Solar Biomass Reforming and Hydrogen Production with Earth‐Abundant Si‐Based Photocatalysts

Abstract Efficient electrochemical hydrogen production and biomass refinery are crucial for the decarbonization of various sectors. However, their energy‐intensive nature and low efficiency have hindered their practical application. In this study, earth‐abundant and non‐toxic photocatalysts that can produce hydrogen and reform biomass efficiently, utilizing unlimited solar energy, are presented. The approach involves using low‐bandgap Si flakes (SiF) for efficient light‐harvesting, followed by modification with Ni‐coordinated N‐doped graphene quantum dots (Ni‐NGQDs) to enable efficient and stable light‐driven biomass reforming and hydrogen production. When using kraft lignin as a model biomass, SiF/Ni‐NQGDs facilitate record‐high hydrogen productivity at 14.2 mmol g_cat⁻¹ h⁻¹ and vanillin yield of 147.1 mg g_lignin⁻¹ under simulated sunlight without any buffering agent and sacrificial electron donors. SiF/Ni‐NQGDs can be readily recycled without any noticeable performance degradation owing to the prevention of deactivation of Si via oxidation. This strategy provides valuable insights into the efficient utilization of solar energy and practical applications of electro‐synthesis and biomass refinement.