Recent Advances in Application of Graphitic Carbon Nitride‐Based Catalysts for Photocatalytic Nitrogen Fixation

Ammonia, the second most-produced chemical, is widely used in agricultural and industrial applications. However, traditional industrial ammonia production dominated by the Haber-Bosch process presents huge resource and environment issues due to the massive energy consumption and CO₂ emission. The newly emerged nitrogen fixation technology, photocatalytic N₂ reduction reaction (p-NRR), uses clean solar energy with zero-emission, holding great prospect to achieve sustainable ammonia synthesis. Although great efforts are made, the p-NRR catalysts still suffer from poor N₂ adsorption and activation, inferior light absorption, and fast recombination of photocarriers. Due to the tunable electronic structure of the metal-free polymeric graphitic carbon nitride (g-C₃ N₄ ), the above-mentioned issues can be significantly alleviated, making it the most promising p-NRR photocatalyst. This review summarizes the recent development of g-C₃ N₄ -based catalysts for p-NRR, including the working principle of p-NRR catalysts, the challenges of developing p-NRR catalysts, and corresponding solutions. Particularly, the roles of defect engineering and heterojunction construction on g-C₃ N₄ to the enhancement of photocatalytic performances are emphasized. In addition, computational studies are introduced to deepen the understanding of reaction pathways. At last, perspectives are provided on the development of p-NRR catalysts.