Highly Efficient and Selective Photocatalytic Nonoxidative Coupling of Methane to Ethylene over Pd-Zn Synergistic Catalytic Sites
Photocatalytic nonoxidative coupling of CH4 to multicarbon (C2+) hydrocarbons (e.g., C2H4) and H2 under ambient conditions provides a promising energy-conserving approach for utilization of carbon resource. However, as the methyl intermediates prefer to undergo self-coupling to produce ethane, it is...
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| Format: | Article |
| Language: | English |
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American Association for the Advancement of Science (AAAS)
2022-01-01
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| Series: | Research |
| Online Access: | http://dx.doi.org/10.34133/2022/9831340 |
| _version_ | 1827335063109369856 |
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| author | Yanduo Liu Yihong Chen Wenbin Jiang Tingting Kong Pedro H. C. Camargo Chao Gao Yujie Xiong |
| author_facet | Yanduo Liu Yihong Chen Wenbin Jiang Tingting Kong Pedro H. C. Camargo Chao Gao Yujie Xiong |
| author_sort | Yanduo Liu |
| collection | DOAJ |
| description | Photocatalytic nonoxidative coupling of CH4 to multicarbon (C2+) hydrocarbons (e.g., C2H4) and H2 under ambient conditions provides a promising energy-conserving approach for utilization of carbon resource. However, as the methyl intermediates prefer to undergo self-coupling to produce ethane, it is a challenging task to control the selective conversion of CH4 to higher value-added C2H4. Herein, we adopt a synergistic catalysis strategy by integrating Pd-Zn active sites on visible light-responsive defective WO3 nanosheets for synergizing the adsorption, activation, and dehydrogenation processes in CH4 to C2H4 conversion. Benefiting from the synergy, our model catalyst achieves a remarkable C2+ compounds yield of 31.85 μmol·g-1·h-1 with an exceptionally high C2H4 selectivity of 75.3% and a stoichiometric H2 evolution. In situ spectroscopic studies reveal that the Zn sites promote the adsorption and activation of CH4 molecules to generate methyl and methoxy intermediates with the assistance of lattice oxygen, while the Pd sites facilitate the dehydrogenation of methoxy to methylene radicals for producing C2H4 and suppress overoxidation. This work demonstrates a strategy for designing efficient photocatalysts toward selective coupling of CH4 to higher value-added chemicals and highlights the importance of synergistic active sites to the synergy of key steps in catalytic reactions. |
| first_indexed | 2024-03-07T18:09:06Z |
| format | Article |
| id | doaj.art-f7bd2c72e1414c5380bacddabd88daa1 |
| institution | Directory Open Access Journal |
| issn | 2639-5274 |
| language | English |
| last_indexed | 2024-03-07T18:09:06Z |
| publishDate | 2022-01-01 |
| publisher | American Association for the Advancement of Science (AAAS) |
| record_format | Article |
| series | Research |
| spelling | doaj.art-f7bd2c72e1414c5380bacddabd88daa12024-03-02T07:55:43ZengAmerican Association for the Advancement of Science (AAAS)Research2639-52742022-01-01202210.34133/2022/9831340Highly Efficient and Selective Photocatalytic Nonoxidative Coupling of Methane to Ethylene over Pd-Zn Synergistic Catalytic SitesYanduo Liu0Yihong Chen1Wenbin Jiang2Tingting Kong3Pedro H. C. Camargo4Chao Gao5Yujie Xiong6School of Chemistry and Materials Science, University of Science and Technology of China, Hefei, Anhui 230026, China; Institute of Energy Hefei Comprehensive National Science Center, Hefei, Anhui 230031, ChinaSchool of Chemistry and Materials Science, University of Science and Technology of China, Hefei, Anhui 230026, ChinaSchool of Chemistry and Materials Science, University of Science and Technology of China, Hefei, Anhui 230026, ChinaKey Laboratory of Functional Molecular Solids, Ministry of Education, Anhui Engineering Research Center of Carbon Neutrality, College of Chemistry and Materials Science, Anhui Normal University, Wuhu, Anhui 241000, ChinaDepartment of Chemistry, University of Helsinki, FIN-00014, FinlandSchool of Chemistry and Materials Science, University of Science and Technology of China, Hefei, Anhui 230026, ChinaSchool of Chemistry and Materials Science, University of Science and Technology of China, Hefei, Anhui 230026, China; Institute of Energy Hefei Comprehensive National Science Center, Hefei, Anhui 230031, China; Key Laboratory of Functional Molecular Solids, Ministry of Education, Anhui Engineering Research Center of Carbon Neutrality, College of Chemistry and Materials Science, Anhui Normal University, Wuhu, Anhui 241000, ChinaPhotocatalytic nonoxidative coupling of CH4 to multicarbon (C2+) hydrocarbons (e.g., C2H4) and H2 under ambient conditions provides a promising energy-conserving approach for utilization of carbon resource. However, as the methyl intermediates prefer to undergo self-coupling to produce ethane, it is a challenging task to control the selective conversion of CH4 to higher value-added C2H4. Herein, we adopt a synergistic catalysis strategy by integrating Pd-Zn active sites on visible light-responsive defective WO3 nanosheets for synergizing the adsorption, activation, and dehydrogenation processes in CH4 to C2H4 conversion. Benefiting from the synergy, our model catalyst achieves a remarkable C2+ compounds yield of 31.85 μmol·g-1·h-1 with an exceptionally high C2H4 selectivity of 75.3% and a stoichiometric H2 evolution. In situ spectroscopic studies reveal that the Zn sites promote the adsorption and activation of CH4 molecules to generate methyl and methoxy intermediates with the assistance of lattice oxygen, while the Pd sites facilitate the dehydrogenation of methoxy to methylene radicals for producing C2H4 and suppress overoxidation. This work demonstrates a strategy for designing efficient photocatalysts toward selective coupling of CH4 to higher value-added chemicals and highlights the importance of synergistic active sites to the synergy of key steps in catalytic reactions.http://dx.doi.org/10.34133/2022/9831340 |
| spellingShingle | Yanduo Liu Yihong Chen Wenbin Jiang Tingting Kong Pedro H. C. Camargo Chao Gao Yujie Xiong Highly Efficient and Selective Photocatalytic Nonoxidative Coupling of Methane to Ethylene over Pd-Zn Synergistic Catalytic Sites Research |
| title | Highly Efficient and Selective Photocatalytic Nonoxidative Coupling of Methane to Ethylene over Pd-Zn Synergistic Catalytic Sites |
| title_full | Highly Efficient and Selective Photocatalytic Nonoxidative Coupling of Methane to Ethylene over Pd-Zn Synergistic Catalytic Sites |
| title_fullStr | Highly Efficient and Selective Photocatalytic Nonoxidative Coupling of Methane to Ethylene over Pd-Zn Synergistic Catalytic Sites |
| title_full_unstemmed | Highly Efficient and Selective Photocatalytic Nonoxidative Coupling of Methane to Ethylene over Pd-Zn Synergistic Catalytic Sites |
| title_short | Highly Efficient and Selective Photocatalytic Nonoxidative Coupling of Methane to Ethylene over Pd-Zn Synergistic Catalytic Sites |
| title_sort | highly efficient and selective photocatalytic nonoxidative coupling of methane to ethylene over pd zn synergistic catalytic sites |
| url | http://dx.doi.org/10.34133/2022/9831340 |
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