Theoretical insight into effect of cation–anion pairs on CO<sub>2</sub> reduction on bismuth electrocatalysts
<p dir="ltr">This study presents theoretical insight into the mechanism of the CO<sub>2</sub> reduction reaction (CO<sub>2</sub>RR) to formic acid (HCOOH) on Bi (0 1 2) surfaces in the presence of alkali metal cations (M<sup>+</sup>: Cs<sup>+...
محفوظ في:
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| مؤلفون آخرون: | , , , |
| منشور في: |
2020
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| _version_ | 1864513558808625152 |
|---|---|
| author | Sun Hee Yoon (7179263) |
| author2 | Guangxia Piao (7320776) Hyunwoong Park (1521754) Nimir O. Elbashir (1850563) Dong Suk Han (1748989) |
| author2_role | author author author author |
| author_facet | Sun Hee Yoon (7179263) Guangxia Piao (7320776) Hyunwoong Park (1521754) Nimir O. Elbashir (1850563) Dong Suk Han (1748989) |
| author_role | author |
| dc.creator.none.fl_str_mv | Sun Hee Yoon (7179263) Guangxia Piao (7320776) Hyunwoong Park (1521754) Nimir O. Elbashir (1850563) Dong Suk Han (1748989) |
| dc.date.none.fl_str_mv | 2020-12-01T00:00:00Z |
| dc.identifier.none.fl_str_mv | 10.1016/j.apsusc.2020.147459 |
| dc.relation.none.fl_str_mv | https://figshare.com/articles/journal_contribution/Theoretical_insight_into_effect_of_cation_anion_pairs_on_CO_sub_2_sub_reduction_on_bismuth_electrocatalysts/24270292 |
| dc.rights.none.fl_str_mv | CC BY 4.0 info:eu-repo/semantics/openAccess |
| dc.subject.none.fl_str_mv | Chemical sciences Physical chemistry Engineering Materials engineering Physical sciences Condensed matter physics CO2 reduction Single ion adsorption Mixed ion adsorption Adsorption energy Work function Reaction pathway |
| dc.title.none.fl_str_mv | Theoretical insight into effect of cation–anion pairs on CO<sub>2</sub> reduction on bismuth electrocatalysts |
| dc.type.none.fl_str_mv | Text Journal contribution info:eu-repo/semantics/publishedVersion text contribution to journal |
| description | <p dir="ltr">This study presents theoretical insight into the mechanism of the CO<sub>2</sub> reduction reaction (CO<sub>2</sub>RR) to formic acid (HCOOH) on Bi (0 1 2) surfaces in the presence of alkali metal cations (M<sup>+</sup>: Cs<sup>+</sup>, K<sup>+</sup>, and Li<sup>+</sup>) and/or halide anions (X<sup>−</sup>: Cl<sup>−</sup>, Br<sup>−</sup>, and I<sup>−</sup>) using density functional theory (DFT). The adsorption energy (Eads) and work function (Wf) of the anions increases with decreasing anion size (i.e., Cl<sup>−</sup> > Br<sup>−</sup> > I<sup>−</sup>). On the other hand, the larger the cation size is, the higher is the Eads (i.e., Li<sup>+ </sup>< K<sup>+</sup> < Cs<sup>+</sup>) but the lower is the Wf (i.e., Cs<sup>+</sup> < K<sup>+</sup> < Li<sup>+</sup>). In the presence of the cation–anion pairs (M<sup>+</sup>/X<sup>−</sup>), Eads of the pairs on hydrated Bi (Bi-2H) becomes more negative than that in the cases of anions or cations alone, particularly when the ionic radius of the paired cation and anion do not differ significantly. Such a synergistic effect of the mixed ions is also observed for the work function values. In the case of anions alone, CO<sub>2</sub> molecules prefer to coordinate directly with hydrated Bi atoms via the oxygen bidentate mode; in the case of cations alone, CO<sub>2</sub> molecules directly bind to the cations via the oxygen monodentate mode, rather than the hydrated Bi atoms. Between two possible CO2RR pathways involving *OCHO and *COOH intermediates on Bi-2H pre-adsorbed with M<sup>+</sup>/X<sup>−</sup>, the former pathway requires less energy for all M<sup>+</sup>/X<sup>−</sup> pairs. In addition, cascaded reaction profiles from CO<sub>2</sub>* to HCOOH are obtained with Cs<sup>+</sup>/Cl<sup>−</sup> and K<sup>+</sup>/Cl<sup>−</sup> pairs in the former. This indicates that once CO<sub>2</sub> is adsorbed, the following reactions proceed spontaneously on Bi-2H with Cs<sup>+</sup>/Cl<sup>−</sup> or K<sup>+</sup>/Cl<sup>− </sup>pairs. This study thus shed light on the positive effects of supporting electrolytes (e.g., CsCl and KCl) on catalytic CO<sub>2</sub>RR.</p><h2>Other Information</h2><p dir="ltr">Published in: Applied Surface Science<br>License: <a href="http://creativecommons.org/licenses/by/4.0/" target="_blank">http://creativecommons.org/licenses/by/4.0/</a><br>See article on publisher's website: <a href="https://dx.doi.org/10.1016/j.apsusc.2020.147459" target="_blank">https://dx.doi.org/10.1016/j.apsusc.2020.147459</a></p> |
| eu_rights_str_mv | openAccess |
| id | Manara2_fd5f030d834195b364e283b844af53ff |
| identifier_str_mv | 10.1016/j.apsusc.2020.147459 |
| network_acronym_str | Manara2 |
| network_name_str | Manara2 |
| oai_identifier_str | oai:figshare.com:article/24270292 |
| publishDate | 2020 |
| repository.mail.fl_str_mv | |
| repository.name.fl_str_mv | |
| repository_id_str | |
| rights_invalid_str_mv | CC BY 4.0 |
| spelling | Theoretical insight into effect of cation–anion pairs on CO<sub>2</sub> reduction on bismuth electrocatalystsSun Hee Yoon (7179263)Guangxia Piao (7320776)Hyunwoong Park (1521754)Nimir O. Elbashir (1850563)Dong Suk Han (1748989)Chemical sciencesPhysical chemistryEngineeringMaterials engineeringPhysical sciencesCondensed matter physicsCO2 reductionSingle ion adsorptionMixed ion adsorptionAdsorption energyWork functionReaction pathway<p dir="ltr">This study presents theoretical insight into the mechanism of the CO<sub>2</sub> reduction reaction (CO<sub>2</sub>RR) to formic acid (HCOOH) on Bi (0 1 2) surfaces in the presence of alkali metal cations (M<sup>+</sup>: Cs<sup>+</sup>, K<sup>+</sup>, and Li<sup>+</sup>) and/or halide anions (X<sup>−</sup>: Cl<sup>−</sup>, Br<sup>−</sup>, and I<sup>−</sup>) using density functional theory (DFT). The adsorption energy (Eads) and work function (Wf) of the anions increases with decreasing anion size (i.e., Cl<sup>−</sup> > Br<sup>−</sup> > I<sup>−</sup>). On the other hand, the larger the cation size is, the higher is the Eads (i.e., Li<sup>+ </sup>< K<sup>+</sup> < Cs<sup>+</sup>) but the lower is the Wf (i.e., Cs<sup>+</sup> < K<sup>+</sup> < Li<sup>+</sup>). In the presence of the cation–anion pairs (M<sup>+</sup>/X<sup>−</sup>), Eads of the pairs on hydrated Bi (Bi-2H) becomes more negative than that in the cases of anions or cations alone, particularly when the ionic radius of the paired cation and anion do not differ significantly. Such a synergistic effect of the mixed ions is also observed for the work function values. In the case of anions alone, CO<sub>2</sub> molecules prefer to coordinate directly with hydrated Bi atoms via the oxygen bidentate mode; in the case of cations alone, CO<sub>2</sub> molecules directly bind to the cations via the oxygen monodentate mode, rather than the hydrated Bi atoms. Between two possible CO2RR pathways involving *OCHO and *COOH intermediates on Bi-2H pre-adsorbed with M<sup>+</sup>/X<sup>−</sup>, the former pathway requires less energy for all M<sup>+</sup>/X<sup>−</sup> pairs. In addition, cascaded reaction profiles from CO<sub>2</sub>* to HCOOH are obtained with Cs<sup>+</sup>/Cl<sup>−</sup> and K<sup>+</sup>/Cl<sup>−</sup> pairs in the former. This indicates that once CO<sub>2</sub> is adsorbed, the following reactions proceed spontaneously on Bi-2H with Cs<sup>+</sup>/Cl<sup>−</sup> or K<sup>+</sup>/Cl<sup>− </sup>pairs. This study thus shed light on the positive effects of supporting electrolytes (e.g., CsCl and KCl) on catalytic CO<sub>2</sub>RR.</p><h2>Other Information</h2><p dir="ltr">Published in: Applied Surface Science<br>License: <a href="http://creativecommons.org/licenses/by/4.0/" target="_blank">http://creativecommons.org/licenses/by/4.0/</a><br>See article on publisher's website: <a href="https://dx.doi.org/10.1016/j.apsusc.2020.147459" target="_blank">https://dx.doi.org/10.1016/j.apsusc.2020.147459</a></p>2020-12-01T00:00:00ZTextJournal contributioninfo:eu-repo/semantics/publishedVersiontextcontribution to journal10.1016/j.apsusc.2020.147459https://figshare.com/articles/journal_contribution/Theoretical_insight_into_effect_of_cation_anion_pairs_on_CO_sub_2_sub_reduction_on_bismuth_electrocatalysts/24270292CC BY 4.0info:eu-repo/semantics/openAccessoai:figshare.com:article/242702922020-12-01T00:00:00Z |
| spellingShingle | Theoretical insight into effect of cation–anion pairs on CO<sub>2</sub> reduction on bismuth electrocatalysts Sun Hee Yoon (7179263) Chemical sciences Physical chemistry Engineering Materials engineering Physical sciences Condensed matter physics CO2 reduction Single ion adsorption Mixed ion adsorption Adsorption energy Work function Reaction pathway |
| status_str | publishedVersion |
| title | Theoretical insight into effect of cation–anion pairs on CO<sub>2</sub> reduction on bismuth electrocatalysts |
| title_full | Theoretical insight into effect of cation–anion pairs on CO<sub>2</sub> reduction on bismuth electrocatalysts |
| title_fullStr | Theoretical insight into effect of cation–anion pairs on CO<sub>2</sub> reduction on bismuth electrocatalysts |
| title_full_unstemmed | Theoretical insight into effect of cation–anion pairs on CO<sub>2</sub> reduction on bismuth electrocatalysts |
| title_short | Theoretical insight into effect of cation–anion pairs on CO<sub>2</sub> reduction on bismuth electrocatalysts |
| title_sort | Theoretical insight into effect of cation–anion pairs on CO<sub>2</sub> reduction on bismuth electrocatalysts |
| topic | Chemical sciences Physical chemistry Engineering Materials engineering Physical sciences Condensed matter physics CO2 reduction Single ion adsorption Mixed ion adsorption Adsorption energy Work function Reaction pathway |