Unveiling Enhanced PEC Water Oxidation: Morphology Tuning and Interfacial Phase Change in α-Fe₂O₃@K-OMS-2 Branched Core–Shell Nanoarrays

Abstract

A simple fabrication method that involves two steps of hydrothermal reaction has been demonstrated for the growth of α-Fe 2 O 3 @K-OMS-2 branched core−shell nanoarrays. Different reactant concentrations in the shell-forming step led to different morphologies in the resultant composites, denoted as 0.25 OC, 0.5 OC, and 1.0 OC. Both 0.25 OC and 0.5 OC formed perfect branched core−shell structures, with 0.5 OC possessing longer branches, which were observed by SEM and TEM. The core K-OMS-2 and shell α-Fe 2 O 3 were confirmed by grazing incidence Xray diffraction (GIXRD), EDS mapping, and atomic alignment from high-resolution STEM images. Further investigation with high-resolution HAADF-STEM, EELS, and XPS indicated the existence of an ultrathin layer of Mn 3 O 4 sandwiched at the interface. All composite materials offered greatly enhanced photocurrent density at 1.23 V RHE , compared to the pristine Fe 2 O 3 photoanode (0.33 mA/cm 2 ), and sample 0.5 OC showed the highest photocurrent density of 2.81 mA/cm 2 . Photoelectrochemical (PEC) performance was evaluated for the samples by conducting linear sweep voltammetry (LSV), applied bias photo-to-current efficiency (ABPE), electrochemical impedance spectroscopy (EIS), incident-photo-to-current efficiency (IPCE), transient photocurrent responses, and stability tests. The charge separation and transfer efficiencies, together with the electrochemically active surface area, were also investigated. The significant enhancement in sample 0.5 OC is ascribed to the synergetic effect brought by the longer branches in the core−shell structure, the conductive K-OMS-2 core, and the formation of the Mn 3 O 4 thin layer formed between the core and shell.