Abstract
Photoelectrochemical performance of BiVO4 photoanode is limited by poor light absorption, charge separation and transfer efficiencies. For the first time in the literature, Li doped nano-porous BiVO4 photoanode showed complete bulk charge separation efficiency (~100%) at 1.23 V vs RHE along with enhanced light absorption for water splitting. Li doping showed an increase (>20 times) in the photoelectrochemical water splitting compared to pristine BiVO4 photoanode. In particular, oxygen evolution catalyst was also employed for further improving the photoelectrochemical performance (4.2 ± 0.18 mA cm−2) of Li:BiVO4 photoanodes. The density functional theory calculations showing the formation of inter-band with band gap reduction due to interstitial Li doping in BiVO4 structure support enhancement in photoelectrochemical performance. In addition, Li doping in the BiVO4 lattice void positions led to a record photocurrent density of 7.3 ± 0.36 mA cm−2 at 1.23 V vs RHE in the presence of hole scavenger under one sun illumination. Further, present study systematically demonstrates role of Li in BiVO4 host for water oxidation through a detailed characterization and study of optical and charge transport properties.
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