Direct Observation of Electron Donation onto the Reactants and a Transient Poisoning Mechanism During CO₂ Electroreduction on Ni Single Atom Catalysts

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dc.contributor.authorLeverett, J.
dc.contributor.authorBaghestani, G.
dc.contributor.authorTran-Phu, T.
dc.contributor.authorYuwono, J.A.
dc.contributor.authorKumar, P.
dc.contributor.authorJohannessen, B.
dc.contributor.authorSimondson, D.
dc.contributor.authorWen, H.
dc.contributor.authorChang, S.L.Y.
dc.contributor.authorTricoli, A.
dc.contributor.authorSimonov, A.N.
dc.contributor.authorDai, L.
dc.contributor.authorAmal, R.
dc.contributor.authorDaiyan, R.
dc.contributor.authorHocking, R.K.
dc.date.issued2025
dc.description.abstractSingle atom catalysts (SACs) are an important class of materials that mediate chemical reduction reactions, a key subset of which is Ni within a carbon support for the electrochemical CO₂ reduction reaction (CO₂RR). However, how the metal atom/clusters and the carbon-based support act in concert to catalyze CO₂RR is not well understood, with most reports attributing activity solely to the Ni-Nₓ/C moieties. To address this gap, we have undertaken a mechanistic investigation, employing in situ X-ray absorption spectroscopy (XAS) coupled with electrochemical studies and density functional theory (DFT) calculations to further understand how Ni single atoms work in conjunction with the nitrogen-doped carbon matrix to promote CO₂RR to CO, and how the presence of impurities such as those present in CO₂-containing waste flue gases (including NOₓ, and CN¯) changes the catalyst upon reduction. In contrast to previous works, we do not find strong evidence for a purely metal-based reduction upon application of negative reductive potentials. Instead, we present evidence for an increase in the equatorial vs. axial splitting of Ni, consistent with electrons moving onto the reactants via the Ni single atom 3dz² orbital. In addition, we demonstrate a transient poisoning mechanism of the Ni SAC by nitrite and thiocyanate, explaining the recovery of activity during CO₂RR. These insights can aid the design of practical CO₂ valorization technologies.
dc.description.statementofresponsibilityJosh Leverett, Ghazal Baghestani, Thanh Tran-Phu, Jodie A. Yuwono, Priyank Kumar, Bernt Johannessen, Darcy Simondson, Haotien Wen, Shery L. Y. Chang, Antonio Tricoli, Alexandr N. Simonov, Liming Dai, Rose Amal, Rahman Daiyan, and Rosalie K. Hocking
dc.identifier.citationAngewandte Chemie International Edition, 2025; 64(18):e202424087-1-e202424087-11
dc.identifier.doi10.1002/anie.202424087
dc.identifier.issn1433-7851
dc.identifier.issn1521-3773
dc.identifier.orcidYuwono, J.A. [0000-0002-0915-0756]
dc.identifier.urihttps://hdl.handle.net/2440/146397
dc.language.isoen
dc.publisherWiley
dc.relation.granthttp://purl.org/au-research/grants/arc/IH18010002
dc.relation.granthttp://purl.org/au-research/grants/arc/CE23010003
dc.relation.granthttp://purl.org/au-research/grants/arc/IC20010002
dc.relation.granthttp://purl.org/au-research/grants/arc/DP2001018
dc.relation.granthttp://purl.org/au-research/grants/arc/DE230101396
dc.relation.granthttp://purl.org/au-research/grants/arc/FT230100054
dc.relation.granthttp://purl.org/au-research/grants/arc/FT200100317
dc.relation.granthttp://purl.org/au-research/grants/arc/FT200100939
dc.rights© 2025 The Author(s). Angewandte Chemie International Editionpublished by Wiley-VCH GmbH. This is an open access article under the terms of the Creative Commons Attribution Non-Commercial License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited and is not usedfor commercial purposes.
dc.source.urihttps://doi.org/10.1002/anie.202424087
dc.subjectCO₂RR; single atom catalyst; XAS; catalyst poisoning; impurity tolerance
dc.titleDirect Observation of Electron Donation onto the Reactants and a Transient Poisoning Mechanism During CO₂ Electroreduction on Ni Single Atom Catalysts
dc.typeJournal article
pubs.publication-statusPublished online

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