氨基酸或多肽诱导氮掺杂石墨烯/金属氮化物纳米薄膜组装合成与其电催化性能研究

Fuel cell, as an advanced energy generator, has many merits such as its simple structure, high efficiency, environmentally friendliness and a wide range of fuel sources. Because of these advantages, it can be used in various aspects and still has a great potential to be developed. However, since noble metal is rare and expensive, the searching of good performance and low cost replacement has been the main issue of fuel cell's catalyst research.In this project, we skillfully ultilize the amino acid (or polypeptide) induction affect and the properties of graphene oxide easily be formed into the thin film to assemble and synthesize the nitrogen-doped graphene/Metal nitride nanofilm with a three-dimensional structure. Then, we characterize and test the nanofilms for the oxygen reduction reaction , and research the synthesized mechanism of the nanofilm and relationship between the structure and catalytical performance. In our project, we combine nitrogen-doped graphene and metal nitride together, utilizing their features on electrochemical catalysis and caustic tolerance. Also, the nanofilm has a three-dimensional structure, which is very important for the catalytical performance of the graphene nanocomposite. This multilayer film will be an excellent material for electrochemical catalysis for oxygen reduction reaction. This research is of great importance not only because of the novel synthesized method for the nitrogen-doped graphene composite material, but also beause of the new way to develop excellent and cheap non-platinum catalysts for fuel cell.

燃料电池由于具有结构简单、能量转换效率高、对环境无污染、燃料来源广泛等优点而极具有发展潜力和应用前景。但因目前应用的铂系电催化剂价格昂贵且原材料稀少，因此寻找性能优良、价格低廉的非铂催化剂已成为燃料电池阴极电催化剂研究的主要方向。本项目将巧妙地利用氨基酸或多肽的诱导作用和氧化石墨烯容易成薄膜的性能，组装合成具有三维结构的氮掺杂石墨烯/金属氮化物纳米复合薄膜，对其表征和测定氧气电还原催化性能，研究薄膜组装合成机理和薄膜结构与电催化性能之间的关系，获得性能十分优良的燃料电池阴极催化剂。本项目特点在于将氮化石墨烯良好的电催化性能与金属氮化物较高的电催化活性及抗腐蚀性有机地结合，并保持材料十分重要的三维结构，充分发挥石墨烯三维结构的优势，从而获得性能优良的电催化剂。该研究不仅发展了一种合成氮掺杂石墨烯纳米复合材料新颖方法，而且为发展性能优秀、价格低廉的燃料电池非铂催化剂提供一个新的思路。

燃料电池由于具有结构简单、能量转换效率高、对环境无污染、燃料来源广泛等优点而极具有发展潜力和应用前景。但目前应用的铂系电催化剂价格昂贵且原材料稀少，因此寻找性能优良、价格低廉的非铂催化剂已成为燃料电池阴极电催化剂（氧气电还原催化剂）研究的主要方向。本项目组装合成了氮掺杂石墨烯/氮化金属氧化物(如氮化二氧化钛纳米棒)纳米薄膜，建立了在高温氨气气氛下同时对石墨烯和金属氧化物进行氮化的方法。以氧化石墨烯、有序介孔碳和醋酸钴为原料，在氨气气氛下高温热处理，组装合成氮钴复合的石墨烯/介孔碳三维结构纳米复合物。以壳聚糖为碳源和氮源，制备了Co/Co3O4复合纳米颗粒负载的氮掺杂碳三维结构纳米复合物；以氧化石墨烯和预先氧化的碳纳米管为原料，合成了氮掺杂石墨烯/氮掺杂纳米管三维结构复合物；用易得、绿色和可再生的天然生物质为原材料，制备出氮元素掺杂的多孔碳纳米片材料，氮、铁和钴三重掺杂碳纳米管/纳米多孔碳复合物，氮、磷和铁三掺杂纳米多孔碳片材料；以苯二胺为原料，制备出氮和铁共掺杂的多孔纳米碳球材料，氮和铁共掺杂的纳米碳纳米线/纳米球复合物。对这些材料表征和测定氧气电还原催化性能(碱性介质和酸性介质中)，研究这些材料组装合成机理以及其结构与电催化性能之间的关系，获得了性能优良（起始电位或半峰电位高、还原电流大、稳定性好、抗燃料分子如甲醇能力强）的燃料电池阴极催化剂。在碱性介质中，部分材料氧气电还原催化性能（启始电位与还原电流）与商业铂碳（20%）几乎相同，甚至有显著超过商业铂碳（产物起始电位比商业铂碳高30 mV），稳定性和抗甲醇性能显著优越于商业铂碳。部分材料在酸性介质中显示出很好的氧气电还原催化性能，产物起始电位比商业铂碳仅差60 mV，稳定性和抗甲醇性能显著优越于商业铂碳。该研究对燃料电池阴极催化剂发展具有重要意义。在Energy & Environmental Science, Advanced Materials, Nano Energy, Journal of Materials Chemistry A，Journal of the Electrochemical Society，Acs Applied Materials and Interfaces等国际知名学术期刊上发表论文13篇。2篇论文入选ESI的Highly Cited Paper。