DC Field | Value | Language |
---|---|---|
dc.contributor.author | Wang, Jin Ming | ko |
dc.contributor.author | Zhu, Qin Yao | ko |
dc.contributor.author | Lee, Jeong Heon | ko |
dc.contributor.author | Woo, Tae Gyun | ko |
dc.contributor.author | Zhang, Yue Xing | ko |
dc.contributor.author | Jang, Woo-Dong | ko |
dc.contributor.author | Kim, Tae Kyu | ko |
dc.date.accessioned | 2024-03-04T10:00:21Z | - |
dc.date.available | 2024-03-04T10:00:21Z | - |
dc.date.created | 2024-02-28 | - |
dc.date.created | 2024-02-28 | - |
dc.date.issued | 2023-06 | - |
dc.identifier.citation | NATURE COMMUNICATIONS, v.14, no.1 | - |
dc.identifier.issn | 2041-1723 | - |
dc.identifier.uri | http://hdl.handle.net/10203/318378 | - |
dc.description.abstract | Diatomic-site catalysts (DACs) garner tremendous attention for selective CO2 photoreduction, especially in the thermodynamical and kinetical mechanism of CO2 to C2+ products. Herein, we first engineer a novel Zn-porphyrin/RuCu-pincer complex DAC (ZnPor-RuCuDAC). The heteronuclear ZnPor-RuCuDAC exhibits the best acetate selectivity (95.1%), while the homoatomic counterparts (ZnPor-Ru(2)DAC and ZnPor-Cu(2)DAC) present the best CO selectivity. In-situ spectroscopic measurements reveal that the heteronuclear Ru-Cu sites easily appear C-1 intermediate coupling. The in-depth analyses confirm that due to the strong gradient orbital coupling of Ru4d-Cu3d resonance, two formed *CO intermediates of Ru-Cu heteroatom show a significantly weaker electrostatic repulsion for an asymmetric charge distribution, which result from a side-to-side absorption and narrow dihedral angle distortion. Moreover, the strongly overlapped Ru/Cu-d and CO molecular orbitals split into bonding and antibonding orbitals easily, resulting in decreasing energy splitting levels of C-1 intermediates. These results collectively augment the collision probability of the two *CO intermediates on heteronuclear DACs. This work first provides a crucial perspective on the symmetry-forbidden coupling mechanism of C-1 intermediates on diatomic sites. Molecular insights into the selectivity mechanism of dual-atom sites are required to engineer efficient solar-fuel catalysts. Here, the authors reveal symmetry-forbidden coupling mechanism of C1 intermediates on diatomic sites by manipulating metal gradient orbital interaction over diatomic COFs. | - |
dc.language | English | - |
dc.publisher | NATURE PORTFOLIO | - |
dc.title | Asymmetric gradient orbital interaction of hetero-diatomic active sites for promoting C - C coupling | - |
dc.type | Article | - |
dc.identifier.wosid | 001022863800002 | - |
dc.identifier.scopusid | 2-s2.0-85163314619 | - |
dc.type.rims | ART | - |
dc.citation.volume | 14 | - |
dc.citation.issue | 1 | - |
dc.citation.publicationname | NATURE COMMUNICATIONS | - |
dc.identifier.doi | 10.1038/s41467-023-39580-5 | - |
dc.contributor.localauthor | Kim, Tae Kyu | - |
dc.contributor.nonIdAuthor | Wang, Jin Ming | - |
dc.contributor.nonIdAuthor | Zhu, Qin Yao | - |
dc.contributor.nonIdAuthor | Lee, Jeong Heon | - |
dc.contributor.nonIdAuthor | Woo, Tae Gyun | - |
dc.contributor.nonIdAuthor | Zhang, Yue Xing | - |
dc.contributor.nonIdAuthor | Jang, Woo-Dong | - |
dc.description.isOpenAccess | N | - |
dc.type.journalArticle | Article | - |
dc.subject.keywordPlus | SELECTIVE CO2 PHOTOREDUCTION | - |
dc.subject.keywordPlus | REDUCTION | - |
dc.subject.keywordPlus | COMPLEXES | - |
dc.subject.keywordPlus | ALCOHOLS | - |
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