煤焦油是炼焦工业煤热解生产的粗煤气产物之一，是一种复杂的混合物，可通过分离与加工制备多种高附加值产品，有些产品甚至是石油化工无法替代的，因此研究开发高效率、低污染的煤焦油深加工新技术，不仅可以充分利用宝贵的煤焦油资源，减少对石油的依赖，而且具有广泛的应用前景和良好的经济潜力。本论文以煤焦油中菲为原料，通过“自下而上”的策略设计并实现了六苯并蔻类石墨烯分子新的合成工艺，为提高煤焦油产品的高附加值利用提供了一种新途径。并进一步将N原子掺杂六苯并蔻类石墨烯分子作为燃料电池阴极氧还原催化剂，对其ORR催化性能进行了研究。主要成果总结如下：

（1）以煤焦油中菲为原料，根据逆合成分析的方法，通过“自下而上”的策略，设计了“氧化—克脑文格尔缩合—狄尔斯-阿尔德环加成—氧化环化脱氢”的合成路线，成功制备得到六苯并蔻分子，通过核磁共振氢谱和碳谱、高分辨质谱、红外光谱和紫外-可见吸收光谱对产物的结构进行了表征，并对其产率进行了计算。结果表明：采用此工艺流程合成六苯并蔻分子的产率可高达40.4%，与其它报道的合成路径相比，此工艺很大程度上提高了六苯并蔻的合成产率，同时降低了合成难度与成本。

（2）在六苯并蔻分子制备工艺基础上，使用3-碘吡啶与苯乙炔合成氮原子掺杂的二苯乙炔为原料，将其引入第三步“狄尔斯-阿尔德环加成”反应过程中与环戊二烯酮在二苯醚溶液中反应，合成N掺杂的1,2,3,4-四苯基三亚苯，并最终得到N掺杂的六苯并蔻石墨烯分子衍生物，并通过核磁共振氢谱、高分辨质谱和元素分析对产物的结构进行了表征，并且N掺杂型六苯并蔻石墨烯分子衍生物的合成产率可达到25.3%。

（3）将N掺杂六苯并蔻石墨烯分子衍生物作为燃料电池阴极氧还原催化剂，对其氧还原性能及作用机制进行研究。结果表明，N掺杂六苯并蔻催化剂具有较好的氧还原性能，其氧还原电位为0.78V，极限电流密度约为5.3 mA·cm^-2，半波电位为0.79 V，氧还原反应动力学过程基本接近四电子反应过程。通过稳定性测试，N掺杂六苯并蔻催化剂在持续工作7 h后，依然保持电流密度为91.6 %。在抗甲醇中毒性能测试中，N掺杂六苯并蔻催化剂表现出较好的抗甲醇中毒能力。进一步研究表面，N掺杂六苯并蔻催化剂的氧还原性能优于商业Pt/C催化剂，这是因为 N原子的的电负性比C原子的大，N掺杂六苯并蔻催化剂中的N原子通过进入纳米碳材料的晶格，并利用电负性的差异引发N掺杂六苯并蔻分子电荷的重新排布，激发C原子的电化学活性，引起O₂吸附模式的改变，从而达到O=O键的高效断裂。

      Coal tar is one of the crude gas products produced by coal pyrolysis in the coking industry. It is a complex mixture that can be separated and processed to prepare a variety of high value-added products. Some products cannot even be replaced by petrochemicals. Therefore, research and development are high. New technologies for deep processing of coal tar with high efficiency and low pollution can not only make full use of valuable coal tar resources and reduce dependence on petroleum, but also have broad application prospects and good economic potential. In this thesis, phenanthrene in coal tar is used as raw materials, and a new synthesis process of Hexa-peri-hexabenzocoronene graphene molecules is designed and realized through a "bottom-up" strategy, which provides a way to improve the high value-added utilization of coal tar products. New way. Furthermore, the N atom-doped Hexa-peri-hexabenzocoronene graphene molecule was used as a fuel cell cathode oxygen reduction catalyst, and its ORR catalytic performance was studied. The main results are summarized as follows.

(1) Using phenanthrene in coal tar as the raw material, according to the method of reverse synthesis analysis, through the "bottom-up" strategy, the " oxidation → knoevenger condensation → Diels alder cycloaddition → oxidative cyclization dehydrogenation " was designed. The synthetic route of "dehydrogenation" successfully prepared Hexa-peri-hexabenzocoronene graphene molecules. The structure of the product was characterized by ¹H NMR and ¹³C NMR spectroscopy, HRMS, FT-IR spectroscopy and UV-vis absorption spectroscopy, and its yield was calculated. . The results show that the yield of Hexa-peri-hexabenzocoronene molecules synthesized by this process can be as high as 40.4%. Compared with other reported synthesis routes, this process greatly improves the synthesis yield of Hexa-peri-hexabenzocoronene and reduces Synthesis difficulty and cost.

(2) Based on the preparation process of Hexa-peri-hexabenzocoronene graphene molecules, 3-iodopyridine and phenylacetylene are used to synthesize nitrogen-doped diphenylacetylene as raw materials, which are introduced into the third step "Diels-Alder cycloaddition" reaction process It reacts with cyclopentadienone in diphenyl ether solution to synthesize N-doped 1,2,3,4-tetraphenyltriphenylene, and finally obtain N-doped Hexa-peri-hexabenzocoronene graphene molecular derivative The structure of the product was characterized by hydrogen nuclear magnetic resonance spectroscopy, high-resolution mass spectrometry and elemental analysis, and the synthesis yield of N-doped Hexa-peri-hexabenzocoronene graphene molecular derivatives can reach 25.3%.

(3) The N-doped Hexa-peri-hexabenzocoronene graphene molecular derivative was used as a fuel cell cathode oxygen reduction catalyst, and its oxygen reduction performance and mechanism of action were studied. The results show that the N-doped Hexa-peri-hexabenzocoronene catalyst has good oxygen reduction performance. Its oxygen reduction potential is 0.78V, limiting current density is about 5.3 mA·cm^-2, half-wave potential is 0.79 V, and oxygen reduction reaction kinetics The learning process is basically close to the four-electron reaction process. Through the stability test, the N-doped Hexa-peri-hexabenzocoro- nene catalyst still maintains a current density of 91.6% after 7 hours of continuous operation. In the methanol poisoning resistance test, the N-doped Hexa-peri-hexabenzocoronene catalyst showed good resistance to methanol poisoning. Further study the surface, the oxygen reduction performance of the N-doped hexabenzocoronene catalyst is better than that of the commercial Pt/C catalyst. This is because the electronegativity of the N atom is greater than that of the C atom. N atoms enter the lattice of nano-carbon materials and use the difference in electronegativity to trigger the rearrangement of the charges of the N-doped Hexa-peri-hexabenzocoronene molecules, stimulate the electrochemical activity of the C atoms, and cause changes in the O₂ adsorption mode, thereby achieving Efficient breaking of O=O bonds.

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