Triggering of Low-Valence Molybdenum in Multiphasic MoS₂ for Effective Reactive Oxygen Species Output in Catalytic Fenton-like Reactions

Abstract

Utilization of photocatalytic reactions to trigger persistent large-scale reactions could be an alternative path for practical solar energy conversion to relieve environmental pressure nowadays. We took the view that the photoinduction of transition states was critical for improving the activity of catalytic reactions. On the basis of theoretical predictions, the reaction Gibbs free energy of permonosulfate (PMS) activation can be rapidly reduced by molybdenum with low valence. We therefore constructed a multiphasic molybdenum dichalcogenide (MoS₂) heterostructure-based photosystem that enabled generation of Mo transition states by visible light excitation. According to combination results of electron paramagnetic resonance, photoelectrochemical analysis, and X-ray photoelectron spectroscopy, we confirmed that the optimized 2H/1T heterojunction permitted the transport of excited interfacial electrons from the semiconductive 2H phase to the metallic 1T phase, and synchronously partially reduced Mo(IV) to Mo(III) at the interface. This intensified the charge transfer between the MoS₂ and PMS-containing solution, thereby efficiently splitting the PMS molecules into ^•OH and SO₄^•- radicals. In this system, a type of refractory herbicide, 2,4-dichlorophenoxyacetic acid (2,4-D), can be degraded within 60 min at a rate constant of 6.20 × 10^-2 min^-1 using multiphasic MoS₂ with a 1T/2H ratio of 1:1.