Modified Ni-carbonate interfaces for enhanced CO2 methanation activity: Tuned reaction pathway and reconstructed surface carbonates

• Published in: Journal of catalysis Vol. 413; pp. 48 - 58
• Main Authors: Shen, Xuqiang, Wang, Zizhou, Wang, Qiaojuan, Tumurbaatar, Chantsalmaa, Bold, Tungalagtamir, Liu, Wen, Dai, Yihu, Tang, Yongming, Yang, Yanhui
• Format: Journal Article
• Language: English
• Published: Elsevier Inc 01.09.2022
• Subjects: Carbonate support; CO2 methanation; Heterogeneous catalysis; Metal-support interaction; Ni catalyst; Surface reconstruction; Heterogeneous catalysis; Surface reconstruction; Metal-support interaction; CO2 methanation; Ni catalyst; Carbonate support
• ISSN: 0021-9517; 1090-2694
• DOI: 10.1016/j.jcat.2022.06.001

[Display omitted] •Zr-Modified Ni-La2O2CO3 catalyst efficiently catalyze CO2 methanation reaction.•Zr4+ incorporated in La2O2CO3 lattice enhances Ni dispersion and H2 activation ability.•Zr modification tunes the surface basic property for promoting CO2 chemisorption.•Hydrogenation pathways of CO and formate intermediates are co-existed with relatively high activity.•Surface carbonate species are in dynamic reconstruction and interconversion during reaction. A Ni/Zr-La2O2CO3 catalyst with interfaces between Ni metal and Zr-modified carbonate support was used for atmospheric CO2 methanation reaction, exhibiting 81% conversion and 99.6% CH4 selectivity at 300 °C. The Zr4+ ions incorporated in La2O2CO3 lattices properly strengthened the Ni-carbonate interaction for enhancing the Ni dispersion and hydrogen activation ability of the catalyst. The Zr-modification could also tune the surface basic property for promoting the adsorptive dissociation of CO2. In-situ DRIFT spectra demonstrated that only the hydrogenation reaction pathway of formate intermediates was proceeded in Ni/La2O2CO3-catalyzed CO2 methanation. As a contrast, the hydrogenation pathways of CO and formate intermediates with relatively high activity were co-existed at the modified Ni-Zr-La2O2CO3 interfaces. Furthermore, the isotopic data evidenced that dynamic reconstruction and interconversion of the surface carbonate species occurred in the reaction, which might contribute to the key steps of CO2 dissociation and intermediates transformation.