反应器内壁附着纳米钯复合催化剂的构建及催化Heck反应性能研究

As palladium catalyst, applied to catalyze Heck reaction, restricted by the loss of Pd in the way of wide application, constructing a simple structure, stable performance, high activity, and easy recycle supported palladium catalyst has been attracted a great attention of the researchers. In this paper, we put forward the project to produce composite catalysts of palladium nanaoparticles embedded in nanofibers or micro/nano balls and put these catalysts in the reactor wall by electrostatic spinning technology. In this way, the effects of promoting Heck reaction and avoiding the loss of Pd catalyst has been got. We studied the attachment process and effects of nanaofibers or micro/nano balls on the wall of the reactor by electrospinning to explore optimum process conditions. And we also discussed the effect of the carrier on adsorption and reduction of palladium ions, aiming to prepare the new type supported palladium catalyst and investigate the stability of this system in reactor wall. Studying the catalytic properties of this system is used in catalytic Heck reaction and the relationship between components, morphology and structure of the supported material, to optimize the preparation technology of catalyst system. On the basis of our study, we can establish the structure-components-performance relationship mode of the supported catalyst materials on the reactor wall, which can provide reference for design and synthesis of this novelty kind of supported nanostructure catalyst, and also provide the scientific basis for its widely applications.

催化Heck反应的Pd催化剂的流失制约了其广泛应用, 构建结构简单、性能稳定、高活性、易于回收的负载型钯类催化剂一直是研究者关注的热点。本项目提出以静电纺丝技术为基础在反应器内壁构筑纳米纤维或者微/纳米球承载纳米钯复合催化剂，实现促进催化Heck反应和避免Pd催化剂流失的双重效应。系统研究静电纺丝技术对纳米纤维或者微/纳米球在反应器内壁上的附着过程及效果，探索最佳制备工艺条件；探讨该类载体对钯离子的吸附和还原效应，实现新型负载钯催化剂的制备，考察该体系在反应器内壁上的稳定性；研究该体系用于催化Heck反应催化性能及其与负载材料的组分、形貌、结构之间的关系，并对催化剂体系的制备工艺进行优化，从而建立该类内壁上附着载体催化材料的反应器的结构-组分-性能关系模型，为此类新型、高效的负载型纳米催化剂的设计与合成提供了参考，为其广泛应用提供科学依据。

Heck反应是烯键碳原子上一步生成新的碳-碳键的有效方法，它在有机合成中扮演着很重要的角色，备受研究者们的关注。构建结构简单、性能稳定、高活性、易于回收的负载型钯类催化剂一直是研究者在这一领域中关注的热点。本项目在国家自然科学基金的支持下，以电纺丝技术制备的一维结构的纳米纤维为模板，钯纳米粒子为催化剂的主要组分，并通过高温焙烧等过程，成功地制备出一维钯/高分子、钯/碳纤维和钯/多孔碳纤维复合催化剂；系统研究了调控试验参数对所获得的复合催化材料的结构、形貌及性能的影响，实现了对钯纳米粒子在复合催化剂中的形态及尺寸的可控合成，开辟了一维钯基复合催化剂新的制备方法。项目利用电纺丝制备技术的优势，创新性地将纺丝收集板替换为可作为反应装置的反应器，探索了一维钯基复合催化剂在钢釜反应器、铝制反应器和镀银的石英反应器内壁上可控附着，并研究了内壁附着电纺纤维载钯复合催化剂的反应器催化性能；研究结果表明，反应器上附着的催化剂具有优异催化性能，且稳定性较好。本项目的研究为新型、高效的负载型纳米催化剂的设计与合成提供理论参考与全新的设计方案。. 在国家自然科学基金的资助下，本项目完成了计划任务书中所涉及的全部研究内容，发表SCI收录的论文19篇，申请发明专利1项，超额完成了计划任务。