DFT insight into the effect of potassium on the adsorption, activation and dissociation of CO2 over Fe-based catalysts

Xiaowa Nie, Linlin Meng, Haozhi Wang, Yonggang Chen, Xinwen Guo, Chunshan Song

Research output: Contribution to journalArticle

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Abstract

Catalytic conversion of CO2 including hydrogenation has attracted great attention as a method for chemical fixation of CO2 in combination with other techniques such as CO2 capture and storage. Potassium is a well-known promotor for many industrial catalytic processes such as in Fischer-Tropsch synthesis. In this work, we performed density functional theory (DFT) calculations to investigate the effect of potassium on the adsorption, activation, and dissociation of CO2 over Fe(100), Fe5C2(510) and Fe3O4(111) surfaces. The function of K was analyzed in terms of electronic interactions between co-adsorbed CO2 and K-surfaces which showed conspicuous promotion in the presence of K of the adsorption and activation of CO2. The adsorption strength of CO2 on these surfaces ranks as oct2-Fe3O4(111) > Fe(100) > Fe5C2(510). Generally, we observed a direct proportional correlation between the adsorption strength and the charges on the adsorbates. Adding K on the catalyst surface also reduces the kinetic barrier for CO2 dissociation. CO2 dissociation is more facile to occur on Fe(100) and Fe5C2(510) in the presence of K whereas the Fe3O4(111) surfaces impede CO2 dissociation regardless of the existence of K. Instead, a stable CO3- species is formed upon CO2 adsorption on Fe3O4(111) which will be directly hydrogenated when sufficient H∗ are available on the surface. Our results highlight the origin of the promotion effect of potassium and provide insight for the future design of K-promoted Fe-based catalysts for CO2 hydrogenation.

Original languageEnglish (US)
Pages (from-to)14694-14707
Number of pages14
JournalPhysical Chemistry Chemical Physics
Volume20
Issue number21
DOIs
StatePublished - Jan 1 2018

Fingerprint

Density functional theory
potassium
Potassium
Chemical activation
activation
dissociation
density functional theory
Adsorption
catalysts
Catalysts
adsorption
promotion
Hydrogenation
hydrogenation
Fischer-Tropsch synthesis
Adsorbates
Kinetics
kinetics
synthesis
electronics

All Science Journal Classification (ASJC) codes

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

Cite this

Nie, Xiaowa ; Meng, Linlin ; Wang, Haozhi ; Chen, Yonggang ; Guo, Xinwen ; Song, Chunshan. / DFT insight into the effect of potassium on the adsorption, activation and dissociation of CO2 over Fe-based catalysts. In: Physical Chemistry Chemical Physics. 2018 ; Vol. 20, No. 21. pp. 14694-14707.
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abstract = "Catalytic conversion of CO2 including hydrogenation has attracted great attention as a method for chemical fixation of CO2 in combination with other techniques such as CO2 capture and storage. Potassium is a well-known promotor for many industrial catalytic processes such as in Fischer-Tropsch synthesis. In this work, we performed density functional theory (DFT) calculations to investigate the effect of potassium on the adsorption, activation, and dissociation of CO2 over Fe(100), Fe5C2(510) and Fe3O4(111) surfaces. The function of K was analyzed in terms of electronic interactions between co-adsorbed CO2 and K-surfaces which showed conspicuous promotion in the presence of K of the adsorption and activation of CO2. The adsorption strength of CO2 on these surfaces ranks as oct2-Fe3O4(111) > Fe(100) > Fe5C2(510). Generally, we observed a direct proportional correlation between the adsorption strength and the charges on the adsorbates. Adding K on the catalyst surface also reduces the kinetic barrier for CO2 dissociation. CO2 dissociation is more facile to occur on Fe(100) and Fe5C2(510) in the presence of K whereas the Fe3O4(111) surfaces impede CO2 dissociation regardless of the existence of K. Instead, a stable CO3- species is formed upon CO2 adsorption on Fe3O4(111) which will be directly hydrogenated when sufficient H∗ are available on the surface. Our results highlight the origin of the promotion effect of potassium and provide insight for the future design of K-promoted Fe-based catalysts for CO2 hydrogenation.",
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DFT insight into the effect of potassium on the adsorption, activation and dissociation of CO2 over Fe-based catalysts. / Nie, Xiaowa; Meng, Linlin; Wang, Haozhi; Chen, Yonggang; Guo, Xinwen; Song, Chunshan.

In: Physical Chemistry Chemical Physics, Vol. 20, No. 21, 01.01.2018, p. 14694-14707.

Research output: Contribution to journalArticle

TY - JOUR

T1 - DFT insight into the effect of potassium on the adsorption, activation and dissociation of CO2 over Fe-based catalysts

AU - Nie, Xiaowa

AU - Meng, Linlin

AU - Wang, Haozhi

AU - Chen, Yonggang

AU - Guo, Xinwen

AU - Song, Chunshan

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N2 - Catalytic conversion of CO2 including hydrogenation has attracted great attention as a method for chemical fixation of CO2 in combination with other techniques such as CO2 capture and storage. Potassium is a well-known promotor for many industrial catalytic processes such as in Fischer-Tropsch synthesis. In this work, we performed density functional theory (DFT) calculations to investigate the effect of potassium on the adsorption, activation, and dissociation of CO2 over Fe(100), Fe5C2(510) and Fe3O4(111) surfaces. The function of K was analyzed in terms of electronic interactions between co-adsorbed CO2 and K-surfaces which showed conspicuous promotion in the presence of K of the adsorption and activation of CO2. The adsorption strength of CO2 on these surfaces ranks as oct2-Fe3O4(111) > Fe(100) > Fe5C2(510). Generally, we observed a direct proportional correlation between the adsorption strength and the charges on the adsorbates. Adding K on the catalyst surface also reduces the kinetic barrier for CO2 dissociation. CO2 dissociation is more facile to occur on Fe(100) and Fe5C2(510) in the presence of K whereas the Fe3O4(111) surfaces impede CO2 dissociation regardless of the existence of K. Instead, a stable CO3- species is formed upon CO2 adsorption on Fe3O4(111) which will be directly hydrogenated when sufficient H∗ are available on the surface. Our results highlight the origin of the promotion effect of potassium and provide insight for the future design of K-promoted Fe-based catalysts for CO2 hydrogenation.

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