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Keller, F., Döhn, J., Groß, A. & Busch, M. (2024). Exploring the Mechanism of the Electrochemical Polymerization of CO2 to Hard Carbon over CeO2(110). The Journal of Physical Chemistry C, 128(15), 6280-6293
Open this publication in new window or tab >>Exploring the Mechanism of the Electrochemical Polymerization of CO2 to Hard Carbon over CeO2(110)
2024 (English)In: The Journal of Physical Chemistry C, ISSN 1932-7447, E-ISSN 1932-7455, Vol. 128, no 15, p. 6280-6293Article in journal (Refereed) Published
Abstract [en]

Conversion of CO2 to hard carbon is an interesting technology for the removal of carbon dioxide from the atmosphere. Recently, it was shown that CeO2 can selectively catalyze this reaction, but we still lack information regarding the reaction mechanism. Using density functional theory modeling, we explore possible reaction mechanisms that allow for the polymerization of CO2. According to our computations, the reaction is initialized by the adsorption of CO2 in an oxygen vacancy. Owing to the rich defect chemistry of ceria, a large number of suitable sites are available at the surface. C–C bond formation is achieved through an aldol condensation-type mechanism which comprises the electrochemical elimination of water to form a carbene. This carbene then performs a nucleophilic attack on CO2. The reaction mechanism possesses significant similarities to the corresponding reactions in synthetic organic chemistry. Since the mechanism is completely generic, it allows for all relevant steps of the formation of hard carbon like chain growth, chain linkage, and the formation of side chains or aromatic rings. Surprisingly, ceria mainly serves as an anchor for CO2 in an oxygen vacancy, while all other subsequent reaction steps are almost completely independent from the catalyst. These insights are important for the development of novel catalysts for CO2 reduction and may also lead to new reactions for the electrosynthesis of organic molecules. 

Place, publisher, year, edition, pages
American Chemical Society (ACS), 2024
National Category
Physical Chemistry
Research subject
Applied Physics
Identifiers
urn:nbn:se:ltu:diva-105037 (URN)10.1021/acs.jpcc.3c08356 (DOI)2-s2.0-85189973481 (Scopus ID)
Note

Validerad;2024;Nivå 2;2024-04-22 (joosat);

Full text: CC BY license;

Funder: German Bundesministerium für Bildung und Forschung (BMBF) project NETPEC (grant number: 01LS2103A); Dr. Barbara-Mez-Starck foundation;

Available from: 2024-04-09 Created: 2024-04-09 Last updated: 2024-04-22Bibliographically approved
Khakpour, R., Farshadfar, K., Dong, S.-T., Lassalle-Kaiser, B., Laasonen, K. & Busch, M. (2024). Mechanism of CO2 Electroreduction to Multicarbon Products over Iron Phthalocyanine Single-Atom Catalysts. The Journal of Physical Chemistry C, 128(14), 5867-5877
Open this publication in new window or tab >>Mechanism of CO2 Electroreduction to Multicarbon Products over Iron Phthalocyanine Single-Atom Catalysts
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2024 (English)In: The Journal of Physical Chemistry C, ISSN 1932-7447, E-ISSN 1932-7455, Vol. 128, no 14, p. 5867-5877Article in journal (Refereed) Published
Abstract [en]

Carbon dioxide reduction reaction (CO2RR) is a promising method for converting CO2 into value-added products. CO2RR over single-atom catalysts (SACs) is widely known to result in chemical compounds such as carbon monoxide and formic acid that contain only one carbon atom (C1). Indeed, at least two active sites are commonly believed to be required for C–C coupling to synthesize compounds, such as ethanol and propylene (C2+), from CO2. However, experimental evidence suggests that iron phthalocyanine (PcFe), which possesses only a single metal center, can produce a trace amount of C2+ products. To the best of our knowledge, the mechanism by which C2+ products are formed over a SAC such as PcFe is still unknown. Using density functional theory (DFT), we analyzed the mechanism of the CO2RR to C1 and C2+ products over PcFe. Due to the high concentration of bicarbonate at pH 7, CO2RR competes with HCO3– reduction. Our computations indicate that bicarbonate reduction is significantly more favorable. However, the rate of this reaction is influenced by the H3O+ concentration. For the formation of C2+ products, our computations reveal that C–C coupling proceeds through the reaction between in situ-formed CO and PcFe(“0”)–CH2 or PcFe(“-I”)–CH2 intermediates. This reaction step is highly exergonic and requires only low activation energies of 0.44 and 0.24 eV for PcFe(“0”)–CH2 and PcFe(“-I”)–CH2. The DFT results, in line with experimental evidence, suggest that C2+ compounds are produced over PcFe at low potentials whereas CH4 is still the main post-CO product. 

Place, publisher, year, edition, pages
American Chemical Society (ACS), 2024
National Category
Other Chemistry Topics
Research subject
Applied Physics
Identifiers
urn:nbn:se:ltu:diva-105039 (URN)10.1021/acs.jpcc.3c08347 (DOI)2-s2.0-85189532379 (Scopus ID)
Funder
Knut and Alice Wallenberg Foundation
Note

Validerad;2024;Nivå 2;2024-04-12 (joosat);

Funder: Jane and Aatos Erkko Foundation; Dr. Barbara Mez-Starck foundation;

Full text: CC BY license

Available from: 2024-04-09 Created: 2024-04-09 Last updated: 2024-04-12Bibliographically approved
Sotoudeh, M., Laasonen, K. & Busch, M. (2023). Benchmarking the computed proton solvation energy and absolute potential in non-aqueous solvents. Electrochimica Acta, 443, Article ID 141785.
Open this publication in new window or tab >>Benchmarking the computed proton solvation energy and absolute potential in non-aqueous solvents
2023 (English)In: Electrochimica Acta, ISSN 0013-4686, E-ISSN 1873-3859, Vol. 443, article id 141785Article in journal (Refereed) Published
Identifiers
urn:nbn:se:ltu:diva-104057 (URN)10.1016/j.electacta.2022.141785 (DOI)2-s2.0-85146658300 (Scopus ID)
Funder
German Research Foundation (DFG)
Available from: 2024-02-01 Created: 2024-02-01 Last updated: 2024-03-07Bibliographically approved
Sellin, A., Busch, M., Wildlock, M., Ahlberg, E. & Simic, N. (2023). Can Telluric Acid Replace Chromate as a Homogeneous Catalyst in the Chlorate Process?. ChemElectroChem, 10(22)
Open this publication in new window or tab >>Can Telluric Acid Replace Chromate as a Homogeneous Catalyst in the Chlorate Process?
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2023 (English)In: ChemElectroChem, E-ISSN 2196-0216, Vol. 10, no 22Article in journal (Refereed) Published
National Category
Chemical Engineering Chemical Sciences
Identifiers
urn:nbn:se:ltu:diva-104048 (URN)10.1002/celc.202300304 (DOI)001101849100001 ()2-s2.0-85176546765 (Scopus ID)
Available from: 2024-02-01 Created: 2024-02-01 Last updated: 2024-03-09Bibliographically approved
Khakpour, R., Lindberg, D., Laasonen, K. & Busch, M. (2023). CO2 or Carbonates – What is the Active Species in Electrochemical CO2 Reduction over Fe-Porphyrin?. ChemCatChem, 15(6), Article ID e202201671.
Open this publication in new window or tab >>CO2 or Carbonates – What is the Active Species in Electrochemical CO2 Reduction over Fe-Porphyrin?
2023 (English)In: ChemCatChem, ISSN 1867-3880, E-ISSN 1867-3899, Vol. 15, no 6, article id e202201671Article in journal (Refereed) Published
Place, publisher, year, edition, pages
John Wiley & Sons, 2023
National Category
Chemical Sciences
Identifiers
urn:nbn:se:ltu:diva-104056 (URN)10.1002/cctc.202201671 (DOI)000939117500001 ()2-s2.0-85148111778 (Scopus ID)
Available from: 2024-02-01 Created: 2024-02-01 Last updated: 2024-03-09Bibliographically approved
Hashemi, A., Khakpour, R., Mahdian, A., Busch, M., Peljo, P. & Laasonen, K. (2023). Density functional theory and machine learning for electrochemical square-scheme prediction: an application to quinone-type molecules relevant to redox flow batteries. Digital Discovery, 2(5), 1565-1576
Open this publication in new window or tab >>Density functional theory and machine learning for electrochemical square-scheme prediction: an application to quinone-type molecules relevant to redox flow batteries
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2023 (English)In: Digital Discovery, E-ISSN 2635-098X, Vol. 2, no 5, p. 1565-1576Article in journal (Refereed) Published
National Category
Chemical Sciences
Identifiers
urn:nbn:se:ltu:diva-104054 (URN)10.1039/d3dd00091e (DOI)001105264600001 ()2-s2.0-85172795641 (Scopus ID)
Funder
Academy of Finland, 315739EU, Horizon 2020, 875565
Available from: 2024-02-01 Created: 2024-02-01 Last updated: 2024-03-09Bibliographically approved
Khakpour, R., Laasonen, K. & Busch, M. (2023). Selectivity of CO2, carbonic acid and bicarbonate electroreduction over Iron-porphyrin catalyst: A DFT study. Electrochimica Acta, 442, Article ID 141784.
Open this publication in new window or tab >>Selectivity of CO2, carbonic acid and bicarbonate electroreduction over Iron-porphyrin catalyst: A DFT study
2023 (English)In: Electrochimica Acta, ISSN 0013-4686, E-ISSN 1873-3859, Vol. 442, article id 141784Article in journal (Refereed) Published
Place, publisher, year, edition, pages
Elsevier, 2023
National Category
Other Chemical Engineering
Identifiers
urn:nbn:se:ltu:diva-104045 (URN)10.1016/j.electacta.2022.141784 (DOI)000927375000001 ()2-s2.0-85149721893 (Scopus ID)
Available from: 2024-02-01 Created: 2024-02-01 Last updated: 2024-03-09Bibliographically approved
Busch, M. & Sotoudeh, M. (2023). The role of exact exchange on the structure of water dimer radical cation: Hydrogen bond vs hemibond. Journal of Chemical Physics, 159(3), Article ID 034303.
Open this publication in new window or tab >>The role of exact exchange on the structure of water dimer radical cation: Hydrogen bond vs hemibond
2023 (English)In: Journal of Chemical Physics, ISSN 0021-9606, E-ISSN 1089-7690, Vol. 159, no 3, article id 034303Article in journal (Refereed) Published
Place, publisher, year, edition, pages
American Institute of Physics (AIP), 2023
National Category
Chemical Sciences Physical Sciences
Identifiers
urn:nbn:se:ltu:diva-104055 (URN)10.1063/5.0153759 (DOI)2-s2.0-85166158975 (Scopus ID)
Funder
German Research Foundation (DFG), INST 40/575-1 FUGG (JUSTUS 2 cluster)German Research Foundation (DFG), Project ID 390874152 (POLiS Cluster of Excellence)
Available from: 2024-02-01 Created: 2024-02-01 Last updated: 2024-03-09Bibliographically approved
Busch, M., Wildlock, M., Simic, N. & Ahlberg, E. (2022). Can We Replace Cr(VI) as a Homogeneous Catalyst in the Chlorate Process?. The Journal of Physical Chemistry C, 126(24), 10061-10072
Open this publication in new window or tab >>Can We Replace Cr(VI) as a Homogeneous Catalyst in the Chlorate Process?
2022 (English)In: The Journal of Physical Chemistry C, ISSN 1932-7447, E-ISSN 1932-7455, Vol. 126, no 24, p. 10061-10072Article in journal (Refereed) Published
Place, publisher, year, edition, pages
American Chemical Society (ACS), 2022
National Category
Other Materials Engineering
Identifiers
urn:nbn:se:ltu:diva-104040 (URN)10.1021/acs.jpcc.2c02717 (DOI)000818995700001 ()2-s2.0-85134633335 (Scopus ID)
Available from: 2024-02-01 Created: 2024-02-01 Last updated: 2024-03-09Bibliographically approved
Busch, M., Simic, N. & Ahlberg, E. (2022). Exploring the Mechanism of Cr(VI) Catalyzed Hypochlorous Acid Decomposition. ChemCatChem, 14(15)
Open this publication in new window or tab >>Exploring the Mechanism of Cr(VI) Catalyzed Hypochlorous Acid Decomposition
2022 (English)In: ChemCatChem, ISSN 1867-3880, E-ISSN 1867-3899, Vol. 14, no 15Article in journal (Refereed) Published
Place, publisher, year, edition, pages
Wiley-Blackwell, 2022
National Category
Other Chemical Engineering
Identifiers
urn:nbn:se:ltu:diva-104042 (URN)10.1002/cctc.202101850 (DOI)000778018900001 ()2-s2.0-85127201906 (Scopus ID)
Available from: 2024-02-01 Created: 2024-02-01 Last updated: 2024-03-09Bibliographically approved
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ORCID iD: ORCID iD iconorcid.org/0000-0003-3883-2868

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