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助剂Ni对Cu(111)表面催化NH3还原NO反应影响的理论研究
Theoretical study on effect of additive Ni on catalytic reduction of NO by NH3 on Cu(111) surface
- 低碳化学与化工 2024, 49(10): 66-71.
- 作者机构：
1.山西大学 电力与建筑学院，山西 太原 030006
2.中国能源建设集团广东火电工程有限公司，广东 广州 510735
- 作者简介：
王旭慧（1984—），博士，讲师，研究方向为大气污染物控制的理论计算，E-mail：wangxuhui@sxu.edu.cn。
- 基金信息：山西省应用基础研究计划青年基金(20210302124126;202103021223031)
DOI：10.12434/j.issn.2097-2547.20230415
中图分类号： TQ426;O643.32纸质出版日期：2024-10-25，
收稿日期：2023-12-18，
修回日期：2024-01-24，
- 稿件说明：
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王旭慧,郭洋,吴娇等.助剂Ni对Cu(111)表面催化NH3还原NO反应影响的理论研究[J].低碳化学与化工,2024,49(10):66-71.
WANG Xuhui,GUO Yang,WU Jiao,et al.Theoretical study on effect of additive Ni on catalytic reduction of NO by NH3 on Cu(111) surface[J].Low-carbon Chemistry and Chemical Engineering,2024,49(10):66-71.
王旭慧,郭洋,吴娇等.助剂Ni对Cu(111)表面催化NH3还原NO反应影响的理论研究[J].低碳化学与化工,2024,49(10):66-71. DOI： 10.12434/j.issn.2097-2547.20230415.
WANG Xuhui,GUO Yang,WU Jiao,et al.Theoretical study on effect of additive Ni on catalytic reduction of NO by NH3 on Cu(111) surface[J].Low-carbon Chemistry and Chemical Engineering,2024,49(10):66-71. DOI： 10.12434/j.issn.2097-2547.20230415.
摘要
针对商用钒钛脱硝催化剂存在的环境污染和易中毒问题，采用无毒环保的单金属铜催化剂并使用助剂Ni掺杂提高其脱硝性能。基于密度泛函理论（DFT），探究了助剂Ni对Cu(111)表面催化NH
3
还原NO反应的影响。通过分析催化剂表面反应物种的吸附、反应机理和电子结构，对比了助剂Ni掺杂前后Cu(111)表面的催化活性。结果表明，所有反应物种在CuNi(111)表面上的吸附效果均优于在Cu(111)表面的吸附效果。CuNi(111)表面发生的三步基元反应需克服的能垒均低于Cu(111)表面，其中，速控步骤（NH
2
NO → N
2
+ H
2
O）的能垒降低了63.6 kJ/mol，可见CuNi(111)表面催化活性明显较高。相比Cu(111)表面，CuNi(111)表面的
d
带中心更靠近费米能级，说明助剂Ni的掺杂增强了Cu(111)表面电子的活跃性，从而提高了其催化活性。
Abstract
In view of the environmental pollution and easy poisoning problems of commercial vanadium-titanium denitrification catalys
ts
a non-toxic and environmentally friendly single-metal copper catalyst was used and the addition of additive Ni was used to improve its denitrification performance. Based on density functional theory (DFT)
the effect of additive Ni on the catalytic reduction of NO by NH
3
on Cu(111) surface was investigated. By analyzing the adsorption of reactive species
reaction mechanism and electronic structure on the catalysts surface
the catalytic activities of Cu(111) surface before and after additive Ni doping were compared. The results show that the adsorption effect of all reactive species on the CuNi(111) surface is better than that on the Cu(111) surface. The energy barriers for the three elementary reactions occurring on the CuNi(111) surface are lower than those on the Cu(111) surface
among which the energy barrier for the rate-determining step (NH
2
NO → N
2
+ H
2
O) decreases by 63.6 kJ/mol
indicating that the catalytic activity of CuNi(111) surface is significantly higher. Compared with the Cu(111) surface
the
d
-band center of the CuNi(111) surface is closer to the Fermi level
indicating that the doping of additive Ni enhances the electronic activity of the Cu(111) surface
thereby improving its catalytic activity.
关键词
Cu表面Ni助剂脱硝密度泛函理论
Keywords
Cu surfaceadditive Nidenitrificationdensity functional theory
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