Optically and Electrocatalytically Decoupled Si Photocathodes with a Porous Carbon Nitride Catalyst for Nitrogen Reduction with Over 61.8% Faradaic Efficiency

Abstract The photoelectrochemical (PEC) approach is attractive as a promising route for the nitrogen reduction reaction (NRR) toward ammonia (NH₃) synthesis. However, the challenges in synergistic management of optical, electrical, and catalytic properties have limited the efficiency of PEC NRR devices. Herein, to enhance light‐harvesting, carrier separation/transport, and the catalytic reactions, a concept of decoupling light‐harvesting and electrocatalysis by employing a cascade n⁺np⁺‐Si photocathode is implemented. Such a decoupling design not only abolishes the parasitic light blocking but also concurrently improves the optical and electrical properties of the n⁺np⁺‐Si photocathode without compromising the efficiency. Experimental and density functional theory studies reveal that the porous architecture and N‐vacancies promote N₂ adsorption of the Au/porous carbon nitride (PCN) catalyst. Impressively, an n⁺np⁺‐Si photocathode integrating the Au/PCN catalyst exhibits an outstanding PEC NRR performance with maximum Faradaic efficiency (FE) of 61.8% and NH₃ production yield of 13.8 µg h^–1 cm^–2 at −0.10 V versus reversible hydrogen electrode (RHE), which is the highest FE at low applied potential ever reported for the PEC NRR.