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

Abstract 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.