系列新型氮掺杂石墨烯一维中空纳米结构的构筑、性能及协同机理研究

Recently, the N-doped graphene one-dimensional nanostructures have attracted extensive attention because of the inherent physical and chemical properties of the N-doped graphene combining with the unique properties of one-dimensional hollow nanostructures. So that, developing effective new approaches for obtaining a series of novel N-doped graphene one-dimensional (1D) hollow nanostructures and exploring their various innovative properties have became a very challenging and urgent research subject. In this project, the study on the construction, properties and synergistic mechanism of a series of novel N-doped graphene 1D hollow nanostructures is innovatively carried out. Main research contents as following: 1) Novel N-doped graphene 1D hollow nanostructures with tubular shapes, homojunction (heterojunction) coatings and helical shapes are prepared via a template-free chemical vapor reaction method, and the key fabrication techniques are mastered, the growth, doping and modification mechanisms of the obtained products are elucidated and the corresponding theoretical models are established, respectively. 2) The effects of morphology, microstructure, component, nitrogen bonding configurations and doping content on the field emission, photoluminescence and electrochemical performances of the products are systematic studied, and according to band theory, chemical absorption/desorption and redox theory etc, the performances optimization mechanism of the products are interpreted. 3) Electricity property of the various monomer products and mechanics performance of the helical monomer products are investigated systematically, and the change regularity and mechanism of the electricity property of the different monomer products and the deformation rules of the helical monomer products in the microscales are obtained.

基于氮掺杂石墨烯固有的物化属性和一维中空纳米结构的性能特点，氮掺杂石墨烯一维中空纳米结构已引起广泛关注，开发有效新途径以获得系列新型氮掺杂石墨烯一维中空纳米结构，进而探索其各种新颖性能，已经成为一项极具挑战而又亟待解决的研究课题。本项目创新性地开展系列新型氮掺杂石墨烯一维中空纳米结构的构筑、性能及协同机理研究。主要研究内容：1）采用无模板化学气相反应法获得管状、同（异）质结包覆、螺旋状等新型氮掺杂石墨烯一维中空纳米结构，掌握其关键制备技术，揭示其生长、掺杂和修饰改性机理，建立相应的理论模型；2）系统研究产物形貌、微观结构、组分、氮的键合构型及掺杂量对其场发射、光致发光及电化学性能的影响规律，并结合能带理论、化学吸脱附及氧化还原等理论，诠释产物性能优化机理；3）系统探究单体系列产物的电学性能及单体螺旋状产物的力学性能，获得微尺度下不同产物原位电学性能的变化规律与机理及单体螺旋状产物的形变规律

完成了项目书中的全部内容：1）采用无模板一步化学气相法及两步掺氮法（NH3为N源）制备出不同氮掺杂量的石墨烯一维中空纳米结构，提出了改进的VLS产物形核-生长机理，并掌握了其关键制备技术。2) 采用无模板一步化学气相反应法制备出同质（多层碳、多褶皱石墨烯）、异质（SiO2）包覆的氮掺杂石墨烯一维中空纳米结构（N-GNTs@MLC、N-GNTs@GS、GNTs@a-SiOx(x=1~2)NPs）；采用化学气相法+水热法，获得了CoNi2S4包覆氮掺杂石墨烯一维中空纳米结构（N-GNTs@ CoNi2S4），并掌握了关键制备技术。基于介观生长热、动力学及异质形核理论，提出了系列同、异质复合材料的生长机理。3）以Ar/H2 混合气为反应气氛，采用化学气相反应法获得了螺旋状氮掺杂石墨烯一维中空纳米结构，掌握了其关键制备技术，并从催化剂与H2反应气氛两个角度阐述螺旋状产物的生长机理。4）获得了具有优异场发射、光致发光及电化学性能的系列氮掺杂石墨烯一维中空纳米结构及其复合材料，并从能带弯曲、缺陷密度等角度建立了氮掺杂管状石墨烯及其与活性材料协同作用下的性能优化机理；5) 在耦合有Nanofactory电学样品杆的透射电镜JEOL2010中，结合电子束诱导沉积技术，对单体氮掺杂石墨烯一维中空纳米结构实现了原位实时电学性能测量，采用基于电子束与聚焦离子束双束系统的探针-悬臂梁纳米材料力学测试系统，对单体氮掺杂石墨烯一维中空纳米结构进行拉伸加载测试，探索了产物在微尺度下的电子输运行为和弹性变形行为。.拓展性工作：1) 采用水热法制备了Fe2O3包覆氮掺杂石墨烯管复合材料，获得了具有高比电容及倍率性能的复合电极材料和优选制备工艺；2）采用水热法、电沉积法制备了MoS2及MoS2/Ni(OH)2包覆氮掺杂石墨烯管纳米复合材料，获得了具有优异析氢性能的复合电极材料和优选制备工艺，并探讨了其性能优化机理。.取得的成果：获青岛市自然科学一、二等奖各1项，中石化协会科技进步二等奖1项、三等奖2项，省高校科研成果一等1项、二等奖2项；申请国家发明专利19项，授权12项；发表论文77篇，其中SCI收录68篇次，大于5.0的31篇；培养青年教师3名，博士4名，硕士24名，远超项目计划中“发表高水平论文8~15篇，申请国家发明专利2~3项”的任务指标。所获创新成果具有原创性，达到国内外同类技术领先水平。