CoOx clusters-decorated IrO2 electrocatalyst activates NO3 - mediator for benzylic C-H activation
Abstract Electrochemical conversion of petrochemical-derived hydrocarbons to high-value oxygenates can utilize renewable energy and reduce carbon emissions. However, this involves the challenging activation of inert C(sp 3)-H bonds at room temperature. Here, we introduce an electrocatalyst:mediator...
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| Format: | Article |
| Language: | English |
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Nature Portfolio
2025-04-01
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| Series: | Nature Communications |
| Online Access: | https://doi.org/10.1038/s41467-025-58733-2 |
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| author | Ziyu Mi Yuke Li Chao Wu Mingsheng Zhang Xun Cao Shibo Xi Jia Zhang Wan Ru Leow |
| author_facet | Ziyu Mi Yuke Li Chao Wu Mingsheng Zhang Xun Cao Shibo Xi Jia Zhang Wan Ru Leow |
| author_sort | Ziyu Mi |
| collection | DOAJ |
| description | Abstract Electrochemical conversion of petrochemical-derived hydrocarbons to high-value oxygenates can utilize renewable energy and reduce carbon emissions. However, this involves the challenging activation of inert C(sp 3)-H bonds at room temperature. Here, we introduce an electrocatalyst:mediator assembly in which CoOx clusters-decorated IrO2 electrocatalyst activates NO3 - mediator to a highly reactive radical capable of abstracting a hydrogen atom from benzylic C-H. The interface between CoOx and IrO2 promotes NO3 - activation by facilitating the desorption of NO3 ● radical for subsequent reaction. Our strategy is demonstrated through the selective oxidation of toluene to benzaldehyde with high Faradaic efficiency of 86( ±1)% at 25 mA/cm2, a factor of >3 times higher than the bare electrocatalyst. The electrocatalyst:mediator assembly is operated stably for 100 h, with minimal decline in performance. When translated into a flow system, a Faradaic efficiency of 60( ±4)% at 200 mA/cm2 was achieved. |
| format | Article |
| id | doaj-art-7355a47aa9f341c59331b96a3fc6d76f |
| institution | OA Journals |
| issn | 2041-1723 |
| language | English |
| publishDate | 2025-04-01 |
| publisher | Nature Portfolio |
| record_format | Article |
| series | Nature Communications |
| spelling | doaj-art-7355a47aa9f341c59331b96a3fc6d76f2025-08-20T02:17:13ZengNature PortfolioNature Communications2041-17232025-04-0116111010.1038/s41467-025-58733-2CoOx clusters-decorated IrO2 electrocatalyst activates NO3 - mediator for benzylic C-H activationZiyu Mi0Yuke Li1Chao Wu2Mingsheng Zhang3Xun Cao4Shibo Xi5Jia Zhang6Wan Ru Leow7School of Chemistry, Chemical Engineering and Biotechnology, Nanyang Technological University; 21 Nanyang Link, Nanyang Technological UniversityInstitute of High Performance Computing (IHPC), Agency for Science, Technology and Research (A*STAR); 1 Fusionopolis Way, #16-16 ConnexisInstitute of Sustainability for Chemicals. Energy and Environment (ISCE, Agency for Science, Technology and Research (A*STAR); 1 Pesek Road Jurong IslandInstitute of Materials Research and Engineering (IMRE), Agency for Science, Technology and Research (A*STAR); 2 Fusionopolis Way, #08-03 InnovisInstitute of Sustainability for Chemicals. Energy and Environment (ISCE, Agency for Science, Technology and Research (A*STAR); 1 Pesek Road Jurong IslandInstitute of Sustainability for Chemicals. Energy and Environment (ISCE, Agency for Science, Technology and Research (A*STAR); 1 Pesek Road Jurong IslandInstitute of High Performance Computing (IHPC), Agency for Science, Technology and Research (A*STAR); 1 Fusionopolis Way, #16-16 ConnexisSchool of Chemistry, Chemical Engineering and Biotechnology, Nanyang Technological University; 21 Nanyang Link, Nanyang Technological UniversityAbstract Electrochemical conversion of petrochemical-derived hydrocarbons to high-value oxygenates can utilize renewable energy and reduce carbon emissions. However, this involves the challenging activation of inert C(sp 3)-H bonds at room temperature. Here, we introduce an electrocatalyst:mediator assembly in which CoOx clusters-decorated IrO2 electrocatalyst activates NO3 - mediator to a highly reactive radical capable of abstracting a hydrogen atom from benzylic C-H. The interface between CoOx and IrO2 promotes NO3 - activation by facilitating the desorption of NO3 ● radical for subsequent reaction. Our strategy is demonstrated through the selective oxidation of toluene to benzaldehyde with high Faradaic efficiency of 86( ±1)% at 25 mA/cm2, a factor of >3 times higher than the bare electrocatalyst. The electrocatalyst:mediator assembly is operated stably for 100 h, with minimal decline in performance. When translated into a flow system, a Faradaic efficiency of 60( ±4)% at 200 mA/cm2 was achieved.https://doi.org/10.1038/s41467-025-58733-2 |
| spellingShingle | Ziyu Mi Yuke Li Chao Wu Mingsheng Zhang Xun Cao Shibo Xi Jia Zhang Wan Ru Leow CoOx clusters-decorated IrO2 electrocatalyst activates NO3 - mediator for benzylic C-H activation Nature Communications |
| title | CoOx clusters-decorated IrO2 electrocatalyst activates NO3 - mediator for benzylic C-H activation |
| title_full | CoOx clusters-decorated IrO2 electrocatalyst activates NO3 - mediator for benzylic C-H activation |
| title_fullStr | CoOx clusters-decorated IrO2 electrocatalyst activates NO3 - mediator for benzylic C-H activation |
| title_full_unstemmed | CoOx clusters-decorated IrO2 electrocatalyst activates NO3 - mediator for benzylic C-H activation |
| title_short | CoOx clusters-decorated IrO2 electrocatalyst activates NO3 - mediator for benzylic C-H activation |
| title_sort | coox clusters decorated iro2 electrocatalyst activates no3 mediator for benzylic c h activation |
| url | https://doi.org/10.1038/s41467-025-58733-2 |
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