Zhangliu Tian1,2, Cheng Han3, Yao Zhao2,4, Wenrui Dai2, Xu Lian2, Yanan Wang5, Yue Zheng5, Yi Shi2, Xuan Pan1,5, Zhichao Huang1,5, Hexing Li6, Wei Chen7,8,9. 1. SZU-NUS Collaborative Innovation Center for Optoelectronic Science & Technology, International Collaborative Laboratory of 2D Materials for Optoelectronics Science and Technology of Ministry of Education, Institute of Microscale Optoelectronics, Shenzhen University, Shenzhen, China. 2. Department of Chemistry, National University of Singapore, 3 Science Drive 3, Singapore, Singapore. 3. SZU-NUS Collaborative Innovation Center for Optoelectronic Science & Technology, International Collaborative Laboratory of 2D Materials for Optoelectronics Science and Technology of Ministry of Education, Institute of Microscale Optoelectronics, Shenzhen University, Shenzhen, China. hancheng@szu.edu.cn. 4. Joint School of National University of Singapore and Tianjin University, International Campus of Tianjin University, Binhai New City, Fuzhou, China. 5. Department of Physics, National University of Singapore, 2 Science Drive 3, Singapore, Singapore. 6. International Joint Lab on Resource Chemistry, College of Chemistry and Materials Science, Shanghai Normal University, Shanghai, China. 7. Department of Chemistry, National University of Singapore, 3 Science Drive 3, Singapore, Singapore. phycw@nus.edu.sg. 8. Joint School of National University of Singapore and Tianjin University, International Campus of Tianjin University, Binhai New City, Fuzhou, China. phycw@nus.edu.sg. 9. Department of Physics, National University of Singapore, 2 Science Drive 3, Singapore, Singapore. phycw@nus.edu.sg.
Abstract
Photocatalytic hydrogen peroxide (H2O2) generation represents a promising approach for artificial photosynthesis. However, the sluggish half-reaction of water oxidation significantly limits the efficiency of H2O2 generation. Here, a benzylamine oxidation with more favorable thermodynamics is employed as the half-reaction to couple with H2O2 generation in water by using defective zirconium trisulfide (ZrS3) nanobelts as a photocatalyst. The ZrS3 nanobelts with disulfide (S22-) and sulfide anion (S2-) vacancies exhibit an excellent photocatalytic performance for H2O2 generation and simultaneous oxidation of benzylamine to benzonitrile with a high selectivity of >99%. More importantly, the S22- and S2- vacancies can be separately introduced into ZrS3 nanobelts in a controlled manner. The S22- vacancies are further revealed to facilitate the separation of photogenerated charge carriers. The S2- vacancies can significantly improve the electron conduction, hole extraction, and kinetics of benzylamine oxidation. As a result, the use of defective ZrS3 nanobelts yields a high production rate of 78.1 ± 1.5 and 32.0 ± 1.2 μmol h-1 for H2O2 and benzonitrile, respectively, under a simulated sunlight irradiation.
Photocatalytic pan class="Chemical">hydrogen peroxide (H2O2) generation represents a promising approach for artificial photosynthesis. However, the sluggish half-reaction of water oxidation significantly limits the efficiency of H2O2 generation. Here, a benzylamine oxidation with more favorable thermodynamics is employed as the half-reaction to couple with H2O2 generation in water by using defective zirconium trisulfide (ZrS3) nanobelts as a photocatalyst. The ZrS3 nanobelts with disulfide (S22-) and sulfide anion (S2-) vacancies exhibit an excellent photocatalytic performance for H2O2 generation and simultaneous oxidation of benzylamine to benzonitrile with a high selectivity of >99%. More importantly, the S22- and S2- vacancies can be separately introduced into ZrS3 nanobelts in a controlled manner. The S22- vacancies are further revealed to facilitate the separation of photogenerated charge carriers. The S2- vacancies can significantly improve the electron conduction, hole extraction, and kinetics of benzylamine oxidation. As a result, the use of defective ZrS3 nanobelts yields a high production rate of 78.1 ± 1.5 and 32.0 ± 1.2 μmol h-1 for H2O2 and benzonitrile, respectively, under a simulated sunlight irradiation.
Authors: Kyle M Lambert; James M Bobbitt; Sherif A Eldirany; Liam E Kissane; Rose K Sheridan; Zachary D Stempel; Francis H Sternberg; William F Bailey Journal: Chemistry Date: 2016-02-22 Impact factor: 5.236