Protonation‐Assisted Exfoliation of N‐Containing 2D Conjugated Polymers

Abstract Ultrathin 2D conjugated polymer nanosheets are an emerging class of photocatalysts for solar‐to‐chemical energy conversion. Until now, the majority of ultrathin 2D polymer photocatalysts are produced through exfoliation of layered polymers. Unfortunately, it still remains a great challenge to exfoliate layered polymers into ultrathin nanosheets with high yields. In this work, a liquid‐phase protonation‐assisted exfoliation is demonstrated to enable remarkably improved exfoliation yields of various 2D N‐containing conjugated polymers such as g‐C 3 N 4 , C 2 N, and aza‐CMP. The exfoliation yields are only 2–15% in pure water whereas they can be substantially improved to 41–56% in 12 m HCl. The exfoliated ultrathin nanosheets possess average thicknesses less than 5 nm and can be easily dispersed in aqueous solutions. More importantly, the exfoliated nanosheets exhibit significantly enhanced photocatalytic activity toward photocatalytic water splitting compared to their bulk counterparts. Further characterizations and computational calculations reveal that protonation of the heterocyclic nitrogen sites in the conjugated polymer frameworks can lead to strong hydrogen bonding between the polymer surfaces and water molecules, resulting in facilitated exfoliation of polymers into the liquid phase. This study unveils an important protocol toward producing ultrathin 2D N‐containing conjugated polymer nanosheets for future solar energy conversion.