Dynamics of Charge-Transfer Behavior in a Plasmon-Induced Quasi-Type-II p–n/n–n Dual Heterojunction in Ag@Ag₃PO₄/g-C₃N₄/NiFe LDH Nanocomposites for Photocatalytic Cr(VI) Reduction and Phenol Oxidation

Abstract

In this work, a series of heterostructure Ag@Ag₃PO₄/g-C₃N₄/NiFe layered double hydroxide (LDH) nanocomposites were prepared by a combination of an electrostatic self-assembly and in situ photoreduction method. In this method, positively charged p-type Ag₃PO₄ was electrostatically bonded to the self-assembled negatively charged surface of the n-n-type g-C₃N₄/NiFe (CNLDH) LDH hybrid material with partial reduction of Ag⁺ to metallic Ag nanoparticles (NPs) by the photogenerated electrons and available surface -OH groups of LDH under visible light irradiation. The presence of Ag₃PO₄ as a p-type semiconductor, the surface plasmon resonance (SPR) effect of metallic Ag NPs, and oxygen vacancies as O_v-type defects in NiFe LDH could greatly achieve the quasi-type-II p-n/n-n dual heterojunctions, which was revealed by the shifted conduction band and valence band potentials in Mott-Schottky (M-S) analysis. Among all the optimized heterostructures, CNLDHAgP4 could achieve the highest photocatalytic Cr(VI) reduction rate of 97% and phenol oxidation rate of 90% in 2 h. The heterostructure CNLDHAgP4 photocatalyst possesses a unique morphology consisting of cubic phases of both Ag NPs and Ag₃PO₄, which adhered to the thin and curvy layers of the CNLDH hybrid for smooth electronic and ionic charge transport. Furthermore, the intimate Schottky barriers formed at the interface of quasi-type-II p-n/n-n dual heterojunctions were verified by the photoluminescence, linear sweep voltammetry, M-S, electrochemical impedance study, high-resolution transmission electron microscopy, and X-ray photoelectron spectroscopy studies. The SPR effect of Ag NPs and oxygen vacancies as O_v-type defect in NiFe LDH can effectively accelerate the threshold of charge separation and be the main reason for the enhanced activity achieved by the as-fabricated heterostructure photocatalyst.