H2分子在Mg3N2表面吸附的第一性原理研究

doi:10.6023/A17030107

化学学报 ›› 2017, Vol. 75 ›› Issue (7): 708-714.DOI: 10.6023/A17030107 上一篇下一篇

研究论文

H₂分子在Mg₃N₂表面吸附的第一性原理研究

陈玉红^a,b, 刘婷婷^a,b, 张梅玲^b, 元丽华^b, 张材荣^a,b

a 兰州理工大学省部共建有色金属先进加工与再利用国家重点实验室兰州 730050;
b 兰州理工大学理学院兰州 730050

投稿日期:2017-03-16 发布日期:2017-04-25
通讯作者: 陈玉红 E-mail:chenyh@lut.cn
基金资助:
国家自然科学基金（No.51562022）、省部共建有色金属先进加工与再利用国家重点实验室开放基金（No.SKLAB02014004）、甘肃省高校基本科研业务费项目（No.05-0342）和NSFC-广东联合基金（第2期）超级计算科学应用研究专项资助项目.

First Principles Study on the Adsorption of H₂ Molecules on Mg₃N₂ Surface

Chen Yuhong^a,b, Liu Tingtinga^a,b, Zhang Meiling^b, Yuan Lihua^b, Zhang Caironga^a,b

a State Key Laboratory of Advanced Processing and Recycling of Non-ferrous Metals, Lanzhou University of Technology, Lanzhou 730050;
b School of Science, Lanzhou University of Technology, Lanzhou 730050

Received:2017-03-16 Published:2017-04-25
Contact: 10.6023/A17030107 E-mail:chenyh@lut.cn
Supported by:
Project supported by the National Natural Science Foundation of China (No.51562022),the State Key Laboratory of Advanced Processing and Recycling of Non-ferrous Metals,Lanzhou University of Technology (No.SKLAB02014004),Basic scientific Research foundation for Gansu University of China (No.05-0342),Special Program for Applied Research on Super Computation of the NSFC-Guangdong Joint Fund (the second phase).

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摘要/Abstract

采用第一性原理方法，通过计算表面能确定Mg₃N₂（011）为最稳定的吸附表面，分别研究了H₂分子在Mg₃N₂（011）三种终止表面的吸附性质.研究发现H₂分子平行表面放置更有利于吸附，表面能最低的终止表面Model Ⅱ上吸附H₂分子最稳定，主要存在三种化学吸附方式：第一种吸附方式，H₂分子解离成2个H原子分别吸附在N原子上形成双NH基，这是最佳吸附方式；此时H₂分子与Mg₃N₂表面间主要是H原子的1s轨道和N原子的2s、2p轨道发生作用，N—H之间为典型的共价键.第二种吸附方式中H₂分子部分解离，两个H原子吸附在同一个N原子上形成NH₂基.第三种吸附方式中H₂分子解离成两个H原子，一个H原子和表面N原子作用形成NH基，另一个H原子和表面Mg原子作用形成MgH结构.三种吸附方式不存在竞争关系，形成双NH基的吸附方式反应能垒最低，最容易发生.除此之外H₂还能以分子的形式吸附在晶体表面，形成物理吸附.

关键词: 密度泛函理论, Mg₃N₂, 吸附, H₂

The first principles density theory calculations have been performed to investigate different Mg₃N₂ surface and the corresponding properties of H₂ adsorption.The calculation of surface energy present that Mg₃N₂(011) is the most stable surface.The result show that the H₂ parallel to the surface is a favorable adsorption and the most stable structure is H₂ adsorbed onto the Model Ⅱ surface,which have the lowest energy.There are three main modes of chemical adsorption:The first adsorption mode is that H₂ is dissociated into two H,and each H connect with N atom respectively to form double NH.This is the best adsorption model,which mainly results from the interaction between the H 1s orbit and N 1s,2p orbits.By the analysis of the charge distribution variation H atom and N atom lose electrons,Mg obtain electrons.The second mode,H₂ dissociated partly and the two H are adsorbed onto the same N forming one NH₂,forms covalent bond.From the analysis of the bond population,we conclude that the covalent bonds strengthen the structure of NH.In other words,the hydrogen desorption of NH₂ is easier than NH.H₂ is fully dissociated in the third mode.One H atom is adsorbed onto N forming a NH group,which is connected by covalent bond,while the other H atom is adsorbed onto Mg forming MgH,which is forming ionic bond.The reaction energy barrier show that there is no competition among the three adsorption modes.The model of forming two NH is the easiest pathway,which have the lowest reaction energy barrier of 0.848 eV.The second is that the adsorption of H₂ molecules on the surface forming NH₂ have the reaction energy barrier of 1.596 eV.The most unlikely adsorption model is that H₂ is dissociated and forming the structure of NH+MgH,which have the reaction energy barrier of 5.495 eV.In addition,H₂ also can be physically adsorbed onto Mg₃N₂(011) surface.

Key words: density functional theory, Mg₃N₂, adsorption, H₂

引用此文

陈玉红, 刘婷婷, 张梅玲, 元丽华, 张材荣. H₂分子在Mg₃N₂表面吸附的第一性原理研究[J]. 化学学报, 2017, 75(7): 708-714.

Chen Yuhong, Liu Tingtinga, Zhang Meiling, Yuan Lihua, Zhang Caironga. First Principles Study on the Adsorption of H₂ Molecules on Mg₃N₂ Surface[J]. Acta Chim. Sinica, 2017, 75(7): 708-714.

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H₂分子在Mg₃N₂表面吸附的第一性原理研究

First Principles Study on the Adsorption of H₂ Molecules on Mg₃N₂ Surface

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