Synergistic effect of Ru-N₄ sites and Cu-N₃ sites in carbon nitride for highly selective photocatalytic reduction of CO₂ to methane
Developing single-atom photocatalysts for selective conversion of CO2 to valuable fuel is of great attraction but remains challenging. In this work, ruthenium and copper single atoms are for the first time simultaneously incorporated into polymeric carbon nitride (PCN) through a simple preassembly-c...
| Main Authors: | , , , , , , , , |
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| Format: | Journal Article |
| Language: | English |
| Published: |
2022
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| Online Access: | https://hdl.handle.net/10356/157146 |
| _version_ | 1811683233915469824 |
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| author | Zeng, Lei Chen, Jie-Wei Zhong, Lixiang Zhen, Wenlong Tay, Yee Yan Li, Shuzhou Wang, Yanggang Huang, Limin Xue, Can |
| author2 | School of Materials Science and Engineering |
| author_facet | School of Materials Science and Engineering Zeng, Lei Chen, Jie-Wei Zhong, Lixiang Zhen, Wenlong Tay, Yee Yan Li, Shuzhou Wang, Yanggang Huang, Limin Xue, Can |
| author_sort | Zeng, Lei |
| collection | NTU |
| description | Developing single-atom photocatalysts for selective conversion of CO2 to valuable fuel is of great attraction but remains challenging. In this work, ruthenium and copper single atoms are for the first time simultaneously incorporated into polymeric carbon nitride (PCN) through a simple preassembly-coprecipitation-pyrolysis process. The obtained PCN-RuCu sample exhibited much higher selectivity (95%) for CH4 production than the individual Ru or Cu decorated PCN during photocatalytic CO2 reduction under visible-light irradiation. The atomically dispersed Ru-N4 and Cu-N3 moieties were confirmed by spherical aberration-corrected electron microscopy and extended X-ray absorption fine structure spectroscopy. Density function theory (DFT) calculations revealed that the co-existence of Ru-N4 sites and Cu-N3 sites can effectively tune the electronic structure of PCN, making the Ru sites account for photogenerated electron-hole pairs and the Cu sites for CO2 hydrogenation. Moreover, the synergetic effect between Ru and Cu single atoms significantly promotes the consecutive hydrogenation processes of *CO species towards CH4 production. Our studies provide a new understanding of the mechanism for photocatalytic reduction of CO2 to CH4, and pave a new way to design photocatalysts for the selective production of solar fuels. |
| first_indexed | 2024-10-01T04:09:29Z |
| format | Journal Article |
| id | ntu-10356/157146 |
| institution | Nanyang Technological University |
| language | English |
| last_indexed | 2024-10-01T04:09:29Z |
| publishDate | 2022 |
| record_format | dspace |
| spelling | ntu-10356/1571462023-07-14T16:04:24Z Synergistic effect of Ru-N₄ sites and Cu-N₃ sites in carbon nitride for highly selective photocatalytic reduction of CO₂ to methane Zeng, Lei Chen, Jie-Wei Zhong, Lixiang Zhen, Wenlong Tay, Yee Yan Li, Shuzhou Wang, Yanggang Huang, Limin Xue, Can School of Materials Science and Engineering Facility for Advanced Characterization Engineering::Materials Dual-Metal-Atom Methane Production Developing single-atom photocatalysts for selective conversion of CO2 to valuable fuel is of great attraction but remains challenging. In this work, ruthenium and copper single atoms are for the first time simultaneously incorporated into polymeric carbon nitride (PCN) through a simple preassembly-coprecipitation-pyrolysis process. The obtained PCN-RuCu sample exhibited much higher selectivity (95%) for CH4 production than the individual Ru or Cu decorated PCN during photocatalytic CO2 reduction under visible-light irradiation. The atomically dispersed Ru-N4 and Cu-N3 moieties were confirmed by spherical aberration-corrected electron microscopy and extended X-ray absorption fine structure spectroscopy. Density function theory (DFT) calculations revealed that the co-existence of Ru-N4 sites and Cu-N3 sites can effectively tune the electronic structure of PCN, making the Ru sites account for photogenerated electron-hole pairs and the Cu sites for CO2 hydrogenation. Moreover, the synergetic effect between Ru and Cu single atoms significantly promotes the consecutive hydrogenation processes of *CO species towards CH4 production. Our studies provide a new understanding of the mechanism for photocatalytic reduction of CO2 to CH4, and pave a new way to design photocatalysts for the selective production of solar fuels. Ministry of Education (MOE) Submitted/Accepted version This work was supported by the Ministry of Education, Singapore, under AcRF-Tier2 (MOE2018-T2-1-017) and AcRF-Tier1 (MOE2019-T1- 002-012, RG102/19). The authors also thank the support from NTU seed funding for Solar Fuels Laboratory. LH thanks for the financial support from Shenzhen Clean Energy Research Institute (CERI-KY-2019-003). Y. G.W and J.W.C were financially supported by NSFC No. 22022504 of China, Guangdong “Pearl River” Talent Plan (No. 2019QN01L353), Shenzhen Science and Technology Plan (No. JCYJ20210324103608023) and Guangdong Provincial Key Laboratory of Catalysis (No. 2020B121201002). 2022-05-09T02:57:15Z 2022-05-09T02:57:15Z 2022 Journal Article Zeng, L., Chen, J., Zhong, L., Zhen, W., Tay, Y. Y., Li, S., Wang, Y., Huang, L. & Xue, C. (2022). Synergistic effect of Ru-N₄ sites and Cu-N₃ sites in carbon nitride for highly selective photocatalytic reduction of CO₂ to methane. Applied Catalysis B: Environmental, 307, 121154-. https://dx.doi.org/10.1016/j.apcatb.2022.121154 0926-3373 https://hdl.handle.net/10356/157146 10.1016/j.apcatb.2022.121154 2-s2.0-85123936474 307 121154 en MOE2018-T2-1-017 MOE2019-T1- 002-012 RG102/19 Applied Catalysis B: Environmental © 2022 Elsevier B.V. All rights reserved. This paper was published in Applied Catalysis B: Environmental and is made available with permission of Elsevier B.V. application/pdf |
| spellingShingle | Engineering::Materials Dual-Metal-Atom Methane Production Zeng, Lei Chen, Jie-Wei Zhong, Lixiang Zhen, Wenlong Tay, Yee Yan Li, Shuzhou Wang, Yanggang Huang, Limin Xue, Can Synergistic effect of Ru-N₄ sites and Cu-N₃ sites in carbon nitride for highly selective photocatalytic reduction of CO₂ to methane |
| title | Synergistic effect of Ru-N₄ sites and Cu-N₃ sites in carbon nitride for highly selective photocatalytic reduction of CO₂ to methane |
| title_full | Synergistic effect of Ru-N₄ sites and Cu-N₃ sites in carbon nitride for highly selective photocatalytic reduction of CO₂ to methane |
| title_fullStr | Synergistic effect of Ru-N₄ sites and Cu-N₃ sites in carbon nitride for highly selective photocatalytic reduction of CO₂ to methane |
| title_full_unstemmed | Synergistic effect of Ru-N₄ sites and Cu-N₃ sites in carbon nitride for highly selective photocatalytic reduction of CO₂ to methane |
| title_short | Synergistic effect of Ru-N₄ sites and Cu-N₃ sites in carbon nitride for highly selective photocatalytic reduction of CO₂ to methane |
| title_sort | synergistic effect of ru n₄ sites and cu n₃ sites in carbon nitride for highly selective photocatalytic reduction of co₂ to methane |
| topic | Engineering::Materials Dual-Metal-Atom Methane Production |
| url | https://hdl.handle.net/10356/157146 |
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