Enhanced Activity of C2N-Supported Single Co Atom Catalyst by Single Atom Promoter
Enhanced Activity of C2N-Supported Single Co Atom Catalyst by Single Atom Promoter
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单原子促进剂增强 C2N 负载单钴原子催化剂的活性
DOI：
10.1021/acs.jpclett.9b02906
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发表时间：
2019
影响因子：
5.7
通讯作者：
Jiang Jun
中科院分区：
文献类型：
--
作者：
Zhong Wenhui;Zhang Guozhen;Zhang Yachao;Jia Chuanyi;Yang Tongtong;Ji Shentong;Prezhdo Oleg V.;Yuan Jianyong;Luo Yi;Jiang Jun
金属单原子催化剂（SAC）的显著化学活性在于其独特的电子状态与单原子位点的低配位性质有关。然而，电子态的操纵通常需要与其他原子直接接触，这不可避免地改变了低配位环境。在此，我们发现，通过第一性原理计算的活性的钴SAC HCOOH脱氢是明显增强通过电子状态操纵的非接触单原子促进剂。Co原子和Sn/Ge/Pb原子锚定在石墨C2 N单层的同一空腔中。令人惊讶的是，非键助催化剂通过C2 N载体的电荷重新分配使Co的两个远分裂自旋态几乎简并。此外，与Pt或Pd催化剂相比，高自旋Co提供了显著低的反应势垒。我们的研究结果表明，SAC的活性可以通过非接触式启动子进行调节，从而为类石墨烯支持的SAC的电子状态调节提供了新的见解。
The remarkable chemical activity of metal single-atom catalysts (SACs) lies in their unique electronic states associated with the low-coordination nature of single-atom sites. Yet, electronic state manipulation normally requires direct contact with other atoms, which inevitably changes the low-coordination environment. Herein, we found by first-principle calculations that the activity of a Co SAC for HCOOH dehydrogenation is appreciably enhanced via electronic state manipulation by a noncontact single atom promoter. A Co atom and a Sn/Ge/Pb atom are anchored in the same cavity of a graphitic C2N monolayer. Surprisingly, the nonbonded promoter makes two far splitting spin states of Co almost degenerate via charge redistribution of C2N support. Further, the high-spin Co gives a remarkably low reaction barrier comparable to Pt or Pd catalysts. Our results demonstrate that the activity of a SAC can be tuned via a noncontact promoter, casting new insights into electronic state modulation of SACs on graphene-like support.