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Article: Mechanical Interlocking Enhances the Electrocatalytic Oxygen Reduction Activity and Selectivity of Molecular Copper Complexes

TitleMechanical Interlocking Enhances the Electrocatalytic Oxygen Reduction Activity and Selectivity of Molecular Copper Complexes
Authors
Issue Date28-Feb-2023
PublisherAmerican Chemical Society
Citation
Journal of the American Chemical Society, 2023, v. 145, n. 11, p. 6087-6099 How to Cite?
Abstract

Efficient O2 reduction reaction (ORR) for selective H2O generation enables advanced fuel cell technology. Nonprecious metal catalysts are viable and attractive alternatives to state-of-the-art Pt-based materials that are expensive. Cu complexes inspired by Cu-containing O2 reduction enzymes in nature are yet to reach their desired ORR catalytic performance. Here, the concept of mechanical interlocking is introduced to the ligand architecture to enforce dynamic spatial restriction on the Cu coordination site. Interlocked catenane ligands could govern O2 binding mode, promote electron transfer, and facilitate product elimination. Our results show that ligand interlocking as a catenane steers the ORR selectivity to H2O as the major product via the 4e pathway, rivaling the selectivity of Pt, and boosts the onset potential by 130 mV, the mass activity by 1.8 times, and the turnover frequency by 1.5 fold as compared to the noninterlocked counterpart. Our Cu catenane complex represents one of the first examples to take advantage of mechanical interlocking to afford electrocatalysts with enhanced activity and selectivity. The mechanistic insights gained through this integrated experimental and theoretical study are envisioned to be valuable not just to the area of ORR energy catalysis but also with broad implications on interlocked metal complexes that are of critical importance to the general fields in redox reactions involving proton-coupled electron transfer steps.


Persistent Identifierhttp://hdl.handle.net/10722/328529
ISSN
2023 Impact Factor: 14.4
2023 SCImago Journal Rankings: 5.489

 

DC FieldValueLanguage
dc.contributor.authorMo, Xiaoyong-
dc.contributor.authorDeng, Yulin-
dc.contributor.authorLai, Samuel Kin Man-
dc.contributor.authorGao, Xutao-
dc.contributor.authorYu, Hung Ling-
dc.contributor.authorLow, Kam Hung-
dc.contributor.authorGuo, Zhengxiao-
dc.contributor.authorWu, Heng Liang-
dc.contributor.authorAu Yeung, Ho Yu-
dc.contributor.authorTse, Edmund CM-
dc.date.accessioned2023-06-28T04:45:46Z-
dc.date.available2023-06-28T04:45:46Z-
dc.date.issued2023-02-28-
dc.identifier.citationJournal of the American Chemical Society, 2023, v. 145, n. 11, p. 6087-6099-
dc.identifier.issn0002-7863-
dc.identifier.urihttp://hdl.handle.net/10722/328529-
dc.description.abstract<p>Efficient O<sub>2</sub> reduction reaction (ORR) for selective H<sub>2</sub>O generation enables advanced fuel cell technology. Nonprecious metal catalysts are viable and attractive alternatives to state-of-the-art Pt-based materials that are expensive. Cu complexes inspired by Cu-containing O<sub>2</sub> reduction enzymes in nature are yet to reach their desired ORR catalytic performance. Here, the concept of mechanical interlocking is introduced to the ligand architecture to enforce dynamic spatial restriction on the Cu coordination site. Interlocked catenane ligands could govern O<sub>2</sub> binding mode, promote electron transfer, and facilitate product elimination. Our results show that ligand interlocking as a catenane steers the ORR selectivity to H<sub>2</sub>O as the major product via the 4e<sup>–</sup> pathway, rivaling the selectivity of Pt, and boosts the onset potential by 130 mV, the mass activity by 1.8 times, and the turnover frequency by 1.5 fold as compared to the noninterlocked counterpart. Our Cu catenane complex represents one of the first examples to take advantage of mechanical interlocking to afford electrocatalysts with enhanced activity and selectivity. The mechanistic insights gained through this integrated experimental and theoretical study are envisioned to be valuable not just to the area of ORR energy catalysis but also with broad implications on interlocked metal complexes that are of critical importance to the general fields in redox reactions involving proton-coupled electron transfer steps.</p>-
dc.languageeng-
dc.publisherAmerican Chemical Society-
dc.relation.ispartofJournal of the American Chemical Society-
dc.titleMechanical Interlocking Enhances the Electrocatalytic Oxygen Reduction Activity and Selectivity of Molecular Copper Complexes-
dc.typeArticle-
dc.identifier.doi10.1021/jacs.2c10988-
dc.identifier.volume145-
dc.identifier.issue11-
dc.identifier.spage6087-
dc.identifier.epage6099-
dc.identifier.eissn1520-5126-
dc.identifier.issnl0002-7863-

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