Engineering p‐Orbital States via Molecular Modules in All‐Organic Electrocatalysts toward Direct Water Oxidation
Abstract Oxygen evolution reaction (OER) is an indispensable anode reaction for sustainable hydrogen production from water electrolysis, yet overreliance on metal‐based catalysts featured with vibrant d‐electrons. It still has notable gap between metal‐free and metal‐based electrocatalysts, due to l...
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Wiley
2025-02-01
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| Series: | Advanced Science |
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| Online Access: | https://doi.org/10.1002/advs.202410507 |
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| author | Li‐Hong Yu Xue‐Feng Zhang Zi‐Ming Ye Hong‐Gang Du Li‐Dong Wang Ping‐Ping Xu Yuhai Dou Li‐Ming Cao Chun‐Ting He |
| author_facet | Li‐Hong Yu Xue‐Feng Zhang Zi‐Ming Ye Hong‐Gang Du Li‐Dong Wang Ping‐Ping Xu Yuhai Dou Li‐Ming Cao Chun‐Ting He |
| author_sort | Li‐Hong Yu |
| collection | DOAJ |
| description | Abstract Oxygen evolution reaction (OER) is an indispensable anode reaction for sustainable hydrogen production from water electrolysis, yet overreliance on metal‐based catalysts featured with vibrant d‐electrons. It still has notable gap between metal‐free and metal‐based electrocatalysts, due to lacking accurate and efficient p‐band regulation methods on non‐metal atoms. Herein, a molecular modularization strategy is proposed for fine‐tuning the p‐orbital states of series metal‐free covalent organic frameworks (COFs) for realizing OER performance beyond benchmark precious metal catalysts. Optimized combination of benzodioxazole/benzodiimide‐based building blocks achieves an impressive applied potential of 1.670 ± 0.004 V versus reversible hydrogen electrode (RHE) and 1.735 ± 0.006 V versus RHE to deliver enhanced current densities of 0.5 and 1.0 A cm−2, respectively. Moreover, it holds a notable charge transfer amount (stands for a long service life) within operation period that outperforms all reported metal‐free electrocatalysts. Operando differential electrochemical mass spectrometry (DEMS) with isotope labeling identifies the adsorbate evolution mechanism (AEM). A variety of spectroscopic techniques and density functional theory (DFT) calculations reveal that the p‐band center of these catalysts can be shifted stepwise to optimize the oxygen intermediate adsorption and lower the reaction energy barrier. This work provides a novel perspective for enhancing the electrocatalytic performance of metal‐free COFs. |
| format | Article |
| id | doaj-art-f8ca55b1b86c461291efff5198b3355a |
| institution | Kabale University |
| issn | 2198-3844 |
| language | English |
| publishDate | 2025-02-01 |
| publisher | Wiley |
| record_format | Article |
| series | Advanced Science |
| spelling | doaj-art-f8ca55b1b86c461291efff5198b3355a2025-02-04T13:14:54ZengWileyAdvanced Science2198-38442025-02-01125n/an/a10.1002/advs.202410507Engineering p‐Orbital States via Molecular Modules in All‐Organic Electrocatalysts toward Direct Water OxidationLi‐Hong Yu0Xue‐Feng Zhang1Zi‐Ming Ye2Hong‐Gang Du3Li‐Dong Wang4Ping‐Ping Xu5Yuhai Dou6Li‐Ming Cao7Chun‐Ting He8Key Lab of Fluorine and Silicon for Energy Materials and Chemistry of Ministry of Education College of Chemistry and Materials Jiangxi Normal University Nanchang 330022 ChinaKey Lab of Fluorine and Silicon for Energy Materials and Chemistry of Ministry of Education College of Chemistry and Materials Jiangxi Normal University Nanchang 330022 ChinaDepartment of Chemistry Northwestern University Evanston IL 60208 USAKey Lab of Fluorine and Silicon for Energy Materials and Chemistry of Ministry of Education College of Chemistry and Materials Jiangxi Normal University Nanchang 330022 ChinaKey Lab of Fluorine and Silicon for Energy Materials and Chemistry of Ministry of Education College of Chemistry and Materials Jiangxi Normal University Nanchang 330022 ChinaKey Lab of Fluorine and Silicon for Energy Materials and Chemistry of Ministry of Education College of Chemistry and Materials Jiangxi Normal University Nanchang 330022 ChinaInstitute of Energy Materials Science University of Shanghai for Science and Technology Shanghai 200093 ChinaKey Lab of Fluorine and Silicon for Energy Materials and Chemistry of Ministry of Education College of Chemistry and Materials Jiangxi Normal University Nanchang 330022 ChinaKey Lab of Fluorine and Silicon for Energy Materials and Chemistry of Ministry of Education College of Chemistry and Materials Jiangxi Normal University Nanchang 330022 ChinaAbstract Oxygen evolution reaction (OER) is an indispensable anode reaction for sustainable hydrogen production from water electrolysis, yet overreliance on metal‐based catalysts featured with vibrant d‐electrons. It still has notable gap between metal‐free and metal‐based electrocatalysts, due to lacking accurate and efficient p‐band regulation methods on non‐metal atoms. Herein, a molecular modularization strategy is proposed for fine‐tuning the p‐orbital states of series metal‐free covalent organic frameworks (COFs) for realizing OER performance beyond benchmark precious metal catalysts. Optimized combination of benzodioxazole/benzodiimide‐based building blocks achieves an impressive applied potential of 1.670 ± 0.004 V versus reversible hydrogen electrode (RHE) and 1.735 ± 0.006 V versus RHE to deliver enhanced current densities of 0.5 and 1.0 A cm−2, respectively. Moreover, it holds a notable charge transfer amount (stands for a long service life) within operation period that outperforms all reported metal‐free electrocatalysts. Operando differential electrochemical mass spectrometry (DEMS) with isotope labeling identifies the adsorbate evolution mechanism (AEM). A variety of spectroscopic techniques and density functional theory (DFT) calculations reveal that the p‐band center of these catalysts can be shifted stepwise to optimize the oxygen intermediate adsorption and lower the reaction energy barrier. This work provides a novel perspective for enhancing the electrocatalytic performance of metal‐free COFs.https://doi.org/10.1002/advs.202410507catalytic mechanismcovalent organic frameworks (COFs)electrocatalystsoxygen evolution reaction (OER) |
| spellingShingle | Li‐Hong Yu Xue‐Feng Zhang Zi‐Ming Ye Hong‐Gang Du Li‐Dong Wang Ping‐Ping Xu Yuhai Dou Li‐Ming Cao Chun‐Ting He Engineering p‐Orbital States via Molecular Modules in All‐Organic Electrocatalysts toward Direct Water Oxidation Advanced Science catalytic mechanism covalent organic frameworks (COFs) electrocatalysts oxygen evolution reaction (OER) |
| title | Engineering p‐Orbital States via Molecular Modules in All‐Organic Electrocatalysts toward Direct Water Oxidation |
| title_full | Engineering p‐Orbital States via Molecular Modules in All‐Organic Electrocatalysts toward Direct Water Oxidation |
| title_fullStr | Engineering p‐Orbital States via Molecular Modules in All‐Organic Electrocatalysts toward Direct Water Oxidation |
| title_full_unstemmed | Engineering p‐Orbital States via Molecular Modules in All‐Organic Electrocatalysts toward Direct Water Oxidation |
| title_short | Engineering p‐Orbital States via Molecular Modules in All‐Organic Electrocatalysts toward Direct Water Oxidation |
| title_sort | engineering p orbital states via molecular modules in all organic electrocatalysts toward direct water oxidation |
| topic | catalytic mechanism covalent organic frameworks (COFs) electrocatalysts oxygen evolution reaction (OER) |
| url | https://doi.org/10.1002/advs.202410507 |
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