Surface and bulk structure modification is an effective strategy to improve the photocatalytic performance of g-C3N4 (CN). In this work, dilute NaOH solution was used in situ to regulate the CN structure for enhanced photocatalytic hydrogen evolution reaction (HER). Characterization results indicate that after treatment with dilute NaOH solution, the surface of CN was hydroxylated, resulting in the change of CN structure and the increase of BET specific surface area. Furthermore, some Na+ ions can be intercalated into the framework of CN, and form the Na–N bond. These modifications boost the HER activity of CN. The test carried out in 7.5 mM NaOH solution shows the highest activity and it is almost 3.7 times higher than that performed in water. Control tests indicate that hydroxides of other alkali and alkali earth metals such as LiOH, KOH, Ca(OH)2, and Ba(OH)2 have similar promotion effects. This work demonstrates a valid and simple way to enhance the HER activity of CN through performing the reaction in a weakly alkaline solution.
