Embedding Carbon Quantum Dots into Crystalline Polyimide Covalent Organic Frameworks to Enhance Water Oxidation for Achieving Dual-Channel Photocatalytic H₂O₂ Generation in a Wide pH Range

Abstract

Photocatalytic technique is regarded as the cleanest approach for producing H₂O₂. Herein, two kinds of novel polyimide COFs decorated with CQDs (namely, MPa-COFs/CQDs and MNd-COFs/CQDs) were constructed by using the one-pot hydrothermal method. Due to the electron donor role of CQDs, the recombination of photoinduced electrons and holes was suppressed after the combination of polyimide COFs with CQDs. Importantly, the introduction of CQDs not only boosted the absorbing ability of polyimide COFs toward visible light but also reduced the impedance and improved the charge transfer efficiency. After CQDs were embedded into polyimide COFs, the surface hydrophilicity of catalysts was significantly improved, which provided convenience for the water oxidation reaction. Benefiting from the electron donor-acceptor interaction between polyimide COFs and CQDs, a step-by-step two-electron oxygen reduction reaction over polyimide COFs was enhanced. More interestingly, the embedding of CQDs can create a direct two-electron water oxidation reaction pathway, which played an important role in photocatalytic H₂O₂ generation. Meanwhile, H⁺ generated from water oxidation can also be used for the reduction of oxygen to form H₂O₂. Under the synergistic effects of water oxidation and oxygen reduction, as-prepared MPa-COFs/CQDs-2 displayed excellent performance in photocatalytic H₂O₂ generation, and its yield was as high as 540 μmol/g within 60 min. In short, the current work shared an effective strategy to improve the performance of polyimide COFs in photocatalytic H₂O₂ production.