LAUSR

The application of photoelectrochemical (PEC) water splitting is limited by the sluggish surface oxygen evolution reaction (OER) kinetics. OER kinetics can be effectively improved through cocatalyst engineering. However, the tardy transfer process and serious recombination of carriers are the key factors restricting the cocatalyst development. Taking BiVO4 as an example, a Co‐modified heme film rich in large conjugated ring structures is introduced onto the photoanode surface using a solvothermal method. This film functions as an efficient cocatalyst. It considerably reduces the surface overpotential, promotes the transfer of photogenerated holes, and boosts the kinetics of OER by specifically affecting the formation of OOH*. Simultaneously, the formed CoOV bonds induce strong interaction at the photoanode/cocatalyst interfaces, reducing the recombination of photogenerated carriers. Consequently, the onset potential of the optimized photoanode decreases from 0.45 to 0.07 V and the photocurrent density at 1.23 V versus reversible hydrogen electrode boosts to 5.3 mA cm−2. This work demonstrates a facile strategy for designing cocatalysts to obtain rapid hole transfer capability and reduced carrier recombination for improved PEC performance.