Molybdenum tailored Co0/Co2+ active pairs on a perovskite-type oxide for direct ethanol synthesis from syngas

doi:10.1016/j.cjche.2023.01.018

Abstract

Abstract: Selective synthesis of ethanol from syngas under the Co-based catalysts is still challenging due to the hard of regulating the active site Co⁰ and Co²⁺ ratio. In this work, a series of CaTi_0.9-xCo_xMo_0.1O₃ (x = 0, 0.1-0.4) and CaTi_0.7Co_0.3O₃ catalysts were prepared by using citric acid complexation method to promote the synthesis of ethanol. It was found that Mo species in the perovskite lattice can regulate the Co⁰ and Co²⁺ ratio through the domain-limiting effect of perovskite and the degree of Co reduction could be adjusted by changing the Co/Mo molar ratio. Among these investigated catalysts, the total selectivity of alcohols over the catalyst with the optimal Co/Mo ratio CaTi_0.6Co_0.3Mo_0.1O₃ reached 39.1%, with ethanol accounting for 74.7%, which was ascribed to the moderate and tightly bound ratio of dissociative to non-dissociative adsorption sites on the surface and the balance of CH_x-CH_y coupling and CO insertion.

Key words: Direct ethanol synthesis, Cobalt, Molybdenum, Syngas, Perovskite-type oxides

摘要： Selective synthesis of ethanol from syngas under the Co-based catalysts is still challenging due to the hard of regulating the active site Co⁰ and Co²⁺ ratio. In this work, a series of CaTi_0.9-xCo_xMo_0.1O₃ (x = 0, 0.1-0.4) and CaTi_0.7Co_0.3O₃ catalysts were prepared by using citric acid complexation method to promote the synthesis of ethanol. It was found that Mo species in the perovskite lattice can regulate the Co⁰ and Co²⁺ ratio through the domain-limiting effect of perovskite and the degree of Co reduction could be adjusted by changing the Co/Mo molar ratio. Among these investigated catalysts, the total selectivity of alcohols over the catalyst with the optimal Co/Mo ratio CaTi_0.6Co_0.3Mo_0.1O₃ reached 39.1%, with ethanol accounting for 74.7%, which was ascribed to the moderate and tightly bound ratio of dissociative to non-dissociative adsorption sites on the surface and the balance of CH_x-CH_y coupling and CO insertion.

关键词: Direct ethanol synthesis, Cobalt, Molybdenum, Syngas, Perovskite-type oxides

Yi Wu, Pengfei Song, Ningyan Li, Yanan Jiang, Yuan Liu. Molybdenum tailored Co⁰/Co²⁺ active pairs on a perovskite-type oxide for direct ethanol synthesis from syngas[J]. Chinese Journal of Chemical Engineering, 2023, 59(7): 279-289.

Yi Wu, Pengfei Song, Ningyan Li, Yanan Jiang, Yuan Liu. Molybdenum tailored Co⁰/Co²⁺ active pairs on a perovskite-type oxide for direct ethanol synthesis from syngas[J]. 中国化学工程学报, 2023, 59(7): 279-289.

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Molybdenum tailored Co⁰/Co²⁺ active pairs on a perovskite-type oxide for direct ethanol synthesis from syngas

Molybdenum tailored Co⁰/Co²⁺ active pairs on a perovskite-type oxide for direct ethanol synthesis from syngas

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