三维石墨烯气凝胶微结构调控用于高效催化降解PPCPs及其机理研究

Pharmaceutical and personal care products (PPCPs) are difficult to be removed by traditional water treatment processes with ecological toxicity, which possess high potential risks to eco-system and human health. This project aims at controllable assembly of 3D graphene-based aerogels (GBAs) with porous framework and active components, thus synergistically manifesting a great catalytic activity in PMS activation for PPCPs degradation. The structural characteristics, adsorption-catalytic properties and catalytic mechanisms of GBAs will be systematically investigated. Ibuprofen (IBP) and naproxen (NPX) are selected as the representative PPCPs. The effects of oxygen content, pore structure and heteroatoms doping of GBAs on their adsorption-catalytic performances will be investigated for an intrinsic structure-property relationship. Furthermore, a series of high-performance GBAs composites will be synthesized by co-assembly of GBAs with carbon nanotubes (CNTs)/metal oxides, and their synergistic effects on better catalysis and recyclability will be explored. Toward that, the reactive oxygen species (ROS), mineralization degree, degradation pathways of PPCPs and toxicity of intermediates from PPCPs degradation will be probed. The outcomes of the project in the catalytic degradation mechanisms of PPCPs, structure of 3D GBAs and correlation between the structure and performance will provide strong scientific basis for an innovative strategy toward design and modification of 3D GBAs catalysts in AOPs systems for remediating PPCPs in water.

针对水体中药物和个人护理品（PPCPs）生态毒性强、难生物降解等问题，本项目旨在通过水热组装法制备三维石墨烯气凝胶并用于催化活化过硫酸盐，调控三维多孔结构与催化活性位点发挥协同效应，构建基于硫酸根自由基氧化的非均相催化体系高效降解PPCPs。以布洛芬和萘普生这两种典型PPCPs为目标污染物，研究三维石墨烯的含氧量、掺杂程度和孔隙组成对其吸附-降解性能的影响，探讨其构-效关系和调控机制；在此基础上，通过石墨烯与碳纳米管/金属氧化物共组装，研制高活性、稳定的三维石墨烯复合宏观材料，探究其协同催化作用机理和循环再生性能。重点研究PPCPs在催化氧化过程中的活性组分、矿化程度、降解路径和生物毒性，阐明三维石墨烯激活过硫酸盐降解水中PPCPs的作用机理。研究结果将为研发高性能三维石墨烯催化剂及其水污染控制修复提供理论依据和技术支撑。

本课题围绕碳基材料活化过硫酸盐中活性位点与孔结构的协同作用这一核心问题展开研究。以三维石墨烯宏观材料的结构调控和功能组装为前提，研究其耦合过硫酸盐降解水中典型PPCPs的界面行为、作用机理和构-效关系，并基于相关问题提出了对应的碳材料调控策略。首先，通过可控自组装构建了一系列三维石墨烯并对其进行结构表征和催化研究，量化分析了氧官能团含量、掺杂种类/程度、缺陷组分以及孔隙量/比表面积与催化性能之间的构-效关系，揭示了多孔碳材料的表面活性位点与孔结构的耦合机制。在此基础上，构筑了多种金属复合多孔碳材料，系统性地分析了复合材料的协同催化机理以及对水体复合污染界面过程的调控作用，并阐明了催化剂的失活原理和再生策略。最后，重点论述了碳基过硫酸盐高级氧化技术可能存在的反应路径和验证方法，揭示了污染物在非自由基氧化体系中的界面行为和降解路径。项目研究成果将为新型碳质环境功能材料的开发及水体PPCPs的深度处理提供一定的理论依据。