Strategies for Enhancing BiVO4 Photoanodes for PEC Water Splitting: A State-of-the-Art Review

Bismuth vanadate (BiVO4) has attracted significant attention as a photoanode material for photoelectrochemical (PEC) water splitting due to its suitable bandgap (~2.4 eV), strong visible light absorption, chemical stability, and cost-effectiveness. Despite these advantages, its practical application remains constrained by intrinsic limitations, including poor charge carrier mobility, short diffusion length, and sluggish oxygen evolution reaction (OER) kinetics. This review critically summarizes recent advancements aimed at enhancing BiVO4 PEC performance, encompassing synthesis strategies, defect engineering, heterojunction formation, cocatalyst integration, light-harvesting optimization, and stability improvements. Key fabrication methods—such as solution-based, vapor-phase, and electrochemical approaches—along with targeted modifications, including metal/nonmetal doping, surface passivation, and incorporation of electron transport layers, are discussed. Emphasis is placed on strategies to improve light absorption, charge separation efficiency (ηsep), and charge transfer efficiency (ηtrans) through bandgap engineering, optical structure design, and catalytic interface optimization. Approaches to enhance stability via protective overlayers and electrolyte tuning are also reviewed, alongside emerging applications of BiVO4 in tandem PEC systems and selective solar-driven production of value-added chemicals, such as H2O2. Finally, critical challenges, including the scale-up of electrode fabrication and the elucidation of fundamental reaction mechanisms, are highlighted, providing perspectives for bridging the gap between laboratory performance and practical implementation.