Photo‐driven Oxygen Vacancies Extends Charge Carrier Lifetime for Efficient Solar Water Splitting

Abstract

A photocharge/discharge strategy is proposed to initiate the WO₃ photoelectrode and suppress the main charge recombination, which remarkably improves the photoelectrochemical (PEC) performance. The photocharged WO₃ surrounded by a 8-10 nm overlayer and oxygen vacancies could be operated more than 25 cycles with 50 h durability without significant decay on PEC activity. A photocharged WO₃ /CuO photoanode exhibits an outstanding photocurrent of 3.2 mA cm^-2 at 1.23 V_RHE with a low onset potential of 0.6 V_RHE , which is one of the best performances of p-n heterojunction structure. Using nonadiabatic molecular dynamics combined with time-domain DFT, we clarify the prolonged charge carrier lifetime of photocharged WO₃ , as well as how electronic systems of photocharged WO₃ /CuO semiconductors enable the effective photoinduced electrons transfer from WO₃ into CuO. This work provides a feasible route to address excessive defects existed in photoelectrodes without causing extra recombination.