Scalable fabrication of hypercrosslinked nanobeads for dual photocatalysis: Hydrogen evolution and dye degradation

Hypercrosslinked polymers have emerged as a new generation of porous material, offering tailorable functionality and structural definition comparable to crystalline solids. Recent developments in organic catalysts have highlighted their potential. Here, we demonstrate that hypercrosslinking induces long-range atomic order in covalent organic framework nanobeads (Hc-TFpBAD(CN)). These photocatalysts can effectively promote charge separation, while their nanoscale size enhances charge transport properties. First, the loading of cocatalyst increases hydrogen (H₂) evolution, achieving a high H₂ evolution rate of 171.3 μmol h⁻¹ g⁻¹, and remains highly stable for extended photocatalytic operation up to 36 h. Second, the influence of different electron donors on stability and H₂ was investigated, with triethanolamine identified as the most effective donor. Third, the photocatalytic activity was further enhanced by introducing methylene blue (MB) dye as an electron mediator, enabling simultaneous H₂ evolution and dye degradation. The dye degradation results show that Hc-TFpBAD(CN) achieved degradation efficiency of 99.9% within 240 min.