Cu2O/2D COFs Core/Shell Nanocubes with Antiphotocorrosion Ability for Efficient Photocatalytic Hydrogen Evolution

Abstract

Photocorrosion of highly active photocatalysts is an urgent problem to be solved in the field of photocatalysis; however, searching for effective strategies for inhibiting photocorrosion of photocatalysts is still a grand challenge. Herein, we design and construct a class of Cu₂O/2D PyTTA-TPA COFs (PyTTA: 1,3,6,8-Tetrakis(4-aminophenyl)pyrene, TPA: p-benzaldehyde) core/shell nanocubes to greatly boost the performance of photocatalytic hydrogen evolution and significantly inhibit the photocorrosion. The optimal Cu₂O/PyTTA-TPA COFs core/shell nanocubes exhibit an excellent photocatalytic H₂ evolution rate of 12.5 mmol h^-1 g^-1, which is ∼8.0-fold and ∼20.0-fold higher than those of PyTTA-TPA COFs and Cu₂O nanocube, respectively, and also is the best in all the reported metal oxides catalytic materials. The mechanism studies demonstrate that the appropriate matching band gaps and tight integration of PyTTA-TPA COFs and Cu₂O nanocubes can significantly facilitate the separation of photogenerated electron-hole pairs in the Cu₂O/PyTTA-TPA COFs core/shell nanocube during the photocatalytic process, which ameliorates the photocatalytic H₂ evolution activity. Most importantly, the 2D PyTTA-TPA COFs shell with outstanding intrinsic stability protects Cu₂O nanocubes core from photocorrosion by showing no morphology and crystal structure change after 1000 times of photoexcitation.

Keywords: Covalent organic frameworks; Cu2O; antiphotocorrosion; core/shell heterojunction; photocatalytic hydrogen evolution.