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Boosting the photoelectrochemical performance of BiVO4 via element dopant engineering: concurrent optimization of
1State Key Laboratory of Heavy Oil Processing, China University of Petroleum, Beijing 102249, People's Republic of China.
Abstract:
Bismuth vanadate (BiVO4) is hindered by poor hole mobility and oxygen evolution reaction (OER) kinetics, limitations that can be effectively mitigated through elemental doping. This study presents an effective cobalt (Co)-doping strategy that simultaneously modulates the band structure and oxygen vacancy (Ov) concentration of BiVO4, while accelerating surface catalytic reactions through the in situ formation of active cobalt oxides. Experimental results revealed that the Co-doped BiVO4 (Co:BiVO4) sample exhibited an Ov concentration of 7.819 × 10-5 mol/L, which is 45.5-fold higher than that of undoped BiVO4. Under AM 1.5G (Air Mass 1.5 Global) illumination, Co:BiVO4 exhibited a charge injection efficiency of 51.30% and an incident photon-to-current efficiency (IPCE) of 22.34% at 420 nm. Upon cocatalyst loading, Faradaic efficiency for hydrogen and oxygen is >92.7%. Density functional theory (DFT) and in situ characterization revealed that Co doping introduced impurity states, reduced the work function, and narrowed the bandgap. These changes enhanced the built-in electric field (IEF) and suppressed carrier recombination, significantly improving the OER performance. This study confirms that rational doping is an effective strategy for developing high-performance BiVO4 photoanodes.
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