吉林大学于吉红团队研究了增强光催化过氧化氢生产的3D打印COF/沸石复合材料。该项研究成果发表在2025年6月10日出版的《德国应用化学》杂志上。

共价有机框架（COF）具有高孔隙率和精细结构的特点，是生产过氧化氢（H₂O₂）的有前景的光催化剂。然而，它们的疏水性限制了水中的传质，给实现高性能带来了挑战。将COF与亲水性沸石偶联可以潜在地促进H₂O₂的生产，但整合这两种不同类型的多孔材料具有挑战性。

研究组首次应用三维（3D）打印技术制备了COF/沸石复合催化剂，实现了H₂O₂的卓越光合作用。通过精确优化粘合剂和预聚合条件，制备了由沸石纳米晶体和初始聚合物前体组成的均匀油墨，具有适当的流变性，适用于3D打印。 所得具有蜂窝状开放通道的整体有利于COF的原位生长和结晶，因为它促进了溶剂热后处理过程中缩合剂和大共价链段的有效分子转移。

机理研究表明，引入沸石增强了复合材料的亲水性和O₂亲和力，有利于氧还原反应途径。因此，与裸COF相比，COF/沸石复合材料对H₂O₂的光合作用显著提高了52%。这项工作提供了一种通过3D打印集成COF和沸石的简便方法，这可以利用这两种优点开辟这种复合材料的多种应用。

附：英文原文

Title: 3D-Printed COF/Zeolite Composites for Augmented Photocatalytic Hydrogen Peroxide Production

Author: Jingyi Feng, Yingzhen Wei, Xiao Li, Qifei Wang, Bolun Wang, Yunyu Guo, Binyao Feng, Enquan Jin, Jihong Yu

Issue&Volume: 2025-06-10

Abstract: Covalent Organic Frameworks (COFs), characterized by high porosity and fine-tuned structures, are promising photocatalysts for hydrogen peroxide (H2O2) production. However, their hydrophobic nature restricts the mass transfer in water, presenting challenges in achieving high performance. Coupling COFs with hydrophilic zeolites can potentially advance H2O2 production, yet integrating these two distinct types of porous materials is challenging. Herein, we first applied three-dimensional (3D) printing technology to fabricate COF/zeolite composite catalysts, which enabled superior photosynthesis of H2O2. By precisely optimizing binders and pre-polymerization conditions, homogeneous inks composed of zeolite nanocrystals and initial polymeric precursors were prepared with appropriate rheology for 3D printing. The resultant monolith with honeycomb-like open-channels was favorable for the in-situ growth and crystallization of COF by facilitating the efficient molecular transfer of condensing agents and large covalent segments during solvothermal post-treatment. Mechanistic studies indicated that introducing zeolites enhanced the hydrophilicity and O2 affinity within the composite, favoring the oxygen reduction reaction pathway. Consequently, the photosynthesis of H2O2 by the COF/zeolite composite was markedly improved by 52% compared to the bare COFs. This work provides a facile way to integrate COFs and zeolites by 3D printing, which may open diverse applications of such composites by taking advantage of both merits.

DOI: 10.1002/anie.202508226

Source: https://onlinelibrary.wiley.com/doi/10.1002/anie.202508226