Functional Regulation of ZnAl-LDHs and Mechanism of Photocatalytic Reduction of CO<sub>2</sub>: A DFT Study
Defect engineering and heteroatom doping can significantly enhance the activity of zinc-aluminum layered double hydroxides (ZnAl-LDHs) in photocatalytic CO<sub>2</sub> reduction to fuel. However, the in-depth understanding of the associated intrinsic mechanisms is limited. Herein, we sys...
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| Format: | Article |
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MDPI AG
2023-01-01
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| Series: | Molecules |
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| Online Access: | https://www.mdpi.com/1420-3049/28/2/738 |
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| author | Dongcun Xu Gang Fu Zhongming Li Wenqing Zhen Hongyi Wang Meiling Liu Jianmin Sun Jiaxu Zhang Li Yang |
| author_facet | Dongcun Xu Gang Fu Zhongming Li Wenqing Zhen Hongyi Wang Meiling Liu Jianmin Sun Jiaxu Zhang Li Yang |
| author_sort | Dongcun Xu |
| collection | DOAJ |
| description | Defect engineering and heteroatom doping can significantly enhance the activity of zinc-aluminum layered double hydroxides (ZnAl-LDHs) in photocatalytic CO<sub>2</sub> reduction to fuel. However, the in-depth understanding of the associated intrinsic mechanisms is limited. Herein, we systematically investigated Zn vacancies (V<sub>Zn</sub>), oxygen vacancies (V<sub>O</sub>), and Cu doping on the geometry and electronic structure of ZnAl-LDH using density functional theory (DFT). We also revealed the related reaction mechanism. The results reveal the concerted roles of V<sub>O</sub>, V<sub>Zn</sub>, and doped-Cu facilitate the formation of the unsaturated metal complexes (Zn<sup>δ+</sup>-V<sub>O</sub> and Cu<sup>δ+</sup>-V<sub>O</sub>). They can localize the charge density distribution, function as new active centers, and form the intermediate band. Simultaneously, the intermediate band of functionalized ZnAl-LDHs narrows the band gap and lowers the band edge location. Therefore, it can broaden the absorption range of light and improve the selectivity of CO. Additionally, the unsaturated metal complex lowers the Gibbs free energy barrier for effective CO<sub>2</sub> activation by bringing the d-band center level closer to the Fermi level. The work provided guidance for developing LDH photocatalysts with high activity and selectivity. |
| first_indexed | 2024-03-09T11:34:13Z |
| format | Article |
| id | doaj.art-161a3385caaf4016bbf3cf6c7312d99a |
| institution | Directory Open Access Journal |
| issn | 1420-3049 |
| language | English |
| last_indexed | 2024-03-09T11:34:13Z |
| publishDate | 2023-01-01 |
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| series | Molecules |
| spelling | doaj.art-161a3385caaf4016bbf3cf6c7312d99a2023-11-30T23:44:10ZengMDPI AGMolecules1420-30492023-01-0128273810.3390/molecules28020738Functional Regulation of ZnAl-LDHs and Mechanism of Photocatalytic Reduction of CO<sub>2</sub>: A DFT StudyDongcun Xu0Gang Fu1Zhongming Li2Wenqing Zhen3Hongyi Wang4Meiling Liu5Jianmin Sun6Jiaxu Zhang7Li Yang8MIIT Key Laboratory of Critical Materials Technology for New Energy Conversion and Storage, School of Chemistry and Chemical Engineering, State Key Laboratory of Urban Water Resource and Environment, Harbin Institute of Technology, Harbin 150001, ChinaMIIT Key Laboratory of Critical Materials Technology for New Energy Conversion and Storage, School of Chemistry and Chemical Engineering, State Key Laboratory of Urban Water Resource and Environment, Harbin Institute of Technology, Harbin 150001, ChinaXupai Power Co., Ltd., Suqian 223800, ChinaMIIT Key Laboratory of Critical Materials Technology for New Energy Conversion and Storage, School of Chemistry and Chemical Engineering, State Key Laboratory of Urban Water Resource and Environment, Harbin Institute of Technology, Harbin 150001, ChinaMIIT Key Laboratory of Critical Materials Technology for New Energy Conversion and Storage, School of Chemistry and Chemical Engineering, State Key Laboratory of Urban Water Resource and Environment, Harbin Institute of Technology, Harbin 150001, ChinaMIIT Key Laboratory of Critical Materials Technology for New Energy Conversion and Storage, School of Chemistry and Chemical Engineering, State Key Laboratory of Urban Water Resource and Environment, Harbin Institute of Technology, Harbin 150001, ChinaMIIT Key Laboratory of Critical Materials Technology for New Energy Conversion and Storage, School of Chemistry and Chemical Engineering, State Key Laboratory of Urban Water Resource and Environment, Harbin Institute of Technology, Harbin 150001, ChinaMIIT Key Laboratory of Critical Materials Technology for New Energy Conversion and Storage, School of Chemistry and Chemical Engineering, State Key Laboratory of Urban Water Resource and Environment, Harbin Institute of Technology, Harbin 150001, ChinaMIIT Key Laboratory of Critical Materials Technology for New Energy Conversion and Storage, School of Chemistry and Chemical Engineering, State Key Laboratory of Urban Water Resource and Environment, Harbin Institute of Technology, Harbin 150001, ChinaDefect engineering and heteroatom doping can significantly enhance the activity of zinc-aluminum layered double hydroxides (ZnAl-LDHs) in photocatalytic CO<sub>2</sub> reduction to fuel. However, the in-depth understanding of the associated intrinsic mechanisms is limited. Herein, we systematically investigated Zn vacancies (V<sub>Zn</sub>), oxygen vacancies (V<sub>O</sub>), and Cu doping on the geometry and electronic structure of ZnAl-LDH using density functional theory (DFT). We also revealed the related reaction mechanism. The results reveal the concerted roles of V<sub>O</sub>, V<sub>Zn</sub>, and doped-Cu facilitate the formation of the unsaturated metal complexes (Zn<sup>δ+</sup>-V<sub>O</sub> and Cu<sup>δ+</sup>-V<sub>O</sub>). They can localize the charge density distribution, function as new active centers, and form the intermediate band. Simultaneously, the intermediate band of functionalized ZnAl-LDHs narrows the band gap and lowers the band edge location. Therefore, it can broaden the absorption range of light and improve the selectivity of CO. Additionally, the unsaturated metal complex lowers the Gibbs free energy barrier for effective CO<sub>2</sub> activation by bringing the d-band center level closer to the Fermi level. The work provided guidance for developing LDH photocatalysts with high activity and selectivity.https://www.mdpi.com/1420-3049/28/2/738ZnAl-LDHsCO<sub>2</sub>PRDFTreaction mechanismdefect engineeringCu doping |
| spellingShingle | Dongcun Xu Gang Fu Zhongming Li Wenqing Zhen Hongyi Wang Meiling Liu Jianmin Sun Jiaxu Zhang Li Yang Functional Regulation of ZnAl-LDHs and Mechanism of Photocatalytic Reduction of CO<sub>2</sub>: A DFT Study Molecules ZnAl-LDHs CO<sub>2</sub>PR DFT reaction mechanism defect engineering Cu doping |
| title | Functional Regulation of ZnAl-LDHs and Mechanism of Photocatalytic Reduction of CO<sub>2</sub>: A DFT Study |
| title_full | Functional Regulation of ZnAl-LDHs and Mechanism of Photocatalytic Reduction of CO<sub>2</sub>: A DFT Study |
| title_fullStr | Functional Regulation of ZnAl-LDHs and Mechanism of Photocatalytic Reduction of CO<sub>2</sub>: A DFT Study |
| title_full_unstemmed | Functional Regulation of ZnAl-LDHs and Mechanism of Photocatalytic Reduction of CO<sub>2</sub>: A DFT Study |
| title_short | Functional Regulation of ZnAl-LDHs and Mechanism of Photocatalytic Reduction of CO<sub>2</sub>: A DFT Study |
| title_sort | functional regulation of znal ldhs and mechanism of photocatalytic reduction of co sub 2 sub a dft study |
| topic | ZnAl-LDHs CO<sub>2</sub>PR DFT reaction mechanism defect engineering Cu doping |
| url | https://www.mdpi.com/1420-3049/28/2/738 |
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