Freeing the Polarons to Facilitate Charge Transport in BiVO 4 from Oxygen Vacancies with an Oxidative 2D Precursor

The BiVO 4 photoelectrochemical (PEC) electrode in tandem with a photovoltaic (PV) cell has shown great potential to become a compact and cost‐efficient device for solar hydrogen generation. However, the PEC part is still facing problems such as the poor charge transport efficiency owing to the drag of oxygen vacancy bound polarons. In the present work, to effectively suppress oxygen vacancy formation, a new route has been developed to synthesize BiVO 4 photoanodes by using a highly oxidative two‐dimensional (2D) precursor, bismuth oxyiodate (BiOIO 3 ), as an internal oxidant. With the reduced defects, namely the oxygen vacancies, the bound polarons were released, enabling a fast charge transport inside BiVO 4 and doubling the performance in tandem devices based on the oxygen vacancy eliminated BiVO 4 . This work is a new avenue for elaborately designing the precursor and breaking the limitation of charge transport for highly efficient PEC‐PV solar fuel devices.