新型MOFs的合成及其负载贵金属纳米合金对芳硝基化合物的催化选择性还原

Presently, Metal-organic frameworks (MOFs) have attracted growing attention from both academia and industry owing to their outstanding features and thus specific applications, such as luminescence, magnetic properties, gas storage and adsorptive separation, and catalytic properties. In the domain of catalysis, besides the well-demonstrated catalytic activity of pure MOFs, these materials are also attractive candidates for catalyst supports because of their unique porous features. The project intends to prepare a series of MOFs by reaction of easily obtained carboxylic ligands with metal salts, via facile solution-phase methods such as hydrothermal or solvothermal conditions. We will research the factors influencing the structure and properties of MOFs, such as the species of metal salts, reaction temperature, and the concentration of reactants, to attempt to open out their structure–property relationship. We plan to introduce different functional groups by post-functionalization to adjust the microenvironment of the pore, load the noble metal nanoparticles or nanomerer alloy, study its catalytic properties in lower temperatures for selective catalytic reduction of aromatic nitro compounds, and primarily elucidate the relationship between the components, structures, as well as morphologies of catalyst and their catalytic performances. The research of this project will provide experimental and theoretical guidance for the controllable preparation of MOFs and the development of efficient catalytic systems for selective catalytic reduction of aromatic nitro compounds under mild reaction conditions.

金属有机骨架化合物（MOFs）基于其本身的特点在荧光、磁性、气体储存和分离以及催化性质等方面的应用而吸引了诸多的研究兴趣。在催化研究领域，除了纯MOFs作为催化剂以外，这些材料还可以作为催化剂载体。本项目拟研究一系列羧酸配体与过渡金属、稀土金属的反应，通过水热、溶剂热及溶剂挥发等方法，构筑一系列微孔配位聚合物，表征其结构和性质，探讨反应条件（金属盐种类、溶剂、温度等）对于微孔配位聚合物结构和性质的调控作用；通过合成前修饰和后修饰引入不同的官能团，调节孔洞的微环境，并负载贵金属纳米粒子或纳米合金，深入研究其对芳硝基化合物的催化还原性能，初步阐明催化剂的组成、结构和形貌与催化性能之间的关系，以期寻求温和反应条件下的高效催化体系。通过本项目实施，不仅为寻找微孔配位聚合物的合成、结构、性质之间的关系提供信息，也为研究这类化合物负载贵金属纳米粒子或纳米合金对芳硝基化合物的催化性能和催化机理奠定基础。

金属有机框架化合物（MOFs ）作为一种新型的分子功能材料，凭借其独特的结构可剪裁性、多样的拓扑结构和在气体存储、离子交换、吸附、分子识别、催化以及光、电、手性拆分等领域的巨大潜在应用受到了各界科学家们越来越多的关注。本研究中，我们合成了9个新型MOFs（ CP-1--- CP-9），对CP-1-6表征了其组成和结构，研究了部分MOFs的吸附性质和荧光检测性质。其中CP-2具有较高的热稳定性和对水稳定性，且对CO2、C2H6、C3H8等小分子气体具有较高的吸附能力和较大的吸附焓，尤其对CO2有较大的吸附量（在1 atm，298K时为343.7mg g-1），以及CO2对N2和CH4具有较高的吸附选择性。荧光测试结果表明，CP-4-Tb是一种较好的水相Fe3+和Cr2O72-的荧光探针。研究工作将为设计合成新型MOFs用于CO2储存和分离以及C2H6、C3H8储存方面，以及在水相中检测和传感环境污染物方面提供借鉴。