Efficient photocatalytic hydrogen peroxide generation coupled with selective benzylamine oxidation over defective ZrS3 nanobelts

• Published in: Nature communications Vol. 12; no. 1; p. 2039
• Main Authors: Tian, Zhangliu, Han, Cheng, Zhao, Yao, Dai, Wenrui, Lian, Xu, Wang, Yanan, Zheng, Yue, Shi, Yi, Pan, Xuan, Huang, Zhichao, Li, Hexing, Chen, Wei
• Format: Journal Article
• Language: English
• Published: London Nature Publishing Group UK 01.04.2021; Nature Publishing Group; Nature Portfolio
• Subjects: 639/301/299/890; 639/4077/909/4101/4050; 639/925/357; Anions; Benzonitrile; Current carriers; Humanities and Social Sciences; Hydrogen peroxide; Irradiation; multidisciplinary; Oxidation; Photocatalysis; Photosynthesis; Reaction kinetics; Science; Science (multidisciplinary); Selectivity; Stability; Sulfide; Sulfides; Vacancies; Zirconium
• ISSN: 2041-1723; 2041-1723
• DOI: 10.1038/s41467-021-22394-8

Photocatalytic hydrogen peroxide (H 2 O 2 ) generation represents a promising approach for artificial photosynthesis. However, the sluggish half-reaction of water oxidation significantly limits the efficiency of H 2 O 2 generation. Here, a benzylamine oxidation with more favorable thermodynamics is employed as the half-reaction to couple with H 2 O 2 generation in water by using defective zirconium trisulfide (ZrS 3 ) nanobelts as a photocatalyst. The ZrS 3 nanobelts with disulfide (S 2 2− ) and sulfide anion (S 2− ) vacancies exhibit an excellent photocatalytic performance for H 2 O 2 generation and simultaneous oxidation of benzylamine to benzonitrile with a high selectivity of >99%. More importantly, the S 2 2− and S 2− vacancies can be separately introduced into ZrS 3 nanobelts in a controlled manner. The S 2 2− vacancies are further revealed to facilitate the separation of photogenerated charge carriers. The S 2− vacancies can significantly improve the electron conduction, hole extraction, and kinetics of benzylamine oxidation. As a result, the use of defective ZrS 3 nanobelts yields a high production rate of 78.1 ± 1.5 and 32.0 ± 1.2 μmol h −1 for H 2 O 2 and benzonitrile, respectively, under a simulated sunlight irradiation. Photocatalytic H 2 O 2 generation represents a promising approach for artificial photosynthesis. Here, ZrS 3 nanobelts with controllable disulfide and sulfide anion vacancies exhibit an excellent photocatalytic H 2 O 2 generation performance together with selective oxidation of benzylamine to benzonitrile.