MoS2-confined Rh-Zn atomic pair boosts photo-driven methane carbonylation to acetic acid
Abstract Direct carbonylation of CH4 to CH3COOH provides a promising pathway for upgrading of natural gas to transportable liquid chemicals, in which high-efficiency CH4 activation and controllable C–C coupling are both critical but challenging. Herein, we report that highly efficient photo-driven c...
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| Format: | Article |
| Language: | English |
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Nature Portfolio
2025-01-01
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| Series: | Nature Communications |
| Online Access: | https://doi.org/10.1038/s41467-024-54061-z |
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| author | Yanan Li Huan Liu Jun Mao Meng Gao Yunlong Zhang Qiao Zhao Meng Liu Yao Song Jingting Hu Wangwang Zhang Rui Huang Wu Zhou Kaifeng Wu Wei Liu Liang Yu Xiaoju Cui Dehui Deng |
| author_facet | Yanan Li Huan Liu Jun Mao Meng Gao Yunlong Zhang Qiao Zhao Meng Liu Yao Song Jingting Hu Wangwang Zhang Rui Huang Wu Zhou Kaifeng Wu Wei Liu Liang Yu Xiaoju Cui Dehui Deng |
| author_sort | Yanan Li |
| collection | DOAJ |
| description | Abstract Direct carbonylation of CH4 to CH3COOH provides a promising pathway for upgrading of natural gas to transportable liquid chemicals, in which high-efficiency CH4 activation and controllable C–C coupling are both critical but challenging. Herein, we report that highly efficient photo-driven carbonylation of CH4 with CO and O2 to CH3COOH is achieved over MoS2-confined Rh-Zn atomic-pair in conjunction with TiO2. It delivers a high CH3COOH productivity of 152.0 μmol gcat. −1 h−1 and turnover frequency of 62.0 h−1 with a superior selectivity of 96.5%, outperforming previous photocatalytic CH4 carbonylation processes. Mechanistic investigations disclose the key effect of Rh-Zn synergy in combination with photo-excited electrons from TiO2 for CH3COOH formation. The active OH species produced from O2 photoreduction on the Zn site through proton-coupled electron transfer promotes CH4 dissociation to CH3 species, which then facilely couples with adsorbed CO on the adjacent Rh site forming the key CH3CO intermediate for CH3COOH formation. |
| format | Article |
| id | doaj-art-3979190645074fd6bfdbc6c24bd7e537 |
| institution | Kabale University |
| issn | 2041-1723 |
| language | English |
| publishDate | 2025-01-01 |
| publisher | Nature Portfolio |
| record_format | Article |
| series | Nature Communications |
| spelling | doaj-art-3979190645074fd6bfdbc6c24bd7e5372025-01-12T12:30:36ZengNature PortfolioNature Communications2041-17232025-01-0116111010.1038/s41467-024-54061-zMoS2-confined Rh-Zn atomic pair boosts photo-driven methane carbonylation to acetic acidYanan Li0Huan Liu1Jun Mao2Meng Gao3Yunlong Zhang4Qiao Zhao5Meng Liu6Yao Song7Jingting Hu8Wangwang Zhang9Rui Huang10Wu Zhou11Kaifeng Wu12Wei Liu13Liang Yu14Xiaoju Cui15Dehui Deng16State Key Laboratory of Physical Chemistry of Solid Surfaces, Collaborative Innovation Center of Chemistry for Energy Materials, College of Chemistry and Chemical Engineering, Xiamen UniversityState Key Laboratory of Catalysis, Collaborative Innovation Center of Chemistry for Energy Materials, Dalian Institute of Chemical Physics, Chinese Academy of SciencesState Key Laboratory of Physical Chemistry of Solid Surfaces, Collaborative Innovation Center of Chemistry for Energy Materials, College of Chemistry and Chemical Engineering, Xiamen UniversitySchool of Physical Sciences and CAS Key Laboratory of Vacuum Physics, University of Chinese Academy of SciencesState Key Laboratory of Catalysis, Collaborative Innovation Center of Chemistry for Energy Materials, Dalian Institute of Chemical Physics, Chinese Academy of SciencesState Key Laboratory of Catalysis, Collaborative Innovation Center of Chemistry for Energy Materials, Dalian Institute of Chemical Physics, Chinese Academy of SciencesUniversity of Chinese Academy of SciencesState Key Laboratory of Catalysis, Collaborative Innovation Center of Chemistry for Energy Materials, Dalian Institute of Chemical Physics, Chinese Academy of SciencesState Key Laboratory of Catalysis, Collaborative Innovation Center of Chemistry for Energy Materials, Dalian Institute of Chemical Physics, Chinese Academy of SciencesState Key Laboratory of Physical Chemistry of Solid Surfaces, Collaborative Innovation Center of Chemistry for Energy Materials, College of Chemistry and Chemical Engineering, Xiamen UniversityState Key Laboratory of Catalysis, Collaborative Innovation Center of Chemistry for Energy Materials, Dalian Institute of Chemical Physics, Chinese Academy of SciencesSchool of Physical Sciences and CAS Key Laboratory of Vacuum Physics, University of Chinese Academy of SciencesUniversity of Chinese Academy of SciencesState Key Laboratory of Catalysis, Collaborative Innovation Center of Chemistry for Energy Materials, Dalian Institute of Chemical Physics, Chinese Academy of SciencesState Key Laboratory of Catalysis, Collaborative Innovation Center of Chemistry for Energy Materials, Dalian Institute of Chemical Physics, Chinese Academy of SciencesState Key Laboratory of Catalysis, Collaborative Innovation Center of Chemistry for Energy Materials, Dalian Institute of Chemical Physics, Chinese Academy of SciencesState Key Laboratory of Physical Chemistry of Solid Surfaces, Collaborative Innovation Center of Chemistry for Energy Materials, College of Chemistry and Chemical Engineering, Xiamen UniversityAbstract Direct carbonylation of CH4 to CH3COOH provides a promising pathway for upgrading of natural gas to transportable liquid chemicals, in which high-efficiency CH4 activation and controllable C–C coupling are both critical but challenging. Herein, we report that highly efficient photo-driven carbonylation of CH4 with CO and O2 to CH3COOH is achieved over MoS2-confined Rh-Zn atomic-pair in conjunction with TiO2. It delivers a high CH3COOH productivity of 152.0 μmol gcat. −1 h−1 and turnover frequency of 62.0 h−1 with a superior selectivity of 96.5%, outperforming previous photocatalytic CH4 carbonylation processes. Mechanistic investigations disclose the key effect of Rh-Zn synergy in combination with photo-excited electrons from TiO2 for CH3COOH formation. The active OH species produced from O2 photoreduction on the Zn site through proton-coupled electron transfer promotes CH4 dissociation to CH3 species, which then facilely couples with adsorbed CO on the adjacent Rh site forming the key CH3CO intermediate for CH3COOH formation.https://doi.org/10.1038/s41467-024-54061-z |
| spellingShingle | Yanan Li Huan Liu Jun Mao Meng Gao Yunlong Zhang Qiao Zhao Meng Liu Yao Song Jingting Hu Wangwang Zhang Rui Huang Wu Zhou Kaifeng Wu Wei Liu Liang Yu Xiaoju Cui Dehui Deng MoS2-confined Rh-Zn atomic pair boosts photo-driven methane carbonylation to acetic acid Nature Communications |
| title | MoS2-confined Rh-Zn atomic pair boosts photo-driven methane carbonylation to acetic acid |
| title_full | MoS2-confined Rh-Zn atomic pair boosts photo-driven methane carbonylation to acetic acid |
| title_fullStr | MoS2-confined Rh-Zn atomic pair boosts photo-driven methane carbonylation to acetic acid |
| title_full_unstemmed | MoS2-confined Rh-Zn atomic pair boosts photo-driven methane carbonylation to acetic acid |
| title_short | MoS2-confined Rh-Zn atomic pair boosts photo-driven methane carbonylation to acetic acid |
| title_sort | mos2 confined rh zn atomic pair boosts photo driven methane carbonylation to acetic acid |
| url | https://doi.org/10.1038/s41467-024-54061-z |
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