掺杂b和p石墨烯吸附特性的密度泛函研究电子科学与技术电路与系统专业论文.docxVIP

华北IU力人学坝I’学位论文摘 华北IU力人学坝I’学位论文 摘 要 基于第一性原理的密度泛函理论(DFT)研究了掺B、掺P以及B，P共掺杂 石墨烯燃料电池电极吸附特性。通过对比不同石墨烯对燃料电池阴极卜氧还原反 应(Oxygen Reduction Reaction，ORR)中问物0、02、OH和OOH的吸附能，键 长，态密度以及电荷转移情况，探讨了不同掺杂体系对吸附特性的影响，进而分 析了在掺杂石墨烯上ORR反应微观机制，并给出了各步反应自由能的变化趋势。 结果表明，石墨烯经B，P掺杂后，明显增强了对ORR反应各中间物的吸附能 力，且对各中间物的吸附能近似存在线性关系，其中掺P石墨烯的吸附能远大于 掺B石墨烯的吸附能，而B，P共掺杂石墨烯的吸附能在掺B，掺P石墨烯之间， 其中近邻共掺杂时更使得OOH直接断裂，表现更强的吸附能力。在ORR反应 中，掺P石墨烯较大的吸附能有利于OOH中O．O键的断裂，掺B石墨烯吸附 能小有利于OH生成H20脱附的反应发生。而B，P共掺杂石墨烯由于掺杂原子 的协同效应，具有比B，P单一掺杂石墨烯更均衡的吸附特性，更有利于反应物 的吸附和生成物的脱附，因此能更好的催化各步反应的发生，具有更好的ORR 催化活性。 关键词：石墨烯；B和P掺杂；吸附；密度泛函 万方数据 华北IU力人学坝J’学位论文Abstract 华北IU力人学坝J’学位论文 Abstract Based on density fu【nctional theory(DFT)，the adsorption characteristics of O、 02、OH and OOH on B·doped、P—doped and B．P codoped graphenes are studied using first—principle calculations．By analyzing the adsorption energy，bond length，density of states and charge transfer，impacts of the different dopants on the intermediates adsorption of fuel cell oxygen reduction reaction(ORR)are evaluated．The ORR steps are discussed，and the free energy changes of each step are further given．The results show that B，P doped can make graphene significantly enhance the adsorption capacity of each intermediate，and the adsorption energy of various intermediates exhibit similar linear relation．The adsorption energy of P-doped graphene is much larger than B—doped grapheme，while B，P codoped graphene is between them．It’S worth noting that nearest neighbor codoped can make OOH fracture directly，shows stronger adsorption ability．In oxygen reduction reaction，the large adsorption energy of P—doped graphene is beneficial to the fracture reaction of O．O bond in OOH．while the small adsorption energy of B—doped graphene can promote the reaction of OH converting to water．Owing to the synergistic effect，the graphene codoped with B and P has a more balanced adsorption characteristics than B，P single doped grapherie， which can more conducive to the adsorption of reactant and desorption of product， then can bet