Chinese Journal of Catalysis ›› 2025, Vol. 75: 9-20.DOI: 10.1016/S1872-2067(25)64743-7

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Interface engineering of oxygen-vacancy-rich MgO/Ni@NiAlO enables low-temperature coke-free methane dry reforming

Wang Qiuyuea, Yang Chenyua, Zhu Shengganb, Zhang Yuansena, Wang Xuana, Li Yongtinga, Ding Weipinga,*(), Guo Xuefenga,c,d,*()   

  1. aKey Laboratory of Mesoscopic Chemistry MOE, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210023, Jiangsu, China
    bZhejiang Titan Design & Engineering Co., Ltd, Hangzhou 310038, Zhejiang, China
    cNanjing University-Yangzhou Institute of Chemistry and Chemical Engineering, Yangzhou 211900, Jiangsu, China
    dJiangsu Key Laboratory of Vehicle Emissions Control, Nanjing University, Nanjing 210023, Jiangsu, China
  • Received:2025-02-18 Accepted:2025-04-18 Online:2025-08-18 Published:2025-07-22
  • Contact: *E-mail: guoxf@nju.edu.cn (X. Guo), dingwp@nju.edu.cn (W. Ding).
  • Supported by:
    National Key Technology Research and Development Program of China(2021YFA1502804);National Science Foundation of China(22172073);National Science Foundation of China(21773112);National Science Foundation of China(21173119);National Science Foundation of China(21273109);Jiangsu Provincial Key Research and Development Program(BE2022611);Natural Science Foundation of Jiangsu Province(BK20221286)

Abstract:

In the past decade, dry reforming of methane (DRM) has garnered increasing interest as it converts CH4 and CO2, two typical greenhouse gases, into synthesis gas (H2 and CO) for the production of high-value-added chemicals and fuels. Nickel-based DRM catalysts, renowned for their high activity and low cost, however, encounter challenges such as severe deactivation from sintering and carbon deposition. Herein, a surrounded NiO@NiAlO precursor derived from Ni(OH)2 nanosheets was modified at both the core and shell interfaces with MgO via wet impregnation. The obtained 0.8MgOWI/Ni@NiAlO catalyst achieved a high CH4 reaction rate of ~177 mmol gNi-1 min-1 and remained stable for 50 h at 600 °C without coke formation. In sharp contrast, other Mg-doped catalysts (MgO modified the core or shell interfaces) and the catalyst without Mg-doping deactivated within 10 h due to coking or Ni particle sintering. The Ni/MgNiO2 interfaces and abundant oxygen vacancies (Ov) generated by Mg-doping contributed to the outstanding resistance to sintering & coking as well as the superior activity and stability of the 0.8MgOWI/Ni@NiAlO catalyst. In-situ investigation further unveiled the reaction mechanism: the activation of CO2 via adsorption on Ov generates active oxygen species (O*), which reacts with CHx* intermediates formed by the dissociation of CH4 on Ni sites, yielding CO and H2. This work not only fabricates coke-free and high-stability Ni-based DRM catalysts via interface engineering but also provides insights and a new strategy for the design of high-efficiency and stable catalysts for DRM.

Key words: Dry reforming of methane, Ni-based catalyst, Coke-free, Oxygen vacancy, Interface engineering