Nanoarchitectonics of S‐Scheme Heterojunction Photocatalysts: A Nanohouse Design Improves Photocatalytic Nitrate Reduction to Ammonia Performance

Photocatalytic nitrate reduction reaction (NitRR) is a promising route for environment remediation and sustainable ammonia synthesis. To design efficient photocatalysts, the recently emerged nanoarchitectonics approach holds great promise. Here, we report a nanohouse-like S-scheme heterjunction photocatalyst with high photocatalytic NitRR performance. The nano-house has a floor of plate-like metal organic framework-based photocatalyst (NH₂-MIL-125), on which another photocatalyst Co(OH)₂ nanosheet is grown while ZIF-8 hollow cages are also constructed as the surrounding wall/roof. Experimental and simulation results indicate that the positively charged, highly porous and hydrophobic ZIF-8 wall can modulate the environment in the nanohouse by (i) NO₃ ^- enrichment/NH₄ ⁺ discharge and (ii) suppression of the competitive hydrogen evolution reaction. In combination with the enhanced electron-hole separation and strong redox capability in the NH₂-MIL-125@Co(OH)₂ S-scheme heterjunction confined in the nano-house, the designed photocatalyst delivers an ammonia yield of 2454.9 μmol g^-1 h^-1 and an apparent quantum yield of 8.02 % at 400 nm in pure water. Our work provides new insights into the design principles of advanced photocatalytic NitRR photocatalyst.