Electrochemical CO2 Reduction Mechanism Exploration: An Integrated Thermodynamic and Kinetic Approach

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School of Chemical Engineering | Doctoral thesis (article-based) | Defence date: 2025-03-26
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Authors

Date

2025

Department

Kemian ja materiaalitieteen laitos
Department of Chemistry and Materials Science

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Mcode

Degree programme

Language

en

Pages

55 + app. 63

Series

Aalto University publication series Doctoral Theses, 53/2025

Abstract

The electrochemical reduction of CO₂ (eCO₂RR) presents a promising strategy to address sustainable energy challenges by converting CO₂ into value-added chemicals and fuels. This thesis employs density functional theory (DFT) to investigate the reaction mechanisms of eCO₂RR, focusing on enhancing computational mthodologies and understanding catalyst performance. Key challenges such as the low reactivity of CO₂ and competition with the hydrogen evolution reaction (HER) are addressed through a systematic evaluation of molecular catalysts including metal porphyrins and phthalocyanines. The research develops advanced computational approaches to accurately model proton-coupled and decoupled electron transfers, essential for analyzing reaction pathways. The findings highlight bicarbonate as a more favorable intermediate compared to CO₂ under neutral pH conditions. Mechanistic insights into post-CO reactions including the formation of C1, C2, and C2+ products elucidate the role of catalyst design and reaction conditions in achieving multi-carbon product formation form single atom catalysts (SACs). Additionally, the study explores pH-dependent selectivity for formaldehyde and methane which aligns computational results with experimental observations. By providing a comprehensive framework for understanding eCO₂RR pathways, this thesis contributes to the rational design of catalytic systems and optimization of reaction conditions for sustainable energy applications and efficient electrocatalysis.

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Supervising professor

Laasonen, Kari, Prof., Aalto University, Department of Chemistry and Materials Science, Finland

Thesis advisor

Busch, Michael, Dr., Luleå University of Technology, Sweden

Keywords

electrochemistry, CO2 reduction, electrocatalyst, density functional theory

Other note

Parts

  • [Publication 1]: Hossain, M. Noor, Reza Khakpour, Michael Busch, Milla Suominen, Kari Laasonen, and Tanja Kallio. Temperature-Controlled Syngas Production via Electrochemical CO2 Reduction on a CoTPP/MWCNT Composite in a Flow Cell. ACS Applied Energy Materials, 6, 1, 267-277, 2022.
    Full text in Acris/Aaltodoc: https://urn.fi/URN:NBN:fi:aalto-202301021014
    DOI: 10.1021/acsaem.2c02873 View at publisher
  • [Publication 2]: Reza Khakpour, Daniel Lindberg, Kari Laasonen, and Michael Busch. CO2 or carbonates–what is the active species in electrochemical CO2 reduction over Fe-Porphyrin? ChemCatChem, 15, 6, e202201671, 2023.
    Full text in Acris/Aaltodoc: https://urn.fi/URN:NBN:fi:aalto-202304052673
    DOI: 10.1002/cctc.202201671 View at publisher
  • [Publication 3]: Reza Khakpour, Kari Laasonen, and Michael Busch. Selectivity of CO2, carbonic acid and bicarbonate electroreduction over Iron-porphyrin catalyst: a DFT study. Electrochimica Acta, 442, 141784, 2023.
    DOI: 10.1016/j.electacta.2022.141784 View at publisher
  • [Publication 4]: Reza Khakpour, Kaveh Farshadfar, Si-Thanh Dong, Benedikt Lassalle-Kaiser, Kari Laasonen, and Michael Busch. Mechanism of CO2 electroreduction to multicarbon products over iron phthalocyanine single-atom catalysts. The Journal of Physical Chemistry C, 128, 14, 5867-5877, 2024.
    Full text in Acris/Aaltodoc: https://urn.fi/URN:NBN:fi:aalto-202405293955
    DOI: 10.1021/acs.jpcc.3c08347 View at publisher
  • [Publication 5]: Ajeet Singh, Afridi Zamader, Reza Khakpour, Kari Laasonen, Michael Busch, and Marc Robert. Molecular electrochemical catalysis of CO-to-formaldehyde conversion with a cobalt complex. Journal of the American Chemical Society, 146, 32, 22129-22133, 2024.
    DOI: 10.1021/jacs.4c06878 View at publisher

Citation

Permanent link to this item

https://urn.fi/URN:ISBN:978-952-64-2444-6

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[diss] Kemian tekniikan korkeakoulu / CHEM