Defect-Engineered Z-Scheme Heterojunction of Fe-MOFs/Bi<sub>2</sub>WO<sub>6</sub> for Solar-Driven CO<sub>2</sub> Conversion: Synergistic Surface Catalysis and Interfacial Charge Dynamics
The urgent need for sustainable CO<sub>2</sub> conversion technologies has driven the development of advanced photocatalysts that harness solar energy. This study employs a CTAB-assisted solvothermal method to fabricate a Z-scheme heterojunction Fe-MOFs/V<sub>O</sub>-Bi<su...
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2025-04-01
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| author | Ting Liu Yun Wu Hao Wang Jichang Lu Yongming Luo |
| author_facet | Ting Liu Yun Wu Hao Wang Jichang Lu Yongming Luo |
| author_sort | Ting Liu |
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| description | The urgent need for sustainable CO<sub>2</sub> conversion technologies has driven the development of advanced photocatalysts that harness solar energy. This study employs a CTAB-assisted solvothermal method to fabricate a Z-scheme heterojunction Fe-MOFs/V<sub>O</sub>-Bi<sub>2</sub>WO<sub>6</sub> (FM/V<sub>O</sub>-BWO) for photocatalytic CO<sub>2</sub> reduction. Positron annihilation lifetime spectroscopy (PALS) was employed to confirm the existence of oxygen vacancies, while spherical aberration-corrected transmission electron microscope (STEM) characterization verified the successful construction of heterointerfaces. X-ray absorption fine structure (XAFS) spectra confirmed that the defect configuration and heterostructure changed the surface chemical valence state. The optimized 1.0FM/V<sub>O</sub>-BWO composite demonstrated exceptional photocatalytic performance, achieving CO and CH<sub>4</sub> yields of 60.48 and 4.3 μmol/g, respectively, under visible-light 11.8- and 1.5-fold enhancements over pristine Bi<sub>2</sub>WO<sub>6</sub>. The enhanced performance is attributed to oxygen vacancy-induced active sites facilitating CO₂ adsorption/activation. In situ molecular spectroscopy confirmed the formation of critical CO<sub>2</sub>-derived intermediates (COOH* and CHO*) through surface interactions involving four-coordinated and two-coordinated hydrogen-bonded water molecules. Furthermore, the accelerated interfacial charge transfer efficiency mediated by the Z-scheme heterojunction has been conclusively demonstrated. This work establishes a paradigm for defect-mediated heterojunction design, offering a sustainable route for solar fuel production. |
| format | Article |
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| institution | OA Journals |
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| language | English |
| publishDate | 2025-04-01 |
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| spelling | doaj-art-0a09838a9a6842938324e931f802ef992025-08-20T02:28:25ZengMDPI AGNanomaterials2079-49912025-04-0115861810.3390/nano15080618Defect-Engineered Z-Scheme Heterojunction of Fe-MOFs/Bi<sub>2</sub>WO<sub>6</sub> for Solar-Driven CO<sub>2</sub> Conversion: Synergistic Surface Catalysis and Interfacial Charge DynamicsTing Liu0Yun Wu1Hao Wang2Jichang Lu3Yongming Luo4Faculty of Chemical Engineering, Kunming University of Science and Technology, Kunming 650500, ChinaFaculty of Chemical Engineering, Kunming University of Science and Technology, Kunming 650500, ChinaFaculty of Chemical Engineering, Kunming University of Science and Technology, Kunming 650500, ChinaKey Laboratory of Yunnan Province for Synthesizing Sulfur-Containing Fine Chemicals, Kunming 650500, ChinaFaculty of Chemical Engineering, Kunming University of Science and Technology, Kunming 650500, ChinaThe urgent need for sustainable CO<sub>2</sub> conversion technologies has driven the development of advanced photocatalysts that harness solar energy. This study employs a CTAB-assisted solvothermal method to fabricate a Z-scheme heterojunction Fe-MOFs/V<sub>O</sub>-Bi<sub>2</sub>WO<sub>6</sub> (FM/V<sub>O</sub>-BWO) for photocatalytic CO<sub>2</sub> reduction. Positron annihilation lifetime spectroscopy (PALS) was employed to confirm the existence of oxygen vacancies, while spherical aberration-corrected transmission electron microscope (STEM) characterization verified the successful construction of heterointerfaces. X-ray absorption fine structure (XAFS) spectra confirmed that the defect configuration and heterostructure changed the surface chemical valence state. The optimized 1.0FM/V<sub>O</sub>-BWO composite demonstrated exceptional photocatalytic performance, achieving CO and CH<sub>4</sub> yields of 60.48 and 4.3 μmol/g, respectively, under visible-light 11.8- and 1.5-fold enhancements over pristine Bi<sub>2</sub>WO<sub>6</sub>. The enhanced performance is attributed to oxygen vacancy-induced active sites facilitating CO₂ adsorption/activation. In situ molecular spectroscopy confirmed the formation of critical CO<sub>2</sub>-derived intermediates (COOH* and CHO*) through surface interactions involving four-coordinated and two-coordinated hydrogen-bonded water molecules. Furthermore, the accelerated interfacial charge transfer efficiency mediated by the Z-scheme heterojunction has been conclusively demonstrated. This work establishes a paradigm for defect-mediated heterojunction design, offering a sustainable route for solar fuel production.https://www.mdpi.com/2079-4991/15/8/618photocatalytic CO<sub>2</sub> reductiondefect-engineeredheterojunctionssurface catalysischarge transfer |
| spellingShingle | Ting Liu Yun Wu Hao Wang Jichang Lu Yongming Luo Defect-Engineered Z-Scheme Heterojunction of Fe-MOFs/Bi<sub>2</sub>WO<sub>6</sub> for Solar-Driven CO<sub>2</sub> Conversion: Synergistic Surface Catalysis and Interfacial Charge Dynamics Nanomaterials photocatalytic CO<sub>2</sub> reduction defect-engineered heterojunctions surface catalysis charge transfer |
| title | Defect-Engineered Z-Scheme Heterojunction of Fe-MOFs/Bi<sub>2</sub>WO<sub>6</sub> for Solar-Driven CO<sub>2</sub> Conversion: Synergistic Surface Catalysis and Interfacial Charge Dynamics |
| title_full | Defect-Engineered Z-Scheme Heterojunction of Fe-MOFs/Bi<sub>2</sub>WO<sub>6</sub> for Solar-Driven CO<sub>2</sub> Conversion: Synergistic Surface Catalysis and Interfacial Charge Dynamics |
| title_fullStr | Defect-Engineered Z-Scheme Heterojunction of Fe-MOFs/Bi<sub>2</sub>WO<sub>6</sub> for Solar-Driven CO<sub>2</sub> Conversion: Synergistic Surface Catalysis and Interfacial Charge Dynamics |
| title_full_unstemmed | Defect-Engineered Z-Scheme Heterojunction of Fe-MOFs/Bi<sub>2</sub>WO<sub>6</sub> for Solar-Driven CO<sub>2</sub> Conversion: Synergistic Surface Catalysis and Interfacial Charge Dynamics |
| title_short | Defect-Engineered Z-Scheme Heterojunction of Fe-MOFs/Bi<sub>2</sub>WO<sub>6</sub> for Solar-Driven CO<sub>2</sub> Conversion: Synergistic Surface Catalysis and Interfacial Charge Dynamics |
| title_sort | defect engineered z scheme heterojunction of fe mofs bi sub 2 sub wo sub 6 sub for solar driven co sub 2 sub conversion synergistic surface catalysis and interfacial charge dynamics |
| topic | photocatalytic CO<sub>2</sub> reduction defect-engineered heterojunctions surface catalysis charge transfer |
| url | https://www.mdpi.com/2079-4991/15/8/618 |
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