SCI和EI收录∣中国化工学会会刊

中国化学工程学报 ›› 2021, Vol. 37 ›› Issue (9): 175-183.DOI: 10.1016/j.cjche.2021.02.006

• Resources and Environmental Technology • 上一篇    下一篇

Theoretical study of reduction mechanism of Fe2O3 by H2 during chemical looping combustion

Feng Liu, Jing Liu, Yu Li, Ruixue Fang   

  1. State Key Laboratory of Coal Combustion, School of Energy and Power Engineering, Huazhong University of Science and Technology, Wuhan 430074, China
  • 收稿日期:2020-08-31 修回日期:2021-02-03 出版日期:2021-09-28 发布日期:2021-11-02
  • 通讯作者: Jing Liu
  • 基金资助:
    This work was supported by National Natural Science Foundation of China (51976071) and Fundamental Research Funds for the Central Universities (2019kfyRCPY021).

Theoretical study of reduction mechanism of Fe2O3 by H2 during chemical looping combustion

Feng Liu, Jing Liu, Yu Li, Ruixue Fang   

  1. State Key Laboratory of Coal Combustion, School of Energy and Power Engineering, Huazhong University of Science and Technology, Wuhan 430074, China
  • Received:2020-08-31 Revised:2021-02-03 Online:2021-09-28 Published:2021-11-02
  • Contact: Jing Liu
  • Supported by:
    This work was supported by National Natural Science Foundation of China (51976071) and Fundamental Research Funds for the Central Universities (2019kfyRCPY021).

摘要: An atomic-level insight into the H2 adsorption and oxidation on the Fe2O3 surface during chemical-looping combustion was provided on the basis of density functional theory calculations in this study. The results indicated that H2 molecule most likely chemisorbs on the Fe2O3 surface in a dissociative mode. The decomposed H atoms then could adsorb on the Fe and O atoms or on the two neighboring O atoms of the surface. In particular, the H2 molecule adsorbed on an O top site could directly form H2O precursor on the O3-terminated surface. Further, the newly formed H-O bond was activated, and the H atom could migrate from one O site to another, consequently forming the H2O precursor. In the H2 oxidation process, the decomposition of H2 molecule was the rate-determining step for the O3-terminated surface with an activation energy of 1.53 eV. However, the formation of H2O was the rate-determining step for the Fe-terminated surface with an activation energy of 1.64 eV. The Fe-terminated surface is less energetically favorable for H2 oxidation than that the O3-terminated surface owing to the steric hindrance of Fe atom. These results provide a fundamental understanding about the reaction mechanism of Fe2O3 with H2, which is helpful for the rational design of Fe-based oxygen carrier and the usage of green energy resource such as H2.

关键词: Chemical-looping combustion, Fe2O3 oxygen carrier, H2 adsorption, Density functional theory, Reaction mechanism

Abstract: An atomic-level insight into the H2 adsorption and oxidation on the Fe2O3 surface during chemical-looping combustion was provided on the basis of density functional theory calculations in this study. The results indicated that H2 molecule most likely chemisorbs on the Fe2O3 surface in a dissociative mode. The decomposed H atoms then could adsorb on the Fe and O atoms or on the two neighboring O atoms of the surface. In particular, the H2 molecule adsorbed on an O top site could directly form H2O precursor on the O3-terminated surface. Further, the newly formed H-O bond was activated, and the H atom could migrate from one O site to another, consequently forming the H2O precursor. In the H2 oxidation process, the decomposition of H2 molecule was the rate-determining step for the O3-terminated surface with an activation energy of 1.53 eV. However, the formation of H2O was the rate-determining step for the Fe-terminated surface with an activation energy of 1.64 eV. The Fe-terminated surface is less energetically favorable for H2 oxidation than that the O3-terminated surface owing to the steric hindrance of Fe atom. These results provide a fundamental understanding about the reaction mechanism of Fe2O3 with H2, which is helpful for the rational design of Fe-based oxygen carrier and the usage of green energy resource such as H2.

Key words: Chemical-looping combustion, Fe2O3 oxygen carrier, H2 adsorption, Density functional theory, Reaction mechanism