掺杂及卤化调控富勒烯氧化还原电位的DFT研究  

DFT investigation on the redox potential of fullerenes regulated by doping and halogenation

作　　者：李健[1] 孙冰花 王春妮 李奥 吕祥鸿[2] 王晨 代盼 白真权 LI Jian;SUN Bing-Hua;WANG Chun-Ni;LI Ao;LV Xiang-Hong;WANG Chen;DAI Pan;BAI Zhen-Quan(School of New Energy,Xi’an Shiyou University,Xi’an 710000,China;School of Materials Science and Engineering,Xi’an Shiyou University,Xi’an 710000,China;China National Petroleum Engineering Materials Research Institute Co.,Ltd,Xi’an Shiyou University,Xi’an 710000,China)

机构地区：[1]西安石油大学新能源学院,西安710000 [2]西安石油大学材料科学与工程学院,西安710000 [3]中国石油集团工程材料研究院有限公司,西安710000

出　　处：《原子与分子物理学报》2025年第4期65-72,共8页Journal of Atomic and Molecular Physics

基　　金：西安石油大学研究生创新与实践能力培养计划项目(YCS23214290)。

摘　　要：采用基于密度泛函理论(DFT)的模拟计算方法,分别计算了原始富勒烯C_(60)和11种单原子置换(掺杂及卤化)富勒烯材料C_(59)X(X=B、Si、N、P、As、O、S、Se、F、Cl、Br)的氧化还原电位、电子亲合能、分子轨道能级.其中,B、As、P、Si、N、Se、S单原子置换导致氧化还原电位正移,B置换后增幅最高(3.655 V);F、Cl、Br、O单原子置换后,氧化还原电位均负移,F置换后降幅最大(2.476 V).在所考察的12种富勒烯分子中,C_(59)B和C_(59)F的电子亲和能(EA)分别为最小值(-3.901 eV)和最高值(-2.577 eV),二者分别具有最强和最弱的得电子倾向.在C_(59)B和C_(59)F中,B、F置换原子周围存在电荷偏聚,且B、F与周围C原子的成键主要来自于-2.5 eV和-7.5 eV能级附近2p电子的相互作用.The redox potentials,electron affinity energies and molecular orbital of pristine fullerene C_(60) and 11 single-atom replacement(doped and halogenated)fullerene materials C_(59)X(X=B,Si,N,P,As,O,S,Se,F,Cl,Br)are calculated using the simulation calculation method based on the density functional theory(DFT).The single-atom substitutions of B,As,P,Si,N,Se,and S lead to positive shift of redox potential,and the increase of B replacement is the highest(3.655 V).After single atom replacements of F,Cl,Br,and O,the redox potential is negatively shifted,and the decrease of F replacement is the largest(2.476 V).The electron affinity energy(E A)of C_(59)B and C_(59)F are the smallest(-3.901 eV)and the highest(-2.577 eV),which are the strongest and weakest electron-acceptors,respectively.In C_(59)B and C_(59)F,there is charge bias around the B and F displacement atoms,and the bondings between B,F atoms and their adjacent C atoms mainly come from the interactions of 2 p electrons around the energy levels of -2.5 eV and -7.5 eV.

关 键 词：密度泛函理论 富勒烯C_(60) 氧化还原电位 电子结构 

分 类 号：O54[理学—物理]