Comparative computational study of CO 2 dissociation and hydrogenation over Fe-M (M = Pd, Ni, Co) bimetallic catalysts: The effect of surface metal content

Xiaowa Nie, Haozhi Wang, Zhiming Liang, Zhenzi Yu, Jiajin Zhang, Michael J. Janik, Xinwen Guo, Chunshan Song

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Density functional theory (DFT) calculations were performed to study CO 2 adsorption, dissociation and hydrogenation over Fe-M (M = Pd, Ni, Co) bimetallic catalysts, with a focus on probing the effect of surface content of the added transition metals to Fe. Various Fe-M bimetallic surfaces were constructed with varied surface atomic ratios of Fe/(Fe + M), based on which CO 2 and atomic H∗adsorptions were systematically examined. The H∗was found to be energetically favorable adsorbed at the 4-fold hollow site of Fe-M catalysts and the adsorption stability was slightly impacted by the surface content of the introduced transition metal. For CO 2 adsorption, stable bent structures adsorbed on the 4-fold hollow sites were identified on Fe-Ni and Fe-Co surfaces, no matter at which Fe-M formulations. However, on Fe-Pd surfaces, CO 2 adsorption configurations were found to be sensitive to surface Pd content, resulting in large distinctions in adsorption stabilities of CO 2 as compared to Fe-Co and Fe-Ni surfaces. CO 2 dissociation and initial hydrogenation were comparatively investigated on Fe-M bimetallic surfaces, and the calculation results demonstrated that CO 2 conversion properties are similar over Fe-Ni and Fe-Co catalysts, with CO∗and HCOO∗as the preferred intermediates but the barriers are still above 0.8 eV. While on Fe-Pd bimetallic surfaces, CO 2 reactions exhibit significant distinctions with varying the surface Pd content, showing a dramatic preference (E act around 0.3∼0.4 eV) towards HCOO∗and CO∗formation at surface Pd/(Pd + Fe) atomic ratios of 4/9 and 5/9. The superior catalytic activities of Fe-Pd catalysts are attributed to the particular surface structures and electronic features at specific bimetallic formulations which result in unique adsorption configurations of CO 2 and facilitate the stabilization of transition states in CO∗and HCOO∗formation pathways in CO 2 conversion.

Original languageEnglish (US)
Pages (from-to)179-195
Number of pages17
JournalJournal of CO2 Utilization
StatePublished - Jan 2019

All Science Journal Classification (ASJC) codes

  • Chemical Engineering (miscellaneous)
  • Waste Management and Disposal
  • Process Chemistry and Technology


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