Fe3O4协同H2O2气相高级氧化单质汞的机理

doi:10.11949/j.issn.0438-1157.20171236

化工学报 ›› 2018, Vol. 69 ›› Issue (5): 1840-1845.DOI: 10.11949/j.issn.0438-1157.20171236

Fe₃O₄协同H₂O₂气相高级氧化单质汞的机理

周长松^1,2, 杨宏旻¹, 孙佳兴¹, 祁东旭¹, 毛琳¹, 宋子健³, 孙路石³

1. 南京师范大学能源与机械工程学院, 江苏南京 210042;
2. 南京师范大学化学与材料科学学院, 江苏南京 210023;
3. 华中科技大学煤燃烧国家重点实验室, 湖北武汉 430074

收稿日期:2017-09-11 修回日期:2018-01-02 出版日期:2018-05-05 发布日期:2018-05-05
通讯作者: 周长松
基金资助:
国家自然科学基金项目（51676101，51376073）；江苏省自然科学基金项目（BK20161558）；中国博士后科学基金项目（2017M621779）；江苏省高校自然科学基金项目（17KJB470009）。

Mechanism of Hg removal by gaseous advanced oxidation process with Fe₃O₄ and H₂O₂

ZHOU Changsong^1,2, YANG Hongmin¹, SUN Jiaxing¹, QI Dongxu¹, MAO Lin¹, SONG Zijian³, SUN Lushi³

1. School of Energy & Mechanical Engineering, Nanjing Normal University, Nanjing 210042, Jiangsu, China;
2. School of Chemistry and Materials Science, Nanjing Normal University, Nanjing 210023, Jiangsu, China;
3. State Key Laboratory of Coal Combustion, Huazhong University of Science and Technology, Wuhan 430074, Hubei, China

Received:2017-09-11 Revised:2018-01-02 Online:2018-05-05 Published:2018-05-05
Supported by:
supported by the National Natural Science Foundation of China (51676101, 51376073), the Natural Science Foundation of Jiangsu Province (BK20161558), the China Postdoctoral Science Foundation (2017M621779) and the College Natural Science Foundation of Jiangsu Province (17KJB470009).

摘要/Abstract

摘要：

利用密度泛函理论分别研究了H₂O₂分子在Fe₃O₄（111）、（110）和（001）表面分解特性，并对单质汞在H₂O₂/Fe₃O₄体系的反应特性进行了研究。对比不同构型的结合能、Mulliken电荷转移和分态密度分析，详细讨论了H₂O₂分解产生羟基的规律以及Hg⁰的氧化态中间产物成键特性。结果表明：H₂O₂分子在Fe₃O₄（111）、（001） A和（110） A表面更容易分解产生羟基；不同表面产生的羟基对Hg⁰具有不同的氧化活性；Hg⁰在表面羟基的作用下可有效通过电荷转移实现氧化。对比分析了三种表面汞氧化态中间产物的脱附路径，HO—Hg—OH和Hg—OH的表面脱附是主要的反应路径。

关键词: 汞, 氧化, 密度泛函理论, 自由基, 表面

Abstract:

The decomposition properties of H₂O₂ molecule over Fe₃O₄ (111), (110), and (001) surfaces were systematically investigated by using density functional theory (DFT) calculations. Hg adsorption and oxidation mechanisms over H₂O₂/Fe₃O₄ system were studied. Binding energies, optimized geometries, Mulliken population, and molecular orbital analysis of partial density of states (PDOS) between Hg and H₂O₂/Fe₃O₄ surfaces were proposed. The most favored configurations of H₂O₂ decomposition, which was associated with the generation mechanism of OH groups, as well as the intermediates of Hg species were discussed. The results showed that OH radicals were more likely produced on Fe₃O₄ (111), (001) A, and (110) A surfaces. The oxidative activity of OH produced on different surfaces varies a lot. In addition, Mulliken charge population revealed Hg⁰ oxidation when the systems were in equilibrium because a large number of electrons transferred from Hg⁰ to the surface hydroxyl. The calculated binding energies suggested that the process of HO-Hg-OH and Hg-OH generation were exothermic on Fe₃O₄ surface with H₂O₂. The desorption analysis showed that HO-Hg-OH and Hg-OH intermediates had a lower desorption energy when they detached from the surface.

Key words: mercury, oxidation, density functional theory, radical, surface

中图分类号:

TQ534.9

周长松, 杨宏旻, 孙佳兴, 祁东旭, 毛琳, 宋子健, 孙路石. Fe₃O₄协同H₂O₂气相高级氧化单质汞的机理[J]. 化工学报, 2018, 69(5): 1840-1845.

ZHOU Changsong, YANG Hongmin, SUN Jiaxing, QI Dongxu, MAO Lin, SONG Zijian, SUN Lushi. Mechanism of Hg removal by gaseous advanced oxidation process with Fe₃O₄ and H₂O₂[J]. CIESC Journal, 2018, 69(5): 1840-1845.

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Fe₃O₄协同H₂O₂气相高级氧化单质汞的机理

Mechanism of Hg removal by gaseous advanced oxidation process with Fe₃O₄ and H₂O₂

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