Highly Efficient Photocatalytic H2 Evolution from Water using Visible Light and Structure‐Controlled Graphitic Carbon Nitride

Abstract The major challenge of photocatalytic water splitting, the prototypical reaction for the direct production of hydrogen by using solar energy, is to develop low‐cost yet highly efficient and stable semiconductor photocatalysts. Herein, an effective strategy for synthesizing extremely active graphitic carbon nitride (g‐C 3 N 4 ) from a low‐cost precursor, urea, is reported. The g‐C 3 N 4 exhibits an extraordinary hydrogen‐evolution rate (ca. 20 000 μmol h −1 g −1 under full arc), which leads to a high turnover number (TON) of over 641 after 6 h. The reaction proceeds for more than 30 h without activity loss and results in an internal quantum yield of 26.5 % under visible light, which is nearly an order of magnitude higher than that observed for any other existing g‐C 3 N 4 photocatalysts. Furthermore, it was found by experimental analysis and DFT calculations that as the degree of polymerization increases and the proton concentration decreases, the hydrogen‐evolution rate is significantly enhanced.