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Synergistic Effects of the Zr and Sm Co-doped Fe2O3/CeO2 Oxygen Carrier for Chemical Looping Hydrogen Generation

  • Shiwei Ma
    Shiwei Ma
    Engineering Laboratory for Energy System Process Conversion & Emission Control Technology of Jiangsu Province, School of Energy and Mechanical Engineering, Nanjing Normal University, Nanjing, Jiangsu 210023, People’s Republic of China
    Key Laboratory of Energy Thermal Conversion and Control of Ministry of Education, School of Energy and Environment, Southeast University, Nanjing, Jiangsu 210096, People’s Republic of China
    More by Shiwei Ma
  • Shiyi Chen
    Shiyi Chen
    Key Laboratory of Energy Thermal Conversion and Control of Ministry of Education, School of Energy and Environment, Southeast University, Nanjing, Jiangsu 210096, People’s Republic of China
    More by Shiyi Chen
  • Huijun Ge
    Huijun Ge
    Engineering Laboratory for Energy System Process Conversion & Emission Control Technology of Jiangsu Province, School of Energy and Mechanical Engineering, Nanjing Normal University, Nanjing, Jiangsu 210023, People’s Republic of China
    More by Huijun Ge
  • Tao Song
    Tao Song
    Engineering Laboratory for Energy System Process Conversion & Emission Control Technology of Jiangsu Province, School of Energy and Mechanical Engineering, Nanjing Normal University, Nanjing, Jiangsu 210023, People’s Republic of China
    More by Tao Song
  • Ping Lu
    Ping Lu
    Engineering Laboratory for Energy System Process Conversion & Emission Control Technology of Jiangsu Province, School of Energy and Mechanical Engineering, Nanjing Normal University, Nanjing, Jiangsu 210023, People’s Republic of China
    More by Ping Lu
  • , and 
  • Wenguo Xiang*
    Wenguo Xiang
    Key Laboratory of Energy Thermal Conversion and Control of Ministry of Education, School of Energy and Environment, Southeast University, Nanjing, Jiangsu 210096, People’s Republic of China
    *Telephone: +86-25-8379-5545. Fax: +86-25-8771-4489. E-mail: [email protected]
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Cite this: Energy Fuels 2020, 34, 8, 10256–10267
Publication Date (Web):July 6, 2020
https://doi.org/10.1021/acs.energyfuels.0c01027
Copyright © 2020 American Chemical Society
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Abstract

CeO2 is a typical fluorite oxide with desirable lattice oxygen conductivity and can be applied as an active support for the Fe-based oxygen carrier in chemical looping hydrogen generation (CLHG). However, Fe2O3/CeO2 always suffers from low thermal stability and sintering. Doping foreign cations could be a proper way to improve its reactivity and cyclic stability. In this work, Zr4+ and Sm3+, with a smaller ionic radius and lower valence than Ce4+, respectively, were doped into Fe2O3/CeO2 using the co-precipitation method, and the doping effects on the reactivity and redox stability of Fe2O3/CeO2 in CLHG were investigated. Fe2O3/Ce0.6Sm0.15Zr0.25O1.925 provided the best redox reactivity, and the purity of generated hydrogen for all oxygen carriers reached nearly 100% (the detection limit of CO/CO2 was 0.01% in volume). The reactivity followed the sequence Fe2O3/Ce0.6Sm0.15Zr0.25O1.925 > Fe2O3/Ce0.8Sm0.2O1.9 > Fe2O3/Ce0.75Zr0.25O2 > Fe2O3/CeO2. However, the concentration of oxygen vacancy was ranked as Fe2O3/Ce0.8Sm0.2O1.9 > Fe2O3/Ce0.6Sm0.15Zr0.25O1.925 > Fe2O3/Ce0.75Zr0.25O2 > Fe2O3/CeO2. The Zr doping boosted the reactivity of Fe2O3/CeO2 mainly by enhancing its sintering resistance, whereas the Sm doping achieved it mainly by promoting the oxygen conductivity, whose ability to improve the thermal stability of Fe2O3/CeO2 was rather limited. Both Zr and Sm doping could suppress the outward migration of Fe cations in the particles, resulting in higher sintering resistance. Furthermore, Zr and Sm could dissolve into CeO2 for prepared Fe2O3/Ce0.6Sm0.15Zr0.25O1.925; however, the bleeding out of both dopants was observed with Sm0.5Zr0.5O1.75 formation, which could be detrimental to the redox stability of the oxygen carrier.

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This article is cited by 7 publications.

  1. Haibo Zhao, (Managing Guest Editor)Hongguang Jin, (Guest Editor)Laihong Shen, (Guest Editor)Zhenshan Li (Guest Editor). Virtual Special Issue of Recent Research Advances in China: Chemical Looping. Energy & Fuels 2021, 35 (1) , 3-6. https://doi.org/10.1021/acs.energyfuels.0c03947
  2. Manling Xue, Xingbin Liu, Hao Wu, Bo Yu, Fanming Meng. Construction of Cu2+-doped CeO2 nanocrystals hierarchical hollow structure and its enhanced photocatalytic performance. Journal of Materials Science: Materials in Electronics 2021, 32 (23) , 27576-27586. https://doi.org/10.1007/s10854-021-07132-6
  3. Zhihua Gao, Fengyan Fu, Lili Niu, Min Jin, Xiaohong Wang. Effect of support on hydrogen generation over iron oxides in the chemical looping process. RSC Advances 2021, 11 (59) , 37552-37558. https://doi.org/10.1039/D1RA07210B
  4. Fang Cheng, Aijing Yan, Shiwei Ma, Shiyi Chen, Tao Song, Ping Lu, Wenguo Xiang. Evolution of Sm‐Doped Fe 2 O 3 /CeO 2 Oxygen Carriers in Chemical Looping Hydrogen Generation. Energy Technology 2021, 9 (11) , 2100535. https://doi.org/10.1002/ente.202100535
  5. Jie Gao, Ge Pu, Pengcheng Wang, Cong Yuan, Shuaihui Jia. Study on the reaction performance of Ce‐doped NiFe 2 O 4 oxygen carriers in the process of chemical looping hydrogen production. International Journal of Energy Research 2021, 88 https://doi.org/10.1002/er.7346
  6. Airong Yang, Qingyu Hou, Xiang Yin, Shulin Sha. First-principle study of the effects of biaxial strain on the photocatalytic and magnetic mechanisms of ZnO with Sm doping and point defects (VZn, Hi). Vacuum 2021, 189 , 110225. https://doi.org/10.1016/j.vacuum.2021.110225
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