三维材料负载有序介孔MOFs限域TiO2（TiO2@MOFs@3D）整体式催化剂的构建及其光热协同催化多组分VOCs性能研究

Recently, the regional compound pollutions represented by PM 2.5 and O3, which are caused by VOCs, have become one of the major environmental issues. At present, thermo-photocatalysis technology is one of the effective ways to remove VOCs, the preparation of monolithic catalysts with high adsorption capacities, visible light catalytic activity, thermal stability and multistage pore distribution is of great significance in the practical application of thermo-photocatalysis technology. Based on characteristic of nubbly three dimensional material graphene aerogel’ superior charge carrier mobility and ordered mesoporous metal organic frameworks (MOFs) materials’ ordered functional channel and good visible light/thermal catalytic performance, MOFs confined usual TiO2 as photocatalysts are supported on three dimensional materials. The synthesis of TiO2@MOFs@3D solves some key problems of the photoproduction carrier recombination, visible, the aggregation and deactivation of TiO2 system and power catalysts forming, aiming at achieving a high photocatalytic activity for multicomponent VOCs under visible light. The relation between the thermo-photocatalytic activity and the physical characters of TiO2@MOFs@3D catalysts are expounded on in the research. In addition, transmission process of photoproduction carrier, the mechanism of improved photo/thermal conversion efficiency, and the dynamic mechanism of "adsorption-visible light thermo-photocatalysis-regeneration" in the multicomponent VOCs elimination are also discussed, which provide the experimental and theoretical basis for the application of the thermo-photocatalysis technology in gaseous pollutants control.

近年来，由VOCs所引起的以PM2.5和O3为特征的区域性复合污染，成为重大环境课题之一。光热协同催化是去除VOCs的有效方法之一，开发具有高吸附容量、可见光催化活性、热稳定性和多级孔结构的整体式催化剂，对于该技术的应用具有重要的意义。本研究以实现可见光高效去除多组分VOCs为最终目的，选取光催化剂中常用的TiO2，利用块状三维材料石墨烯气凝胶优异的电荷迁移性以及有序介孔金属有机骨架材料（MOFs）孔道有序可功能化、可见光/热催化性能良好的特点，实现三维材料负载MOFs限域TiO2，从根本上解决光生载流子复合、可见光响应、TiO2团聚和粉体催化剂成型的关键问题。通过研究催化剂微观结构与性能之间的内在规律，阐明光生载流子的传输过程，揭示光热转化效率提高的机理，深入探讨其在多组分VOCs消除过程中的“吸附-协同催化-再生”动态作用机制，为该技术在气态污染物治理中的推广提供理论依据和实践基础。

近年来，开发具有高吸附容量、可见光催化活性、热稳定性和多级孔结构的催化剂，对于光热技术去除VOCs具有重要的意义。本项目建立具有良好催化性能的TiO2及MOF基催化剂的稳定可控制备方法，实现对动态气氛中多组分VOCs的高效快速降解；阐明催化剂光热协同催化多组分VOCs的反应机理以及在多组分VOCs消除过程中的“吸附-可见光热催化-再生”动态作用机制，为该类催化剂在气态污染物治理中的推广提供理论依据。主要研究内容如下：（1）制备了一系列Ti基金属有机骨架材料，并以此为前驱体，通过调控温度、时间、气氛煅烧制备出一系列MOFs基TiO2催化剂，结合XRD、物理吸附仪、SEM和TEM等表征手段，研究优化这些MOFs基TiO2功能材料的结构；（2）基于金属有机骨架进行结构改性，探究VOCs在MOFs及其衍生物表面的吸附/脱附性能，研究甲苯吸脱附性能及反应动力学，并对其吸附动力学、热力学、竞争吸附及扩散机理等进行了深入的探究；（3）通过TiO2改性等方式调控催化剂结构，用于VOCs光催化、热催化以及光热协同催化测试。探究单一光、热催化的VOCs降解机制以及光效应在热催化过程中的贡献度及促进机制，提出光热协同催化技术处理VOCs的关键技术参数，探讨催化剂在多组分VOCs消除过程中的“吸附-可见光热催化-再生”动态作用机制，这为今后开发高效消除大气复合型污染催化剂及其工艺奠定实验和理论基础。