单层MoS_(2)表面Fe,Ir掺杂对NO吸附与直接解离反应性能提升的理论计算  

Theoretical Calculations on Enhancement of NO Adsorption and Direct Dissociation Reaction Performance by Fe and Ir Doping on Single Layer MoS_(2) Surface

作　　者：肖香珍 胡林峰[1] XIAO Xiangzhen;HU Linfeng(School of Chemistry and Chemical Engineering,Henan Institute of Science and Technology,Xinxiang 453003,Henan Province,China)

机构地区：[1]河南科技学院化学与化工学院,河南新乡453003

出　　处：《吉林大学学报（理学版）》2024年第1期165-173,共9页Journal of Jilin University:Science Edition

基　　金：河南省科技攻关项目(批准号:212102110148)。

摘　　要：用密度泛函理论中广义梯度近似下的PW91方法,结合周期性平板模型,研究NO分子在掺杂体系TM-MoS_(2)(TM=Fe,Ir)表面的吸附和解离行为.结果表明:与完整MoS_(2)表面的物理吸附(-0.05 eV)不同,Fe,Ir掺杂MoS_(2)表面NO吸附能分别为-3.30,-3.17 eV,说明掺杂表面对NO表现出优异的吸附性能;差分电荷密度分析表明,NO分子吸附后,N原子与掺杂原子Fe,Ir的中间出现电荷增加,形成共价键,掺杂原子周围电荷减少;态密度计算结果表明,NO在掺杂TM-MoS_(2)(TM=Fe,Ir)表面的吸附主要是N原子的2py,2px与掺杂原子Fe的3d_(xy),3d_(yz),3d_(xz)以及Ir的5d_(xy),5d_(yz),5d_(xz)轨道之间存在较强的相互作用;比较分析解离反应的活化能结果表明,相对贵金属Ir,掺杂廉价的Fe后,NO在Fe-MoS_(2)比在Ir-MoS_(2)表面解离的活化能小,且在Fe-MoS_(2)表面的吸附能与活化能非常接近,仅相差0.08 eV,表明在该体系中NO的吸附与解离存在相互竞争.We investigated the adsorption and dissociation behaviors of NO molecules on the surface of TM--MoS_(2)(TM=Fe,Ir)doped systems by using the PW91 method under the generalized gradient approximation in density functional theory in combination with periodic plate model.The results show that,unlike the physical adsorption on the intact MoS_(2)surface(-0.05 eV),the adsorption energies of NO on the surface of Fe and Ir doped MoS_(2)are-3.30,-3.17 eV respectively,indicating that the doped surface exhibits more excellent adsorption performance for NO.Differential charge density analysis shows that after adsorption of NO molecules,there is an increase in charge between the N atoms and the doped atoms Fe and Ir,covalent bonds are formed,and the charge around the doped atoms decreases.The calculation results of the density of states show that the adsorption of NO on the surface of doped TM--MoS_(2)(TM=Fe,Ir)is mainly consisted of strong interactions between 2p y and 2p x of N atoms,and 3d_(xy),3d_(yz),3d_(xz)of doped atom Fe as well as 5d_(xy),5d_(yz),and 5d_(xz)orbitals of Ir.Comparative analysis of the activation energy of the dissociation reaction,the results show that,compared to the noble metal Ir,the activation energy of NO dissociation on the Fe--MoS_(2)surface is smaller than that on the Ir--MoS_(2)surface after doping with inexpensive Fe,and the adsorption energy on the Fe--MoS_(2)surface is nearly close to the activation energy,with only a difference of 0.08 eV,indicating that there is a mutual competition between the adsorption and dissociation of NO in this system.

关 键 词：FE Ir掺杂 单层MoS_(2) 一氧化氮 吸附与解离 密度泛函理论 

分 类 号：O641[理学—物理化学]