MOFs衍生多杂原子/多金属掺杂碳基复合材料协同增强ORR电催化活性研究

The development of high-performance non-noble metal catalyst is the key strategy for the practical application of fuel cell. As an anode material, heteroatoms-doped carbon composite possesses the advantages of good conductivity and stability, low cost and environmental benign. However, the low dispersion, lost surface area and poor catalytic activity seriously limit its practical application. To solve these problems, in this project, we propose a novel strategy using heteroatoms-riched and heterometals metal-organic frameworks (MOFs) as precursors to synthesize heteroatoms/heterometals-doped carbon composites. It is believable that porous carbon composites with high dispersion and surface area can be obtained through optimization of the heteroatoms composition and content, and the porosities of MOFs even the calcination parameters. At the same time, it can also regulate the best chemical states and doping quantities of heteroatoms/heterometals. Moreover, by introducing multiple active sites, the ectronic structures of carbon composites can be modulated and the ORR electrocatalytic performances can be optimized. Also, novel digital holography technology will be introduced to in-situly detect the changes of carbon composite/catalytic interface. Combined with state-of-the-art physical and chemical measurements, the effect law of chemical components, microstructures and morphologies on ORR electrocatalytic performances of carbon composites will be investigated. The project will reveal the influence and the mechanism of multiple doping state, nano-size effect, especially synergetic effect of carbon composites on ORR electrocatalytic activities. The research findings will provide new opinion for the development and application of energy storage material and fuel cell.

高性能非贵金属催化剂的开发是燃料电池应用的关键。杂原子掺杂的碳基复合材料是一种导电性和稳定性好且廉价环保的ORR电催化材料，但存在分散度低、比表面积流失和催化活性较低等问题，难以实际应用。针对这些问题，本项目拟设计含富杂原子和混金属的新型多孔MOFs为前驱体，热解制备多杂原子多金属掺杂的碳基复合材料。通过优化MOFs的杂原子组成、含量、孔隙率及高温热解参数，获得高分散度和高比表面积的多孔碳材料，同时调控杂原子的最佳掺杂化学态和掺杂量，引入多活性位点，进而调变碳材料的电子结构和优化ORR电催化性能。运用现代化的物理与化学测试手段，同时创新的引入数字全息技术，实现对碳材料/催化界面的原位动态监测，研究碳材料的化学组分、微观结构及形貌对ORR电催化的影响规律，揭示多掺杂状态、纳米尺寸效应、尤其是掺杂各组分协同效应对ORR电催化的影响及机理，为储能材料、燃料电池等的研发提供新思路。

开发高效非贵金属ORR电催化剂是金属空气电池和燃料电池走向实际应用的关键。本项目通过调控富氮配体及MOFs晶态材料，优化MOFs杂原子组成、含量及孔隙率，构筑了系列多掺杂、高分散和高比表面积的碳基复合材料。通过先进的表征手段，系统研究了晶态材料及其衍生复合材料的结构和形貌，总结了材料的催化活性位点-ORR性能之间的关系，揭示了它们在ORR性能方面的差异和机理，并进一步探索了材料在可充电锌空电池方面的应用。同时制备得到系列电催化析氢材料和新型储能复合材料，以及若干对温室气体CO2及重金属离子等具有吸附检测性能的MOFs晶态新材料。相关研究结果已在ACS Appl. Mater. Interfaces, Inorg. Chem., Dalton Trans., J. Electroanal. Chem., CrystEngComm, New J. Chem.等国际期刊上发表SCI论文42篇。项目成果为非贵金属ORR电催化剂的构筑提供了科学依据，基本实现了项目预期研究目标。