College of Chemistry, Chemical Engineering and Resource Utilization, Northeast Forestry University; Key Laboratory of Forest Plant Ecology, Ministry of Education, Northeast Forestry University; Engineering Research Center of Forest Bio-Preparation, Ministry of Education, Northeast Forestry University; Heilongjiang Provincial Key Laboratory of Ecological Utilization of Forestry-based Active Substances, Northeast Forestry University, Harbin 150040, China.
Department of Chemistry, Division of Science and Technology, University of Education, Lahore, Pakistan.
J Environ Sci (China). 2025 Jun;152:287-301. doi: 10.1016/j.jes.2024.05.015. Epub 2024 May 17.
Porphyrinic hydrogen-bonded organic frameworks (porph-HOFs) have emerged as highly promising materials in the realm of photocatalysis due to their remarkable attributes, including low density, high surface area, efficient visible light absorption, and notable chemical stability. However, the rapid recombination of photogenerated charges remains a significant concern. In this work, a novel HOF-based photocatalyst, PFC-72/TiO was successfully designed with visible light response and high electron transfer capability. This involved bonding TiO nanoparticles to the PFC-72 framework synthesized using cobalt porphyrin as organic ligand and introducing bridging molecules 4-mercaptopyridine (4-PySH). Moreover, sulfadiazine (SDZ), a highly prevalent antibiotic, was effectively degraded from wastewater using PFC-72/TiO. The high specific surface area of PFC-72 significantly improved the dispersion of TiO in PFC-72/TiO, providing more active sites and improving the ability to adsorb SDZ. Characterizations and density functional theory analysis further confirmed that the photosensitization effect of porph-HOF extended the response range of TiO in PFC-72/TiO and reduced the recombination efficiency of photogenerated charges, consequently enhancing photocatalytic performance. Additionally, due to significantly improved robustness of PFC-72 and its axial coordination interaction with 4-PySH, PFC-72/TiO displayed excellent stability and recyclability. Consequently, optimized PFC-72/TiO exhibited a remarkable SDZ removal efficiency of 93.73% within 120 min, maintaining consistent photoactivity even after undergoing four cycles. Furthermore, intermediate products and degradation pathways were proposed based on UPLC-MS/MS.
卟啉氢键有机骨架（porph-HOFs）由于其低密度、高比表面积、高效可见光吸收和显著的化学稳定性等优异特性，在光催化领域中具有广阔的应用前景。然而，光生载流子的快速复合仍然是一个重大的挑战。在这项工作中，设计了一种新型的基于 HOF 的光催化剂 PFC-72/TiO，具有可见光响应和高电子转移能力。这涉及将 TiO 纳米粒子键合到 PFC-72 骨架上，该骨架是使用钴卟啉作为有机配体合成的，并引入了桥联分子 4-巯基吡啶（4-PySH）。此外，利用 PFC-72/TiO 有效地降解了废水中的磺胺嘧啶（SDZ），这是一种普遍存在的抗生素。PFC-72 的高比表面积显著提高了 TiO 在 PFC-72/TiO 中的分散性，提供了更多的活性位点，提高了对 SDZ 的吸附能力。表征和密度泛函理论分析进一步证实，porph-HOF 的光敏化效应扩展了 TiO 在 PFC-72/TiO 中的响应范围，降低了光生载流子的复合效率，从而提高了光催化性能。此外，由于 PFC-72 的稳定性得到显著提高，以及其与 4-PySH 的轴向配位相互作用，PFC-72/TiO 表现出优异的稳定性和可循环性。因此，优化后的 PFC-72/TiO 在 120 分钟内对 SDZ 的去除效率达到了 93.73%，即使经过四次循环，仍保持一致的光活性。此外，基于 UPLC-MS/MS 提出了中间产物和降解途径。
