Synergistic effect of Fe-Mn bimetallic sites with close proximity for enhanced CO₂ hydrogenation performance

Abstract

The Fe-Mn bimetallic catalyst is a potential candidate for the conversion of CO₂ into value-added chemicals. The interaction between the two metals plays a significant role in determining the catalytic performance, however which remains controversial. In this study, we aim to investigate the impact of tuning the proximity of Fe-Mn bimetallic catalysts with similar nanoparticle size. And its effect on the physicochemical properties of the catalysts and corresponding performance were investigated. It was found that closer Fe-Mn proximity resulted in enhanced CO₂ hydrogenation activity and inhibited CH₄ formation. The physiochemical properties of prepared catalysts were characterized using X-ray diffraction, H₂ temperature programmed reduction, and X-ray photoelectron spectroscopy, revealing that a closer Fe-Mn distance promoted electron transfer from Mn to Fe, thereby facilitating Fe carburization. The adsorption behavior of CO₂ and the identification of reaction intermediates were analyzed using CO₂-temperature programed desorption and in situ Fourier transform infrared spectroscopy, confirming the intimate Fe-Mn sites contributed to CO₂ adsorption and the formation of HCOO* species, ultimately leading to increased CO₂ conversion and hydrocarbon production. The discovery of a synergistic effect at the intimate Fe-Mn sites in this study provides valuable insights into the relationship between active sites and promoters.

Graphical abstract

Keywords

CO₂ hydrogenation / Fe-based catalyst / proximity effect / Mn promoter

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Competing interests

The authors declare that they have no competing interests.

Acknowledgements

This work was supported by National Natural Science Foundation of China (Grant Nos. 22378311, 22108200, and 21938008), Natural Science Foundation of Zhejiang Province (Grant No. LQ22B060013). The authors also thank the Haihe Laboratory of Sustainable Chemical Transformations for financial support.

Electronic Supplementary Material

Supplementary material is available in the online version of this article at https://doi.org/10.1007/s11705-024-2491-4 and is accessible for authorized users.

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