Photoredox Coupling of CO<sub>2</sub> Reduction with Benzyl Alcohol Oxidation over Ternary Metal Chalcogenides (Zn<sub>m</sub>In<sub>2</sub>S<sub>3+m</sub>, m = 1–5) with Regulable Products Selectivity
Integrating photocatalytic CO<sub>2</sub> reduction with selective benzyl alcohol (BA) oxidation in one photoredox reaction system is a promising way for the simultaneous utilization of photogenerated electrons and holes. Herein, Zn<sub>m</sub>In<sub>2</sub>S<s...
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MDPI AG
2023-09-01
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| Series: | Molecules |
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| Online Access: | https://www.mdpi.com/1420-3049/28/18/6553 |
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| author | Zisheng Du Kexin Gong Zhiruo Yu Yang Yang Peixian Wang Xiuzhen Zheng Zhongliao Wang Sujuan Zhang Shifu Chen Sugang Meng |
| author_facet | Zisheng Du Kexin Gong Zhiruo Yu Yang Yang Peixian Wang Xiuzhen Zheng Zhongliao Wang Sujuan Zhang Shifu Chen Sugang Meng |
| author_sort | Zisheng Du |
| collection | DOAJ |
| description | Integrating photocatalytic CO<sub>2</sub> reduction with selective benzyl alcohol (BA) oxidation in one photoredox reaction system is a promising way for the simultaneous utilization of photogenerated electrons and holes. Herein, Zn<sub>m</sub>In<sub>2</sub>S<sub>3+m</sub> (m = 1–5) semiconductors (ZnIn<sub>2</sub>S<sub>4</sub>, Zn<sub>2</sub>In<sub>2</sub>S<sub>5</sub>, Zn<sub>3</sub>In<sub>2</sub>S<sub>6</sub>, Zn<sub>4</sub>In<sub>2</sub>S<sub>7</sub>, and Zn<sub>5</sub>In<sub>2</sub>S<sub>8</sub>) with various composition faults were synthesized via a simple hydrothermal method and used for effective selective dehydrocoupling of benzyl alcohol into high-value C–C coupling products and reduction of CO<sub>2</sub> into syngas under visible light. The absorption edge of Zn<sub>m</sub>In<sub>2</sub>S<sub>3+m</sub> samples shifted to shorter wavelengths as the atomic ratio of Zn/In was increased. The conduction band and valence band position can be adjusted by changing the Zn/In ratio, resulting in controllable photoredox ability for selective BA oxidation and CO<sub>2</sub> reduction. For example, the selectivity of benzaldehyde (BAD) product was reduced from 76% (ZnIn<sub>2</sub>S<sub>4</sub>, ZIS1) to 27% (Zn<sub>4</sub>In<sub>2</sub>S<sub>7</sub>, ZIS4), while the selectivity of hydrobenzoin (HB) was increased from 22% to 56%. Additionally, the H<sub>2</sub> formation rate on ZIS1 (1.6 mmol/g/h) was 1.6 times higher than that of ZIS4 (1.0 mmol/g/h), and the CO formation rate on ZIS4 (0.32 mmol/g/h) was three times higher than that of ZIS1 (0.13 mmol/g/h), demonstrating that syngas with different H<sub>2</sub>/CO ratios can be obtained by controlling the Zn/In ratio in Zn<sub>m</sub>In<sub>2</sub>S<sub>3+m</sub>. This study provides new insights into unveiling the relationship of structure–property of Zn<sub>m</sub>In<sub>2</sub>S<sub>3+m</sub> layered crystals, which are valuable for implementation in a wide range of environment and energy applications. |
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| spelling | doaj.art-b21f0c76d66c4737b1629ffc44c15b592023-11-19T12:09:03ZengMDPI AGMolecules1420-30492023-09-012818655310.3390/molecules28186553Photoredox Coupling of CO<sub>2</sub> Reduction with Benzyl Alcohol Oxidation over Ternary Metal Chalcogenides (Zn<sub>m</sub>In<sub>2</sub>S<sub>3+m</sub>, m = 1–5) with Regulable Products SelectivityZisheng Du0Kexin Gong1Zhiruo Yu2Yang Yang3Peixian Wang4Xiuzhen Zheng5Zhongliao Wang6Sujuan Zhang7Shifu Chen8Sugang Meng9Key Laboratory of Green and Precise Synthetic Chemistry and Applications, Ministry of Education, College of Chemistry and Materials Science, Huaibei Normal University, Huaibei 235000, ChinaKey Laboratory of Pollutant Sensitive Materials and Environmental Remediation, Key Laboratory of Clean Energy and Green Circulation, Huaibei Normal University, Huaibei 235000, ChinaKey Laboratory of Green and Precise Synthetic Chemistry and Applications, Ministry of Education, College of Chemistry and Materials Science, Huaibei Normal University, Huaibei 235000, ChinaKey Laboratory of Green and Precise Synthetic Chemistry and Applications, Ministry of Education, College of Chemistry and Materials Science, Huaibei Normal University, Huaibei 235000, ChinaState Key Laboratory Incubation Base for Green Processing of Chemical Engineering, School of Chemistry and Chemical Engineering, Shihezi 832003, ChinaKey Laboratory of Green and Precise Synthetic Chemistry and Applications, Ministry of Education, College of Chemistry and Materials Science, Huaibei Normal University, Huaibei 235000, ChinaKey Laboratory of Green and Precise Synthetic Chemistry and Applications, Ministry of Education, College of Chemistry and Materials Science, Huaibei Normal University, Huaibei 235000, ChinaKey Laboratory of Green and Precise Synthetic Chemistry and Applications, Ministry of Education, College of Chemistry and Materials Science, Huaibei Normal University, Huaibei 235000, ChinaKey Laboratory of Green and Precise Synthetic Chemistry and Applications, Ministry of Education, College of Chemistry and Materials Science, Huaibei Normal University, Huaibei 235000, ChinaKey Laboratory of Green and Precise Synthetic Chemistry and Applications, Ministry of Education, College of Chemistry and Materials Science, Huaibei Normal University, Huaibei 235000, ChinaIntegrating photocatalytic CO<sub>2</sub> reduction with selective benzyl alcohol (BA) oxidation in one photoredox reaction system is a promising way for the simultaneous utilization of photogenerated electrons and holes. Herein, Zn<sub>m</sub>In<sub>2</sub>S<sub>3+m</sub> (m = 1–5) semiconductors (ZnIn<sub>2</sub>S<sub>4</sub>, Zn<sub>2</sub>In<sub>2</sub>S<sub>5</sub>, Zn<sub>3</sub>In<sub>2</sub>S<sub>6</sub>, Zn<sub>4</sub>In<sub>2</sub>S<sub>7</sub>, and Zn<sub>5</sub>In<sub>2</sub>S<sub>8</sub>) with various composition faults were synthesized via a simple hydrothermal method and used for effective selective dehydrocoupling of benzyl alcohol into high-value C–C coupling products and reduction of CO<sub>2</sub> into syngas under visible light. The absorption edge of Zn<sub>m</sub>In<sub>2</sub>S<sub>3+m</sub> samples shifted to shorter wavelengths as the atomic ratio of Zn/In was increased. The conduction band and valence band position can be adjusted by changing the Zn/In ratio, resulting in controllable photoredox ability for selective BA oxidation and CO<sub>2</sub> reduction. For example, the selectivity of benzaldehyde (BAD) product was reduced from 76% (ZnIn<sub>2</sub>S<sub>4</sub>, ZIS1) to 27% (Zn<sub>4</sub>In<sub>2</sub>S<sub>7</sub>, ZIS4), while the selectivity of hydrobenzoin (HB) was increased from 22% to 56%. Additionally, the H<sub>2</sub> formation rate on ZIS1 (1.6 mmol/g/h) was 1.6 times higher than that of ZIS4 (1.0 mmol/g/h), and the CO formation rate on ZIS4 (0.32 mmol/g/h) was three times higher than that of ZIS1 (0.13 mmol/g/h), demonstrating that syngas with different H<sub>2</sub>/CO ratios can be obtained by controlling the Zn/In ratio in Zn<sub>m</sub>In<sub>2</sub>S<sub>3+m</sub>. This study provides new insights into unveiling the relationship of structure–property of Zn<sub>m</sub>In<sub>2</sub>S<sub>3+m</sub> layered crystals, which are valuable for implementation in a wide range of environment and energy applications.https://www.mdpi.com/1420-3049/28/18/6553photocatalyticCO<sub>2</sub> reductionsyngasbenzyl alcohol oxidationZnIn sulfide |
| spellingShingle | Zisheng Du Kexin Gong Zhiruo Yu Yang Yang Peixian Wang Xiuzhen Zheng Zhongliao Wang Sujuan Zhang Shifu Chen Sugang Meng Photoredox Coupling of CO<sub>2</sub> Reduction with Benzyl Alcohol Oxidation over Ternary Metal Chalcogenides (Zn<sub>m</sub>In<sub>2</sub>S<sub>3+m</sub>, m = 1–5) with Regulable Products Selectivity Molecules photocatalytic CO<sub>2</sub> reduction syngas benzyl alcohol oxidation ZnIn sulfide |
| title | Photoredox Coupling of CO<sub>2</sub> Reduction with Benzyl Alcohol Oxidation over Ternary Metal Chalcogenides (Zn<sub>m</sub>In<sub>2</sub>S<sub>3+m</sub>, m = 1–5) with Regulable Products Selectivity |
| title_full | Photoredox Coupling of CO<sub>2</sub> Reduction with Benzyl Alcohol Oxidation over Ternary Metal Chalcogenides (Zn<sub>m</sub>In<sub>2</sub>S<sub>3+m</sub>, m = 1–5) with Regulable Products Selectivity |
| title_fullStr | Photoredox Coupling of CO<sub>2</sub> Reduction with Benzyl Alcohol Oxidation over Ternary Metal Chalcogenides (Zn<sub>m</sub>In<sub>2</sub>S<sub>3+m</sub>, m = 1–5) with Regulable Products Selectivity |
| title_full_unstemmed | Photoredox Coupling of CO<sub>2</sub> Reduction with Benzyl Alcohol Oxidation over Ternary Metal Chalcogenides (Zn<sub>m</sub>In<sub>2</sub>S<sub>3+m</sub>, m = 1–5) with Regulable Products Selectivity |
| title_short | Photoredox Coupling of CO<sub>2</sub> Reduction with Benzyl Alcohol Oxidation over Ternary Metal Chalcogenides (Zn<sub>m</sub>In<sub>2</sub>S<sub>3+m</sub>, m = 1–5) with Regulable Products Selectivity |
| title_sort | photoredox coupling of co sub 2 sub reduction with benzyl alcohol oxidation over ternary metal chalcogenides zn sub m sub in sub 2 sub s sub 3 m sub m 1 5 with regulable products selectivity |
| topic | photocatalytic CO<sub>2</sub> reduction syngas benzyl alcohol oxidation ZnIn sulfide |
| url | https://www.mdpi.com/1420-3049/28/18/6553 |
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