Defect Control via Compositional Engineering of Zn-Cu-In-S Alloyed QDs for Photocatalytic H2O2 Generation and Micropollutant Degradation: Affecting Parameters, Kinetics, and Insightful Mechanism.

Abstract

Photocatalytic H2O2 production and recalcitrant pollutant degradation are regarded as promising clean technology toward achieving sustainable solar-to-chemical energy conversion. Herein, nonstoichiometric Zn-Cu-In-S (ZCIS) quaternary alloyed quantum dots (QDs) are rationally fabricated via a reflux method toward H2O2 generation and ciprofloxacin degradation under visible light irradiation. The optimum catalyst (ZCIS-2) exhibits a notable H2O2 production of 1685.2 μmole h-1 g-1 (solar-to-chemical conversion efficiency (SCC), 0.19%), which is 5.3 times higher than that of CuInS2 (CIS), and a ciprofloxacin (CIP) degradation efficiency of 96% in 2 h. The observed improvement in activity corresponds to optimized exciton separation/transfer, broad photon absorption, tunable band alignment, and effective adsorption/activation. In addition, oxygen reduction goes through both direct two-electron single-step reduction and single-electron two-step superoxide radical pathways, whereas CIP degradation proceeds via direct •O2- and indirect •OH radical pathways, as confirmed by scavenger experiments. An appropriate amount of defects improves the adsorption/activation of O2 toward H2O2 and active oxygen species generation that facilitates CIP degradation. The effect of operational parameters, such as pH, surrounding environment, presence of ions, sacrificial agent, etc., on both H2O2 formation and CIP removal is vividly studied. Hence, the current study will provide an in-depth insight into O2 photoreduction and micropollutant removal, which encourages further advancement of potent alloyed quantum dot-oriented photocatalytic systems.