Enhancing polyol/sugar cascade oxidation to formic acid with defect rich MnO2 catalysts
Abstract Oxidation of renewable polyol/sugar into formic acid using molecular O2 over heterogeneous catalysts is still challenging due to the insufficient activation of both O2 and organic substrates on coordination-saturated metal oxides. In this study, we develop a defective MnO2 catalyst through...
| Main Authors: | , , , , , , , , , , , , , , , , |
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| Format: | Article |
| Language: | English |
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Nature Portfolio
2023-07-01
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| Series: | Nature Communications |
| Online Access: | https://doi.org/10.1038/s41467-023-40306-w |
| _version_ | 1797769441039089664 |
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| author | Hao Yan Bowen Liu Xin Zhou Fanyu Meng Mingyue Zhao Yue Pan Jie Li Yining Wu Hui Zhao Yibin Liu Xiaobo Chen Lina Li Xiang Feng De Chen Honghong Shan Chaohe Yang Ning Yan |
| author_facet | Hao Yan Bowen Liu Xin Zhou Fanyu Meng Mingyue Zhao Yue Pan Jie Li Yining Wu Hui Zhao Yibin Liu Xiaobo Chen Lina Li Xiang Feng De Chen Honghong Shan Chaohe Yang Ning Yan |
| author_sort | Hao Yan |
| collection | DOAJ |
| description | Abstract Oxidation of renewable polyol/sugar into formic acid using molecular O2 over heterogeneous catalysts is still challenging due to the insufficient activation of both O2 and organic substrates on coordination-saturated metal oxides. In this study, we develop a defective MnO2 catalyst through a coordination number reduction strategy to enhance the aerobic oxidation of various polyols/sugars to formic acid. Compared to common MnO2, the tri-coordinated Mn in the defective MnO2 catalyst displays the electronic reconstruction of surface oxygen charge state and rich surface oxygen vacancies. These oxygen vacancies create more Mnδ+ Lewis acid site together with nearby oxygen as Lewis base sites. This combined structure behaves much like Frustrated Lewis pairs, serving to facilitate the activation of O2, as well as C–C and C–H bonds. As a result, the defective MnO2 catalyst shows high catalytic activity (turnover frequency: 113.5 h−1) and formic acid yield (>80%) comparable to noble metal catalysts for glycerol oxidation. The catalytic system is further extended to the oxidation of other polyols/sugars to formic acid with excellent catalytic performance. |
| first_indexed | 2024-03-12T21:08:03Z |
| format | Article |
| id | doaj.art-721312f68b5842acbe3f91fdd1e310a3 |
| institution | Directory Open Access Journal |
| issn | 2041-1723 |
| language | English |
| last_indexed | 2024-03-12T21:08:03Z |
| publishDate | 2023-07-01 |
| publisher | Nature Portfolio |
| record_format | Article |
| series | Nature Communications |
| spelling | doaj.art-721312f68b5842acbe3f91fdd1e310a32023-07-30T11:19:43ZengNature PortfolioNature Communications2041-17232023-07-0114111110.1038/s41467-023-40306-wEnhancing polyol/sugar cascade oxidation to formic acid with defect rich MnO2 catalystsHao Yan0Bowen Liu1Xin Zhou2Fanyu Meng3Mingyue Zhao4Yue Pan5Jie Li6Yining Wu7Hui Zhao8Yibin Liu9Xiaobo Chen10Lina Li11Xiang Feng12De Chen13Honghong Shan14Chaohe Yang15Ning Yan16State Key Laboratory of Heavy Oil Processing, China University of Petroleum (East China)Department of Chemistry, University of LiverpoolState Key Laboratory of Heavy Oil Processing, China University of Petroleum (East China)State Key Laboratory of Heavy Oil Processing, China University of Petroleum (East China)State Key Laboratory of Heavy Oil Processing, China University of Petroleum (East China)State Key Laboratory of Heavy Oil Processing, China University of Petroleum (East China)State Key Laboratory of Heavy Oil Processing, China University of Petroleum (East China)School of Petroleum Engineering, China University of Petroleum (East China)State Key Laboratory of Heavy Oil Processing, China University of Petroleum (East China)State Key Laboratory of Heavy Oil Processing, China University of Petroleum (East China)State Key Laboratory of Heavy Oil Processing, China University of Petroleum (East China)Shanghai Synchrotron Radiation Facility, Shanghai Advanced Research Institute, Chinese Academy of SciencesState Key Laboratory of Heavy Oil Processing, China University of Petroleum (East China)Department of Chemical Engineering, Norwegian University of Science and TechnologyState Key Laboratory of Heavy Oil Processing, China University of Petroleum (East China)State Key Laboratory of Heavy Oil Processing, China University of Petroleum (East China)Department of Chemical and Biomolecular Engineering, National University of SingaporeAbstract Oxidation of renewable polyol/sugar into formic acid using molecular O2 over heterogeneous catalysts is still challenging due to the insufficient activation of both O2 and organic substrates on coordination-saturated metal oxides. In this study, we develop a defective MnO2 catalyst through a coordination number reduction strategy to enhance the aerobic oxidation of various polyols/sugars to formic acid. Compared to common MnO2, the tri-coordinated Mn in the defective MnO2 catalyst displays the electronic reconstruction of surface oxygen charge state and rich surface oxygen vacancies. These oxygen vacancies create more Mnδ+ Lewis acid site together with nearby oxygen as Lewis base sites. This combined structure behaves much like Frustrated Lewis pairs, serving to facilitate the activation of O2, as well as C–C and C–H bonds. As a result, the defective MnO2 catalyst shows high catalytic activity (turnover frequency: 113.5 h−1) and formic acid yield (>80%) comparable to noble metal catalysts for glycerol oxidation. The catalytic system is further extended to the oxidation of other polyols/sugars to formic acid with excellent catalytic performance.https://doi.org/10.1038/s41467-023-40306-w |
| spellingShingle | Hao Yan Bowen Liu Xin Zhou Fanyu Meng Mingyue Zhao Yue Pan Jie Li Yining Wu Hui Zhao Yibin Liu Xiaobo Chen Lina Li Xiang Feng De Chen Honghong Shan Chaohe Yang Ning Yan Enhancing polyol/sugar cascade oxidation to formic acid with defect rich MnO2 catalysts Nature Communications |
| title | Enhancing polyol/sugar cascade oxidation to formic acid with defect rich MnO2 catalysts |
| title_full | Enhancing polyol/sugar cascade oxidation to formic acid with defect rich MnO2 catalysts |
| title_fullStr | Enhancing polyol/sugar cascade oxidation to formic acid with defect rich MnO2 catalysts |
| title_full_unstemmed | Enhancing polyol/sugar cascade oxidation to formic acid with defect rich MnO2 catalysts |
| title_short | Enhancing polyol/sugar cascade oxidation to formic acid with defect rich MnO2 catalysts |
| title_sort | enhancing polyol sugar cascade oxidation to formic acid with defect rich mno2 catalysts |
| url | https://doi.org/10.1038/s41467-023-40306-w |
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