Elucidating the Influence of Electric Fields toward CO<sub>2</sub> Activation on YSZ (111)
Despite its high thermodynamic stability, the presence of a negative electric field is known to facilitate the activation of CO<sub>2</sub> through electrostatic effects. To utilize electric fields for a reverse water gas shift reaction, it is critical to elucidate the role of an electri...
| Main Authors: | , , , , |
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| Format: | Article |
| Language: | English |
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MDPI AG
2021-02-01
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| Series: | Catalysts |
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| Online Access: | https://www.mdpi.com/2073-4344/11/2/271 |
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| author | Nisa Ulumuddin Fanglin Che Jung-Il Yang Su Ha Jean-Sabin McEwen |
| author_facet | Nisa Ulumuddin Fanglin Che Jung-Il Yang Su Ha Jean-Sabin McEwen |
| author_sort | Nisa Ulumuddin |
| collection | DOAJ |
| description | Despite its high thermodynamic stability, the presence of a negative electric field is known to facilitate the activation of CO<sub>2</sub> through electrostatic effects. To utilize electric fields for a reverse water gas shift reaction, it is critical to elucidate the role of an electric field on a catalyst surface toward activating a CO<sub>2</sub> molecule. We conduct a first-principles study to gain an atomic and electronic description of adsorbed CO<sub>2</sub> on YSZ (111) surfaces when external electric fields of +1 V/Å, 0 V/Å, and −1 V/Å are applied. We find that the application of an external electric field generally destabilizes oxide bonds, where the direction of the field affects the location of the most favorable oxygen vacancy. The direction of the field also drastically impacts how CO<sub>2</sub> adsorbs on the surface. CO<sub>2</sub> is bound by physisorption when a +1 V/Å field is applied, a similar interaction as to how it is adsorbed in the absence of a field. This interaction changes to chemisorption when the surface is exposed to a −1 V/Å field value, resulting in the formation of a CO<sub>3</sub><sup>−</sup> complex. The strong interaction is reflected through a direct charge transfer and an orbital splitting within the O<sub>lattice</sub><i>p</i>-states. While CO<sub>2</sub> remains physisorbed when a +1 V/Å field value is applied, our total density of states analysis indicates that a positive field pulls the charge away from the adsorbate, resulting in a shift of its bonding and antibonding peaks to higher energies, allowing a stronger interaction with YSZ (111). Ultimately, the effect of an electric field toward CO<sub>2</sub> adsorption is not negligible, and there is potential in utilizing electric fields to favor the thermodynamics of CO<sub>2</sub> reduction on heterogeneous catalysts. |
| first_indexed | 2024-03-09T00:46:38Z |
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| institution | Directory Open Access Journal |
| issn | 2073-4344 |
| language | English |
| last_indexed | 2024-03-09T00:46:38Z |
| publishDate | 2021-02-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Catalysts |
| spelling | doaj.art-5dbe2da7139043368f675c9b2150154c2023-12-11T17:27:54ZengMDPI AGCatalysts2073-43442021-02-0111227110.3390/catal11020271Elucidating the Influence of Electric Fields toward CO<sub>2</sub> Activation on YSZ (111)Nisa Ulumuddin0Fanglin Che1Jung-Il Yang2Su Ha3Jean-Sabin McEwen4The Gene & Linda Voiland School of Chemical Engineering and Bioengineering, Washington State University, Pullman, WA 99164, USADepartment of Chemical Engineering, University of Massachusetts, Lowell, MA 01854, USAClean Fuel Laboratory, Korea Institute of Energy Research, Daejeon 34129, KoreaThe Gene & Linda Voiland School of Chemical Engineering and Bioengineering, Washington State University, Pullman, WA 99164, USAThe Gene & Linda Voiland School of Chemical Engineering and Bioengineering, Washington State University, Pullman, WA 99164, USADespite its high thermodynamic stability, the presence of a negative electric field is known to facilitate the activation of CO<sub>2</sub> through electrostatic effects. To utilize electric fields for a reverse water gas shift reaction, it is critical to elucidate the role of an electric field on a catalyst surface toward activating a CO<sub>2</sub> molecule. We conduct a first-principles study to gain an atomic and electronic description of adsorbed CO<sub>2</sub> on YSZ (111) surfaces when external electric fields of +1 V/Å, 0 V/Å, and −1 V/Å are applied. We find that the application of an external electric field generally destabilizes oxide bonds, where the direction of the field affects the location of the most favorable oxygen vacancy. The direction of the field also drastically impacts how CO<sub>2</sub> adsorbs on the surface. CO<sub>2</sub> is bound by physisorption when a +1 V/Å field is applied, a similar interaction as to how it is adsorbed in the absence of a field. This interaction changes to chemisorption when the surface is exposed to a −1 V/Å field value, resulting in the formation of a CO<sub>3</sub><sup>−</sup> complex. The strong interaction is reflected through a direct charge transfer and an orbital splitting within the O<sub>lattice</sub><i>p</i>-states. While CO<sub>2</sub> remains physisorbed when a +1 V/Å field value is applied, our total density of states analysis indicates that a positive field pulls the charge away from the adsorbate, resulting in a shift of its bonding and antibonding peaks to higher energies, allowing a stronger interaction with YSZ (111). Ultimately, the effect of an electric field toward CO<sub>2</sub> adsorption is not negligible, and there is potential in utilizing electric fields to favor the thermodynamics of CO<sub>2</sub> reduction on heterogeneous catalysts.https://www.mdpi.com/2073-4344/11/2/271CO<sub>2</sub> reductionelectric fieldcatalysisdensity functional theoryyttria stabilized zirconia |
| spellingShingle | Nisa Ulumuddin Fanglin Che Jung-Il Yang Su Ha Jean-Sabin McEwen Elucidating the Influence of Electric Fields toward CO<sub>2</sub> Activation on YSZ (111) Catalysts CO<sub>2</sub> reduction electric field catalysis density functional theory yttria stabilized zirconia |
| title | Elucidating the Influence of Electric Fields toward CO<sub>2</sub> Activation on YSZ (111) |
| title_full | Elucidating the Influence of Electric Fields toward CO<sub>2</sub> Activation on YSZ (111) |
| title_fullStr | Elucidating the Influence of Electric Fields toward CO<sub>2</sub> Activation on YSZ (111) |
| title_full_unstemmed | Elucidating the Influence of Electric Fields toward CO<sub>2</sub> Activation on YSZ (111) |
| title_short | Elucidating the Influence of Electric Fields toward CO<sub>2</sub> Activation on YSZ (111) |
| title_sort | elucidating the influence of electric fields toward co sub 2 sub activation on ysz 111 |
| topic | CO<sub>2</sub> reduction electric field catalysis density functional theory yttria stabilized zirconia |
| url | https://www.mdpi.com/2073-4344/11/2/271 |
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