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Reaction mechanisms for CO catalytic oxidation on monodisperse Mo atom-embedded graphene

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Abstract

The geometric stability, electronic structure and catalytic activity of the Mo-embedded graphene (Mo/SV-graphene) are investigated by using the first-principle calculations. Compared with a Mo atom on pristine graphene, the Mo dopant in defective graphene exhibits more positively charged, which helps to weaken the CO adsorption and facilitates the O2 adsorption. Besides, the two mechanisms (Langmuir–Hinshelwood, LH and Eley–Rideal, ER) for the sequential CO oxidation reactions are investigated comparison. Among the reaction processes, the coadsorption of O2 and CO exists at the Mo/SV-graphene surface, the first step (CO + O2 → OOCO) with energy barrier is 0.60 eV and then form a CO2 molecule through the reaction (OOCO → CO2 + Oads) without any energy barrier, and thus the formation of OOCO complex is viewed as rate-controlling step. In the ER reaction, although the CO molecule reacts with the preadsorbed O2 by the low-energy barrier (CO + O2 → CO3, 0.13 eV), the formation of CO3 is more stable than the generating CO2 and Oads (0.84 eV). Hence, the LH mechanism as the starting step is energetically more favorable. The results provide the valuable guidance to fabricate graphene-based catalysis and validate the reactivity of atomic-scale catalyst.

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Acknowledgments

This work was supported by the National Natural Science Foundation of China (Grant Nos. U1404109 51401078 and 11247012), and the Science Fund of Educational Department of Henan Province (Grant Nos. 14B140019, 14A140015 and 14A140010).

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Authors and Affiliations

  1. College of Physics and Electronic Engineering, Zhengzhou Normal University, Zhengzhou, 450044, Henan, People’s Republic of China

    Yanan Tang, Lijun Pan, Weiguang Chen, Chenggang Li, Zigang Shen & Xianqi Dai

  2. Quantum Materials Research Center, Zhengzhou Normal University, Zhengzhou, 450044, Henan, People’s Republic of China

    Yanan Tang, Lijun Pan, Weiguang Chen, Chenggang Li, Zigang Shen & Xianqi Dai

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  1. Yanan Tang
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  2. Lijun Pan
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Correspondence to Yanan Tang or Xianqi Dai.

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Tang, Y., Pan, L., Chen, W. et al. Reaction mechanisms for CO catalytic oxidation on monodisperse Mo atom-embedded graphene. Appl. Phys. A 119, 475–485 (2015). https://doi.org/10.1007/s00339-015-9093-4

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