Publication date: 15th December 2014
BiVO4 is an photoactive semiconducting material with suitable bandgap for water splitting. It has received great progress in solar conversion efficiency in recent years. Nano-porous structuring, in particular, has been demonstrated to show better charge efficiency than most other approaches. However, the reported nano-porous BiVO4 electrodes require the light illuminating from the back side to deliver the best efficiency, which greatly limits its practical usages as most applications require the light coming from the front side. This work presents an facile solution to this front-illumination problem through sophisticated morphology control. It was reckoned that smaller particles can give better charge efficiencies due to shorter path and bigger surface areas. Our findings revealed that this concept is not correct. By controlling the patten of electro-deposited BiOI precursor on ITO glass, we are able to synthesize more densely packed nano-porous BiVO4 with particle sizes around 150nm, which is nearly two times of the reported one. The resulting anodes showed a record high overall performance, i.e., 4mA/cm2 photocurrent was observed for sulfite oxidation using bare electrode at 0.6V vs. RHE, and a photocurrent of 3.2mA/cm2 could be achieved for water oxidation if modified with NiOOH co-catalyst by in-situ formation and activation from vapour deposited Ni. More importantly the morphology change brings another crucial feature that the front-illumination performance of the resulting electrode is almost identical to that under back-illumination. Thus we were able to assemble a back-to-back stack using two pieces of our BiVO4 anodes with the light coming in from the front side of one piece and coming out from the front side of the other piece. As the front electrode will consume less than 80% of the light, the rest 20% light will be further utilized by the back one. By using such an assembly, the light conversion efficiency can be further improved to 2.3%, which represents the highest reported performance for BiVO4 photoanodes.
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