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
Zisheng Du,
Kexin Gong,
Zhiruo Yu,
Yang Yang,
Peixian Wang,
Xiuzhen Zheng,
Zhongliao Wang,
Sujuan Zhang,
Shifu Chen,
Sugang Meng
Affiliations
Zisheng Du
Key Laboratory of Green and Precise Synthetic Chemistry and Applications, Ministry of Education, College of Chemistry and Materials Science, Huaibei Normal University, Huaibei 235000, China
Kexin Gong
Key Laboratory of Pollutant Sensitive Materials and Environmental Remediation, Key Laboratory of Clean Energy and Green Circulation, Huaibei Normal University, Huaibei 235000, China
Zhiruo Yu
Key Laboratory of Green and Precise Synthetic Chemistry and Applications, Ministry of Education, College of Chemistry and Materials Science, Huaibei Normal University, Huaibei 235000, China
Yang Yang
Key Laboratory of Green and Precise Synthetic Chemistry and Applications, Ministry of Education, College of Chemistry and Materials Science, Huaibei Normal University, Huaibei 235000, China
Peixian Wang
State Key Laboratory Incubation Base for Green Processing of Chemical Engineering, School of Chemistry and Chemical Engineering, Shihezi 832003, China
Xiuzhen Zheng
Key Laboratory of Green and Precise Synthetic Chemistry and Applications, Ministry of Education, College of Chemistry and Materials Science, Huaibei Normal University, Huaibei 235000, China
Zhongliao Wang
Key Laboratory of Green and Precise Synthetic Chemistry and Applications, Ministry of Education, College of Chemistry and Materials Science, Huaibei Normal University, Huaibei 235000, China
Sujuan Zhang
Key Laboratory of Green and Precise Synthetic Chemistry and Applications, Ministry of Education, College of Chemistry and Materials Science, Huaibei Normal University, Huaibei 235000, China
Shifu Chen
Key Laboratory of Green and Precise Synthetic Chemistry and Applications, Ministry of Education, College of Chemistry and Materials Science, Huaibei Normal University, Huaibei 235000, China
Sugang Meng
Key Laboratory of Green and Precise Synthetic Chemistry and Applications, Ministry of Education, College of Chemistry and Materials Science, Huaibei Normal University, Huaibei 235000, China
Integrating photocatalytic CO2 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, ZnmIn2S3+m (m = 1–5) semiconductors (ZnIn2S4, Zn2In2S5, Zn3In2S6, Zn4In2S7, and Zn5In2S8) 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 CO2 into syngas under visible light. The absorption edge of ZnmIn2S3+m 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 CO2 reduction. For example, the selectivity of benzaldehyde (BAD) product was reduced from 76% (ZnIn2S4, ZIS1) to 27% (Zn4In2S7, ZIS4), while the selectivity of hydrobenzoin (HB) was increased from 22% to 56%. Additionally, the H2 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 H2/CO ratios can be obtained by controlling the Zn/In ratio in ZnmIn2S3+m. This study provides new insights into unveiling the relationship of structure–property of ZnmIn2S3+m layered crystals, which are valuable for implementation in a wide range of environment and energy applications.
