Ligand-assisted assembly of FeCo-phytate catalytic interfaces on WO3 photoanodes for dual enhancement of charge separation and oxygen evolution kinetics
Abstract
Inefficient separation of surface charges and slow kinetics of oxygen evolution reaction (OER) persist as critical hurdles limiting photoelectrochemical (PEC) water splitting efficiency. Herein, these challenges are addressed via a coordination self-assembly strategy, deploying an ultrathin (~2.5 nm) amorphous phytic acid (PA)-coordinated Fe and Co layer on WO3 nanosheet arrays (WO3@PA-FeCo). Under an applied potential of 1.23 VRHE, the modified photoanode delivers a photocurrent density of 1.93 mA cm−2, representing a 3.62-fold enhancement compared with pristine WO3, with a 150 mV cathodic shift in onset potential. Density functional theory, in situ attenuated total reflection-Fourier transform infrared spectroscopy and surface photovoltage spectroscopy reveal dual enhancements: accelerated OER kinetics via lowered energy barriers for the O→OOH rate-determining step and improved surface charge separation efficiency. PA-coordinated metal complexes display universal applicability, elevating BiVO4, TiO2 and Fe2O3 photoanode performances. This work provides a versatile pathway for designing eco-friendly cocatalysts to synergistically optimize interfacial charge dynamics and catalytic processes in solar energy conversion systems.