Kanokwan Klahan, Gilles Patriarche, Stephan Steinmann, Laureline Treps, Gilles Pécastaings, Osmane Camara, Rüdiger-A. Eichel, Sylvain Chambon, Patrick Garrigue, Cécile Bossy, Sareeya Bureekaew, Gabriel Loget, Pichaya Pattanasattayavong
Although it is known that iron (Fe) significantly alters the electrocatalytic activity of nickel (Ni)-based materials, little attention has been paid to the effects of Fe impurities on the photoelectrochemical (PEC) properties of solar-driven water-splitting photoanodes. Herein, we elucidate the crucial role of Fe in model metal-insulator-semiconductor (MIS) Si photoanodes decorated with Ni nanoparticles (NPs), known for their high performance in photoinduced water splitting. Our results demonstrate that residual Fe strongly influences the photoanodes' junction energetics and photovoltaic properties. We show that the synergistic effects (electrocatalytic/photovoltaic) caused by Fe doping explain the high performance previously reported for these model photoanodes. Crucially, Fe incorporation into the outer shell of Ni NPs and the electrolyte is essential to achieve the reported photovoltage up to 500 mV. Our investigations emphasize the importance of Fe in PEC devices, which has always been neglected in the past.