Jingzhen Zhang,Chunyang Yu,Junyu Lang,Yongfeng Zhou,Baoxue Zhou,Yun Hang Hu,Mingce Long
Photocatalytic H 2 O 2 production (PHOP) on graphitic carbon nitride (GCN) at neutral pHs is limited by the sluggish oxidation of sacrificial alcohols and insufficient protons. In our work, the PHOP over a series of K intercalated triazine (KTCN) or tri-s-triazine units (KTTCN) reached 11–32 folds of GCN in the presence of only 0.5 vol% isopropanol, and a positive correlation between the H 2 O 2 production and the K contents was found. The critical role of K was revealed as that K intercalation creates Lewis acidic sites for isopropanol adsorption and strengthens Lewis basic sites for hydrogen abstraction and proton release. The improved alcohol oxidation and enhanced O 2 chemisorption synergistically result in dramatically accelerated PHOP over KTTCN. The findings provide the understanding of the preliminary active site dependent PHOP mechanism and bring insights for design of carbon nitride polymers with desirable photocatalytic performance.
Improving the charge separation and migration in graphitic carbon nitride (CN) is the critical issue to enhance its photocatalytic performance, but still remains very challenging. Herein, the alkali metals were introduced into the interlayer and intralayer of CN to tackle this challenge. The lithium sodium-modifying carbon nitride layer (LiNaCN2) and the adjacent CN layer formed a van der Waals heterostructures (VDWHs), while the potassium-intercalating served as interlayer charge transfer channels to induce the directional charge flow. Experiments and theoretical calculations indicated that such unique construction provided intrinsic driving force to obtain the electrons from LiNaCN2 to CN via directional potassium channels. In accordance with the theoretical prediction, a dramatically red-shift of the light absorption feature was achieved for interlayer potassium-intercalating and intralayer lithium sodium-modifying co-functionalized carbon nitride (LiNaCN-K-CN2) to show narrowed bandgap energy of 2.15 eV. This directional charge flow in CN resulted in the rapid transfer of charge carriers in both interlayer as well as intralayer of CN, which reduced the electronic localization as well as extended the π conjugative effect. Consequently, the LiNaCN-K-CN2 displayed stable and remarkable hydrogen production rate of about 2.46 mmol g −1 h −1 with apparent quantum yield (AQY) of about 13.68% at 435 nm, which was 22 folds higher than that of the pristine CN. This finding provides the feasible strategy to precisely tune the directions of charge transfer for high-performance CN-based photocatalysts.
危险品化学品经营许可证（带存储）