石墨烯负载Pd_(n)(n=1—3)原子/团簇吸附三氯甲烷分子的第一性原理研究  

A First-principles Study of the Adsorption of Chloroform on Graphene Decorated by Pd_(n)(n=1—3)Atoms/Clusters

作　　者：范青青 安立宝 常春蕊 张志明 贾晓彤 FAN Qingqing;AN Libao;CHANG Chunrui;ZHANG Zhiming;JIA Xiaotong(College of Mechanical Engineering,North China University of Science and Technology,Tangshan 063210,Hebei,China;College of Sciences,North China University of Science and Technology,Tangshan 063210,Hebei,China;College of Materials Science and Engineering,North China University of Science and Technology,Tangshan 063210,Hebei,China;School of Materials Science and Engineering,Beijing Institute of Technology,Beijing 100081,China)

机构地区：[1]华北理工大学机械工程学院,河北唐山063210 [2]华北理工大学理学院,河北唐山063210 [3]华北理工大学材料科学与工程学院,河北唐山063210 [4]北京理工大学材料科学与工程学院,北京100081

出　　处：《材料导报》2023年第21期101-106,共6页Materials Reports

基　　金：国家自然科学基金(51472074);河北省“百人计划”项目(E2012100005)。

摘　　要：采用基于密度泛函理论的第一性原理研究了三氯甲烷(CHCl_(3))分子在负载Pd_n(n=1—3)原子/团簇的石墨烯表面的吸附行为。研究表明,CHCl_(3)分子与本征石墨烯(PG)之间仅为物理吸附,而采用Pd原子/团簇对本征石墨烯进行修饰,可以提高CHCl_(3)分子与石墨烯之间的吸附性能,使得CHCl_(3)分子与负载Pd_(n)(n=1—3)的石墨烯(PG-Pd_n(n=1—3))之间形成稳定的化学吸附。在PG-Pd_n(n=1—3)三种吸附体系中,吸附能计算表明Pd_(3)团簇修饰的石墨烯基底对CHCl_(3)分子的吸附效果最好,电荷转移分析表明CHCl_(3)分子向PG-Pd_(3)转移了大量电荷,电荷密度计算证实CHCl_(3)分子与PG-Pd_(3)之间形成了稳定的化学吸附。CHCl_(3)分子吸附在PG-Pd_(3)表面后,Cl原子p轨道与Pd原子s轨道的态密度发生有效重叠,前线轨道分析也证明PG-Pd_(3)在吸附CHCl_(3)后能隙明显减小、电导率增加。因此,负载Pd_(3)团簇的石墨烯可以作为检测三氯甲烷分子的传感材料。The adsorption behavior of chloroform(CHCl_(3))molecules on the surface of graphene decorated by Pd n(n=1—3)atoms/clusters was stu-died in this paper by using the first-principles based on density functional theory.It has been found that there exists only physical adsorption between CHCl_(3)molecules and pristine graphene(PG),and decorating PG with Pd atoms/clusters can improve the adsorption performance of graphene and lead to stable chemical adsorption between CHCl_(3)and Pd n(n=1—3)decorated graphene(PG-Pd_(n)(n=1—3)).Among the three adsorption systems of PG-Pd n(n=1—3),the calculation of adsorption energy shows that the graphene decorated by the Pd_(3)cluster has the best adsorption effect on CHCl_(3).Charge transfer analysis indicates that CHCl_(3)transfers a large amount of charge to PG-Pd_(3).The calculation of charge density confirms the formation of stable chemical adsorption between CHCl_(3)and PG-Pd_(3).After CHCl_(3)is adsorbed on the surface of PG-Pd_(3),the density of states of the p orbital of the Cl atom effectively overlaps with the s orbital of the Pd atom.Frontier orbital analysis also shows a decrease of the energy gap and an increase of the electrical conductivity of PG-Pd_(3)after CHCl_(3)adsorption.Therefore,graphene decorated by Pd_(3)clusters can be used as a sensing material for the detection of chloroform molecules.

关 键 词：石墨烯 Pd原子/团簇 吸附 三氯甲烷 第一性原理 

分 类 号：TB34[一般工业技术—材料科学与工程]