A robust ALD-protected silicon-based hybrid photoelectrode for hydrogen evolution under aqueous conditions

Hydrogen production through direct sunlight-driven water splitting in photo-electrochemical cells (PECs) is a promising solution for energy sourcing. PECs need to fulfill three criteria: sustainability, cost-effectiveness and stability. Here we report an efficient and stable photocathode platform for H₂ evolution based on Earth-abundant elements. A p-type silicon surface was protected by atomic layer deposition (ALD) with a 15 nm TiO₂ layer, on top of which a 300 nm mesoporous TiO₂ layer was spin-coated. The cobalt diimine-dioxime molecular catalyst was covalently grafted onto TiO₂ through phosphonate anchors and an additional 0.2 nm ALD-TiO₂ layer was applied for stabilization. This assembly catalyzes water reduction into H₂ in phosphate buffer (pH 7) with an onset potential of +0.47 V vs. RHE. The resulting current density is -1.3 ± 0.1 mA cm^-2 at 0 V vs. RHE under AM 1.5 solar irradiation, corresponding to a turnover number of 260 per hour of operation and a turnover frequency of 0.071 s^-1.