Water-Splitting Artificial Leaf Based on a Triple-Junction Silicon Solar Cell: One-Step Fabrication through Photoinduced Deposition of Catalysts and Electrochemical Operando Monitoring.

Solar hydrogen generation via water splitting using a monolithic photoelectrochemical cell, also called artificial leaf, could be a powerful technology to accelerate the transition from fossil to sustainable energy sources. Identification of scalable methods for the fabrication of monolithic devices and gaining insights into their operating mode to identify solutions to improve performance and stability represent great challenges. Herein, we report on the one-step fabrication of a CoWO|ITO|3jn-a-Si|Steel|CoWS monolithic device via the simple photoinduced deposition of CoWO and CoWS as oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) catalyst layers, respectively, onto an illuminated ITO|3jn-a-Si|Steel solar cell using a single-deposition bath containing the [Co(WS 4 ) 2 ] 2- complex. In a pH 7 phosphate buffer solution, the best device achieved a solar-to-hydrogen conversion yield of 1.9%. Evolution of the catalyst layers and that of the 3jn-a-Si light-harvesting core during the operation of the monolithic device are examined by conventional tools such as scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDX), and inductively coupled plasma optical emission spectroscopy (ICP-OES) together with a bipotentiostat measurement. We demonstrate that the device performance degrades due to the partial dissolution of the catalyst. Still, this degradation is healable by simply adding [Co(WS 4 ) 2 ] 2- to the operating solution. However, modifications on the protecting indium-doped tin oxide (ITO) layer are shown to initiate irreversible degradation of the 3jn-a-Si light-harvesting core, resulting in a 10-fold decrease of the performances of the monolithic device.