superoxide species ( O2-) both kinetically and thermodynamically. The active superoxide can further react with CO to form CO via the Eley-Rideal mechanism by passing a stepwise reaction barrier of only 0.20 eV. Ab initio molecular dynamics (AIMD) simulation is carried out to evidence the feasibility of the Eley-Rideal mechanism. In addition, the second CO oxidation takes place with the remaining atomic O without any activation energy barrier. The full catalytic reaction cycles can occur energetically favorable and suggest a two-step Eley-Rideal mechanism for CO oxidation with O catalyzed by the C N fullerene. The catalytic properties of high percentage nitrogen-doped fullerene (C N ) is also examined. This work contributes to designing higher effective carbon-based materials catalysts by a dependable theoretical insight into the catalytic properties of the nitrogen-doped fullerene. © 2017 Wiley Periodicals, Inc.
采用第一性原理计算方法研究了氮掺杂C₅₉N富勒烯上的O活化和CO氧化反应。计算结果表明，C₅₉N富勒烯能够在动力学和热力学上活化O分子，从而形成超氧物种（O₂⁻）。活性超氧物种可以通过仅0.20 eV的逐步反应势垒，进一步与CO通过Eley-Rideal机制反应生成CO₂。进行了从头算分子动力学（AIMD）模拟，以证明Eley-Rideal机制的可行性。此外，第二次CO氧化反应是与剩余的原子O发生的，没有任何活化能垒。整个催化反应循环在能量上是有利的，表明C₅₉N富勒烯催化O氧化CO的两步Eley-Rideal机制。还研究了高百分比氮掺杂富勒烯（C₅₉N）的催化性能。这项工作通过对氮掺杂富勒烯催化性能的可靠理论洞察，为设计更高效率的碳基材料催化剂做出了贡献。© 2017威利期刊公司。
