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• The effect of promoter was evaluated for CO and CO 2 methanation. • Mn, Ce, Mg, V, and Zr are beneficial for both CO and CO 2 methanation activity. • CO 2 methanation is related to the Ni dispersion and relevant CO 2 adsorption. • Ni-V/Al@Al 2 O 3 with the highest Ni dispersion is the best for CO methanation. • The promotional effect of Mn is remarkable for both CO and CO 2 methanation. Effects of metal promoter on CO and CO 2 methanation were examined over Ni-M (M = Mn, Ce, Zr, Mg, K, Zn, or V)/Al@Al 2 O 3 catalysts prepared by the co-impregnation method. Ni-M (M = Mn, Ce, or Zr)/γ-Al 2 O 3 catalysts were also investigated for comparison. The prepared catalysts were characterized with a variety of techniques such as N 2 physisorption, CO 2 chemisorption, H 2 chemisorption, temperature-programmed reduction with H 2 (H 2 -TPR), temperature-programmed desorption of CO 2 (CO 2 -TPD), X-ray diffraction (XRD), high-resolution transmission electron microscopy (HRTEM), X-ray photoelectron spectroscopy (XPS), and in-situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS). Among different promoters, Mn, Ce, Mg, V, and Zr are beneficial to enhance both CO and CO 2 methanation activity due to the improvement of the Ni dispersion. The Ni-V/Al@Al 2 O 3 catalyst performs the highest CO methanation activity due to the largest Ni sites. However, it is not the best one for CO 2 methanation among tested catalysts because of the much decrease in CO 2 adsorption capacity. The promotional effect of Mn is the most remarkable for both CO and CO 2 methanation. On the other hand, the negative effect of K and Zn was observed on both CO and CO 2 methanation by the small number of active Ni sites and the decrease in the amount of basic sites. The CO 2 methanation mechanism over Ni-Mn/Al@Al 2 O 3 catalyst is elucidated by the transform route: adsorbed carbonate species – formate species – methane under hydrogenation process. [ABSTRACT FROM AUTHOR]