基于超分子作用的石墨烯三维自组装及其在电化学研究中的应用

The derivatives of graphene and superamoleclar host will be synthappropriate supramolecular host and guest compounds will be synthesized. Then a system of guests, which can forme inclusion compounds with above host modified on to the surface of guraphene with 2:1 ratio of host to gest will be selected as a bridge linker for the assembly of obove graphene derivatives. Based on the supramolecular interaction, the porous three-dimension self-assembly of graphene will be prepared. The dimension and the amount of the hole in assembly will be controlled by selecting different length of the chain of bridge linker.On this basis, the distribution and loading of metal and metal oxide nanoparticles on the graphene assembly acting as supporter will be studied. The catalysis specific property of graphene assembly loading nanoparticles in organic reaction will be investigated. The rucuction graphene assembly with more conductance will be obtained by deoxidizing assembly of graphene oxide, and then be used to make a modified electrode. The electrochemical behaviour of organic compounds on this modified electrode will be studied. High-performance electrochemical sensors will be constructed by using this modified electrode. At last, Fe2O3 and MnO2, and so on will be loaded and distributed in to the assembly of graphene, which will be worked as a posive materia in lithium-ion.The mechanism of intercalation and de intercalation of lithium-ion on graphene assembly modified electrode will be investigated. The charge-discharge property of positive electrode of lithium-ion battery will be studied. High-performance lithium-ion battery electrode materials will be explored. It is expected that this successful project will help us to extend the application of graphene. It is also helpful for investigating the higher effective catalysis, more powerful electrodes.

通过化学修饰，制备石墨烯-主体化合物衍生物；再选择可与修饰在石墨烯表面的主体化合物形成主客体包合比为2:1的客体分子作为桥链分子，与石墨烯-主体化合物衍生物发生超分子作用，实现石墨烯的三维自组装，生成多孔性石墨烯组装体。改变桥链分子的链长，可调节石墨烯组装体的孔径和孔隙率。研究金属、金属氧化物纳米粒子在石墨烯组装体中的负载和分布特性，探索其催化性能。将氧化石墨烯组装体经化学还原制备导电性更好的还原性石墨烯组装体，并用于制备修饰电极，探索该修饰电极在有机物电化学氧化与还原反应中的催化性能；探索其在高性能电化学传感器构建中的应用；研究负载有Fe2O3、MnO2等纳米金属氧化物粒子的石墨烯组装体作为锂离子正极材料时的充放电特性，开发高性能锂离子正极材料。可以预期，该项目的研究成功，将进一步拓展石墨烯的应用领域，并为开发性能优良的催化剂、高性能电极等提供理论和实验依据。

本项目通过化学修饰或自组装的方式，制备了石墨烯-主体化合物衍生物；再选择可与修饰在石墨烯表面的主体化合物形成主客体包合比为2:1的客体分子作为桥链分子，如金刚烷二聚体、二茂铁二聚体等，与石墨烯-主体化合物衍生物发生超分子作用，实现了石墨烯的三维自组装，生成了多孔性石墨烯组装体。改变桥链分子的链长，可调节石墨烯组装体的孔径和孔隙率。与原始的还原石墨烯相比，自组装3D石墨烯显示出更为优异的比容量、倍率特性和循环稳定性。在此基础上，研究了金属、金属氧化物纳米粒子在石墨烯组装体中的负载和分布特性，探索其催化性能。将氧化石墨烯组装体经化学还原制备导电性更好的还原性石墨烯组装体，并用于制备修饰电极，探索该修饰电极在有机物电化学氧化与还原反应中的催化性能；探索了其在高性能电化学传感器构建中的应用。研究了负载有Fe2O3、MnO2等纳米金属氧化物粒子的石墨烯组装体作为锂离子负极材料时的充放电特性，开发出高性能锂离子正极材料。.本项目还研究了羧基修饰的柱[5]芳烃与胡萝卜素、叶绿素之间的主客体作用；通过双亲柱[6]芳烃与三磷酸腺苷的相互作用实现可控释放；磁响应性双亲柱[5]芳烃超分子囊泡的自组装及其可控释放应用；聚合物环糊精对部分药物的包合特性。此外，采用水热合成方法和静电纺丝方法合成了α-Fe2O3@Li4Ti5O12、多孔碳纳米纤维、多孔碳包覆四氧化三铁纳米纤维等并应用于锂离子负极材料。.根据项目计划书，各项目任务现已完成。项目执行期间取得了较好的研究成果，共计发表SCI论文40篇，申请专利18项。项目执行期间，共有3人参加国际会议1次，10人次参加国内学术会议6次。培养博士5名，硕士11名。超额完成项目计划书中的研究目标。