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Article: Phosphine-Triggered Structural Defects in Au44 Homologues Boost Electrocatalytic CO2 Reduction

TitlePhosphine-Triggered Structural Defects in Au44 Homologues Boost Electrocatalytic CO2 Reduction
Authors
KeywordsCluster Assembly
Gold Nanoclusters
Homologues
Phosphine Ligands
Structural Defects
Issue Date1-Jan-2023
PublisherWiley
Citation
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2023, v. 62 How to Cite?
Abstract

The systematic induction of structural defects at the atomic level is crucial to metal nanocluster research because it endows cluster-based catalysts with highly reactive centers and allows for a comprehensive investigation of viable reaction pathways. Herein, by substituting neutral phosphine ligands for surface anionic thiolate ligands, we establish that one or two Au3 triangular units can be successfully introduced into the double-stranded helical kernel of Au44(TBBT)28, where TBBT = 4-tert-butylbenzenethiolate, resulting in the formation of two atomically precise defective Au44 nanoclusters. Along with the regular face-centered-cubic (fcc) nanocluster, the first series of mixed-ligand cluster homologues is identified, with a unified formula of Au44(PPh3)n(TBBT)28-2n (n = 0–2). The Au44(PPh3)(TBBT)26 nanocluster having major structural defects at the bottom of the fcc lattice demonstrates superior electrocatalytic performance in the CO2 reduction to CO. Density functional theory calculations indicate that the active site near the defects significantly lowers the free energy for the *COOH formation, the rate-determining step in the whole catalytic process.


Persistent Identifierhttp://hdl.handle.net/10722/329057
ISSN
2023 Impact Factor: 16.1
2023 SCImago Journal Rankings: 5.300
ISI Accession Number ID

 

DC FieldValueLanguage
dc.contributor.authorZhuang, Shengli-
dc.contributor.authorChen, Dong-
dc.contributor.authorNg, Wai Pan-
dc.contributor.authorLiu, Li Juan-
dc.contributor.authorSun, Meng Ying-
dc.contributor.authorLiu, Dongyi-
dc.contributor.authorNawaz, Tehseen-
dc.contributor.authorXia, Qi-
dc.contributor.authorWu, Xia-
dc.contributor.authorHuang, Yong-Liang-
dc.contributor.authorLee, Seungkyu-
dc.contributor.authorYang, Jun-
dc.contributor.authorYang, Jun-
dc.contributor.authorHe, Jian-
dc.date.accessioned2023-08-05T07:54:57Z-
dc.date.available2023-08-05T07:54:57Z-
dc.date.issued2023-01-01-
dc.identifier.citationANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2023, v. 62-
dc.identifier.issn1433-7851-
dc.identifier.urihttp://hdl.handle.net/10722/329057-
dc.description.abstract<p>The systematic induction of structural defects at the atomic level is crucial to metal nanocluster research because it endows cluster-based catalysts with highly reactive centers and allows for a comprehensive investigation of viable reaction pathways. Herein, by substituting neutral phosphine ligands for surface anionic thiolate ligands, we establish that one or two Au3 triangular units can be successfully introduced into the double-stranded helical kernel of Au44(TBBT)28, where TBBT = 4-tert-butylbenzenethiolate, resulting in the formation of two atomically precise defective Au44 nanoclusters. Along with the regular face-centered-cubic (fcc) nanocluster, the first series of mixed-ligand cluster homologues is identified, with a unified formula of Au44(PPh3)n(TBBT)28-2n (n = 0–2). The Au44(PPh3)(TBBT)26 nanocluster having major structural defects at the bottom of the fcc lattice demonstrates superior electrocatalytic performance in the CO2 reduction to CO. Density functional theory calculations indicate that the active site near the defects significantly lowers the free energy for the *COOH formation, the rate-determining step in the whole catalytic process.<br></p>-
dc.languageeng-
dc.publisherWiley-
dc.relation.ispartofANGEWANDTE CHEMIE-INTERNATIONAL EDITION-
dc.rightsThis work is licensed under a Creative Commons Attribution-NonCommercial-NoDerivatives 4.0 International License.-
dc.subjectCluster Assembly-
dc.subjectGold Nanoclusters-
dc.subjectHomologues-
dc.subjectPhosphine Ligands-
dc.subjectStructural Defects-
dc.titlePhosphine-Triggered Structural Defects in Au44 Homologues Boost Electrocatalytic CO2 Reduction-
dc.typeArticle-
dc.identifier.doi10.1002/anie.202306696-
dc.identifier.scopuseid_2-s2.0-85164361619-
dc.identifier.volume62-
dc.identifier.eissn1521-3773-
dc.identifier.isiWOS:001030341000001-
dc.identifier.issnl1433-7851-

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