铀是核能技术领域最主要的燃料资源，研究铀的富集分离技术有利于核能工业的可持续发展。吸附法具有诸多优势，被认为是铀富集分离领域最具潜力的方法之一，而合成性能优良的吸附材料是实现有效分离的关键。多孔框架材料兼具多孔性和功能性，在铀的富集分离领域拥有良好的应用潜力，但如何赋予其合适的组织形态以更好地适用于铀的分离是目前面临的关键挑战之一。同时，如何充分发挥多孔框架材料可面向目标进行分子设计和结构调控的优势，合成出对铀吸附性能更佳的新型多孔框架材料，也具有重要的研究价值。为此，本论文针对多孔框架材料的功能导向合成展开系统研究，致力于制备更具实用形态的多孔框架复合材料以及设计合成可高效吸附铀、且结构更稳定的新型多孔框架材料。一方面，以金属有机框架 (MOFs) 材料为主体，研究了其常温合成方法以及在核径迹膜 (PCTM) 孔道内的成核生长行为及其调控因素，在此基础上构建了金属有机框架复合分离膜，实现了水溶液中铀的有效分离。另一方面，基于偕胺肟基团对铀的配位络合机理，从分子设计出发，合成了两类共轭微孔聚合物 (CMPs)，并研究了其对铀酰离子的吸附行为和构效关系。论文的创新性成果包括：第一，研究了不同类型MOFs晶体的常温合成，揭示了合成反应条件对MOFs结构、形貌和晶粒尺寸的影响规律。对比研究了不同MOFs晶体对铀的吸附性能，并阐明了ZIF-8对铀的吸附机理。第二，采用相对扩散合成法研究了PCTM孔道中MOFs晶体的成核生长行为，并借助仿生多巴胺化学，实现孔道中不同类型MOFs晶体界面成核和原位生长过程的有效调控，为广泛制备MOFs复合材料奠定了基础。研究还揭示了PCTM基体因酯交换反应促进MOFs成核的原理以及聚多巴胺对MOFs的锚定作用和结构稳定性增强机制。第三，制备出以核径迹膜为载体的膜支撑ZIF-8复合材料，赋予了纳微米尺度的ZIF-8晶体更适用于分离操作的应用形态。该复合分离膜对铀表现出良好的过滤吸附性能和循环复用能力。第四，基于功能导向的分子设计，合成了两种含有不同偕胺肟基密度的CMPs，对比研究了材料对铀的吸附行为，揭示了材料组成、结构与吸附能力之间的关系。本论文的研究一方面对于深入认识多孔框架材料成核生长行为及其调控机制具有科学意义，有利于制备更具实用形态的多孔框架复合材料，并推进其在铀分离领域的应用；另一方面也为结构更优良的多孔框架材料的设计合成提供了新的思路，并为研究其吸附铀的构效关系提供了理论支持。

Uranium is the primary fuel resourse in the field of nuclear energy technology. Enrichment and separation of uranium is an important way for achieving the sustainable development of nuclear power industry. Adsorption has been regarded as one of most potential methods to realize the enrichment and separation of uranium due to its advantages. Development of high-efficiency adsorbents is the key in adsorption method. Among various adsorbents, porous framework materials, featured by favorable porosity and tailored functionality, show great potential in uranium enrichment and separation. However, one of the key challenges is to prepare porous framework materials with deployable form which facilitate the practical use in uranium separation. Meanwhile, to synthesize porous framework materials with high-performance for uranium adsorption, it is of great value to make full use of the advantages of its task-specific designability and structure controllability. This dissertation presents a systematical study on the function-oriented synthesis of porous framework materials, which is dedicated to the preparation of porous framework composites materials with more conveniently deployable form and the task-specific synthesis of new porous framework materials with better structural stability for highly-efficient uranium adsorption. On the one hand, taking metal-organic frameworks (MOFs) as a model, the room-temperature synthesis MOFs and their nucleation and growth behaviors, as well as the regulating factors, within polycarbonate track-etched membrane (PCTM) were investigated. And on this basis, a MOFs composite separation membrane was synthesized for the preconcentration and separation of uranium. On the other hand, base on the coordination mechanism between amidoxime group and uranyl ion, the design and synthesis of two kinds of conjugated microporous polymers (CMPs) were achieved. And, the adsorption behavior and structure-activity relationship between CMPs and uranyl ions were systematically studied. Innovative achievements of this dissertation include:Firstly, the room-temperature synthesis of different kinds of MOFs was investigated and the effects of synthesis condition on the structure, morphology and crystal size of MOFs were elucidated. Then, the uranium adsorption performance by different MOFs were comparative studied, while the adsorption mechanism of uranium on ZIF-8 was explained. Secondly, using a facile contra-diffusion synthetic strategy, the nucleation and growth behavior of MOFs in PCTM channels was studied. Taking advantage of the bio-inspired polydopamine chemistry, the regulation of heterogeneous nucleation and in situ growth of different MOFs crystals was realized, which paved a way for the synthesis of more MOFs composites. The mechanism of transesterification promoted nucleation as well as the anchoring effect and structural enhancement of MOFs by the polydopamine interfaces were also revealed. Thirdly, a PCTM supported ZIF-8 composite material was synthesized, endowing nano- and micron-scale ZIF-8 crytals with more conveniently deployable form for separation operation. The composite membranes exhibited good adsorption performance and reuseability for uranium. Fourthly, according to function-oriented molecular design, two kinds of CMPs with different amidoxime density were synthesized via the the reaction of Sonogashira-Hagihara coupling. The adsorption behavior of the CMPs toward uranium were comparatively studied, and the relationship between composition, structure and adsorption performance of uranium was revealed.The research in this dissertation, on the one hand, is of scientific significance for further understanding the nucleation and growth behavior as well as regulation mechanism of porous framework materials, which would promote the synthesis of porous framework composite materials with more conveniently deployable form for the application in the field of uranium separation. On the other hand, it also provides a new strategy for the design and synthesis of porous framework materials with optimized structure, as well as theoretical support for the study of the structure-performance relationship on uranium adsorption.