Effect of spin contamination error on surface catalytic reaction: NO reduction by core-shell catalysts
Effect of spin contamination error on surface catalytic reaction: NO reduction by core-shell catalysts
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DOI：
10.1080/00268976.2018.1522457
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发表时间：
2018-09
影响因子：
1.7
通讯作者：
K. Tada;H. Koga;Yoshinori Ato;Akihide Hayashi;M. Okumura;Shingo Tanaka
中科院分区：
文献类型：
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作者：
K. Tada;H. Koga;Yoshinori Ato;Akihide Hayashi;M. Okumura;Shingo Tanaka
摘要采用近似自旋投影方法和平面波基组的非限制密度泛函理论计算，研究了自旋污染误差对TiO 2/Ag和ZrO 2/Cu核壳催化剂模型催化还原NO活化能垒的影响。的TiO 2/Ag系统的估计的势垒增加（0.03 eV），而ZrO 2/Cu系统的自旋污染误差的校正后下降（0.04 eV）。这两个系统的估计障碍的差异可以归因于它们的表面结构的差异。在TiO 2/Ag体系中得到的误差大于气相中得到的误差，即自旋污染误差是由分子/表面相互作用引起的。误差修正也改变了ZrO 2/Cu的速率控制步骤。这些结果表明，自旋污染误差的校正对于催化反应的详细研究的重要性。图形摘要
ABSTRACT The effects of spin contamination errors on the activation barriers of catalytic NO reduction by TiO2/Ag and ZrO2/Cu core-shell catalyst models were investigated using an approximate spin projection method and an unrestricted density functional theory calculation with the plane-wave basis set. The estimated barrier of the TiO2/Ag system increased (0.03 eV), whereas that of the ZrO2/Cu system decreased (0.04 eV) after the correction of the spin contamination error. This difference in the estimated barriers of the two systems can be attributed to the difference in their surface structures. The error obtained for the TiO2/Ag system was larger than that obtained for the gas phase, i.e. the spin contamination error was induced by the molecule/surface interaction. Moreover, the error correction also changed the rate-determining step of ZrO2/Cu. These results demonstrate the importance of the correction of spin contamination errors for the detailed investigation of catalytic reactions. GRAPHICAL ABSTRACT