Metal-Free 2D/2D van der Waals Heterojunction Based on Covalent Organic Frameworks for Highly Efficient Solar Energy Catalysis

Covalent organic frameworks (COFs) have emerged as a kind of rising star materials in photocatalysis. However, their photocatalytic activities are restricted by the high photogenerated electron-hole pairs recombination rate. Herein, a novel metal-free 2D/2D van der Waals heterojunction, composed of a two-dimensional (2D) COF with ketoenamine linkage (TpPa-1-COF) and 2D defective hexagonal boron nitride (h-BN), is successfully constructed through in situ solvothermal method. Benefitting from the presence of VDW heterojunction, larger contact area and intimate electronic coupling can be formed between the interface of TpPa-1-COF and defective h-BN, which make contributions to promoting charge carriers separation. The introduced defects can also endow the h-BN with porous structure, thus providing more reactive sites. Moreover, the TpPa-1-COF will undergo a structural transformation after being integrated with defective h-BN, which can enlarge the gap between the conduction band position of the h-BN and TpPa-1-COF, and suppress electron backflow, corroborated by experimental and density functional theory calculations results. Accordingly, the resulting porous h-BN/TpPa-1-COF metal-free VDW heterojunction displays outstanding solar energy catalytic activity for water splitting without co-catalysts, and the H-2 evolution rate can reach up to 3.15 mmol g(-1) h(-1), which is about 67 times greater than that of pristine TpPa-1-COF, also surpassing that of state-of-the-art metal-free-based photocatalysts reported to date. In particular, it is the first work for constructing COFs-based heterojunctions with the help of h-BN, which may provide new avenue for designing highly efficient metal-free-based photocatalysts for H-2 evolution.

Automated summary

A novel metal-free 2D/2D van der Waals heterojunction was successfully constructed by integrating a two-dimensional COF with ketoenamine linkage and defective hexagonal boron nitride. The presence of VDW heterojunction and introduced defects facilitated charge carriers separation and provided more reactive sites. The resulting heterojunction exhibited excellent solar energy catalytic activity for water splitting, surpassing the performance of pristine COF and other metal-free-based photocatalysts reported to date.