飞灰中的缺陷位SiO<sub>2</sub>对痕量元素As的吸附机理

董静兰; 耿晓; 高正阳; 刘彦丰

飞灰中的缺陷位SiO₂对痕量元素As的吸附机理

华北电力大学能源动力与机械工程学院, 河北保定 071003

基金项目:

中央高校基本科研业务费专项资金资助 2018MS099

详细信息

通讯作者:
DONG Jing-lan, Tel:15930247202, E-mail:jinglan_dong@163.com

中图分类号: X773
计量
- 文章访问数: 96
- HTML全文浏览量: 31
- PDF下载量: 8
- 被引次数: 0
出版历程
- 收稿日期: 2018-05-15
- 修回日期: 2018-08-15
- 网络出版日期: 2021-01-23
- 刊出日期: 2018-11-10

Adsorption mechanism of trace As on the defect sites of SiO₂ in fly ash

School of Energy Power and Mechanical Engineering, North China Electric Power University, Baoding 071003, China

Funds:

the Fundamental Research Funds for the Central Universities 2018MS099

摘要

摘要: 为了认识痕量元素As在飞灰中的富集特性，利用密度泛函理论研究了砷的典型氧化物AsO在飞灰中的主要成分SiO₂模型上的吸附机理，对优化后的吸附构型进行能量计算、AIM理论、Mulliken电荷分析以及定域化轨道指示函数（LOL）填色图分析，剖析了AsO与SiO₂表面的相互作用。结果表明，AsO在无定型SiO₂表面的缺陷位的吸附能均大于50 kJ/mol，吸附构型均为典型的化学吸附。在无定型SiO₂缺陷活性位点形成的As-Si键、Si-O键和As-O键强度较大，均属于共价键；SiO₂与AsO之间为共价相互作用。
- 密度泛函理论 /
- 吸附 /
- AsO /
- SiO₂ /
- AIM理论 /
- LOL
Abstract: To understand the enrichment characteristics of trace As in fly ash, the adsorption mechanism of AsO, a typical arsenic oxide, in SiO₂, the main component of fly ash, was investigated by using density functional theory; energy calculation, AIM theory, Mulliken charge analysis and Localized Orbital Locator(LOL) color map were performed on the optimized adsorption configuration, in order to analyze the interaction between AsO and SiO₂. The results show that the adsorption energy of AsO on the defect sites of amorphous SiO₂ is higher than 50 kJ/mol, typical for the configuration of chemical adsorption. The bonds of As-Si, Si-O and As-O formed at the active defect sites of the amorphous SiO₂ have high strength, belonging to the covalent bond; that is, the interaction between SiO₂ and AsO is covalent.
- density functional theory /
- adsorption /
- AsO /
- SiO₂ /
- AIM theory /
- LOL

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图 1 几种典型的SiO₂分子簇模型

Figure 1 Several typical SiO₂ cluster models

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图 2 SiO₂与AsO的吸附构型

Figure 2 Adsorption configuration of AsO on SiO₂

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图 3 SiO₂-AsO各吸附构型的拓扑分析图

Figure 3 Topological analysis diagram of SiO₂-AsO of various configurations

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图 4 SiO₂-AsO各吸附构型的LOL填色图

Figure 4 LOL color map of SiO₂-AsO of different adsorption configurations

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图 5 各吸附构型中相互作用的两原子间对应的BCP处的LOL值

Figure 5 LOL values at corresponding BCPs between two interacting atoms in each adsorbed configuration

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表 1 SiO₂单体吸附AsO构型的相互作用能

Table 1 Interaction energies between AsO and SiO₂ of various adsorption configurations

Configuration		E_ads /(kJ·mol^-1)	Configuration		E_ads /(kJ·mol^-1)
SiO₂-AsO	A₁	-214.14	SiO₂-AsO	C	-386.76
	A₂	-248.49		D	-408.62
	B₁	-83.04		E	-427.50
	B₂	-210.77

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表 2 SiO₂单体吸附AsO构型的吸附热

Table 2 Adsorption heat of AsO on SiO₂ with different configurations

Configuration		H_ads /(kJ·mol^-1)	Configuration		H_ads /(kJ·mol^-1)
SiO₂-AsO	A₁	225.08	SiO₂-AsO	C	376.52
	A₂	250.65		D	404.94
	B₁	84.00		E	432.04
	B₂	217.07

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表 3 吸附构型中Si-As键临界点(BCP)的拓扑分析性质

Table 3 Topological parameters of the BCP of Si-As bonds in various adsorption configurations

Configuration		Bond	ρ	▽²ρ	G	V	H	\|V\|/G	Mulliken
Configuration		Bond	ρ	▽²ρ	G	V	H	\|V\|/G	As/O	△
SiO₂-AsO	A₁	Si1-As8	0.242	-0.013	0.085	-0.154	-0.204	2.12	0.150	-0.322
	A₂	Si1-O9	0.249	0.342	0.089	-0.183	-0.344	2.15	-0.831	-0.359
	B₁	Si8-As15	0.210	0.145	0.029	-0.060	-0.048	2.07	0.329	-0.143
		Si1-As15	0.211	0.134	0.029	-0.061	-0.047	2.10	0.329	-0.143
	B₂	Si1-O16	0.242	0.385	0.074	-0.153	-0.203	2.08	-0.793	-0.321
		Si8-O16	0.243	0.387	0.072	-0.151	-0.201	2.09	-0.794	-0.322
	C	O2-As9	0.290	0.359	0.104	-0.229	-0.565	2.20	0.947	0.475
	D	O11-As15	0.321	0.406	0.135	-0.348	-0.733	2.58	0.954	0.482
	E	O5-As27	0.323	0.343	0.152	-0.419	-0.665	2.76	1.043	0.571

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参考文献(27)

[1]	赵永椿, 马斯鸣, 杨建平.燃煤电厂污染物超净排放的发展及现状[J].煤炭学报, 2015, 40(11):2629-2640. http://d.old.wanfangdata.com.cn/Periodical/dtsj201620015 ZHAO Yong-chun, MA Si-ming, YANG Jian-ping. Development and status quo of ultra-clean pollutant emissions from coal-fired power plants[J]. J China Coal Soc, 2015, 40(11):2629-2640. http://d.old.wanfangdata.com.cn/Periodical/dtsj201620015
[2]	郭欣, 郑楚光, 陈丹. 300MW煤粉锅炉砷排放特征的实验研究[J].环境科学学报, 2006, 27(4):631-634. http://d.old.wanfangdata.com.cn/Periodical/hjkx200604005 GUO Xin, ZHENG Chu-guang, CHEN Dan. Experimental Study on arsenic emission characteristics of 300MW pulverized coal-fired boiler[J]. J Environ Sci-China, 2006, 27(4):631-634. http://d.old.wanfangdata.com.cn/Periodical/hjkx200604005
[3]	王泉海, 邱建荣, 温存.氧燃烧方式下痕量元素形态转化的试验和模拟研究[J].工程热物理学报, 2006, 27(s2):199-202. http://d.old.wanfangdata.com.cn/Periodical/gcrwlxb2006z2052 WANG Quan-hai, QIU Jian-rong, WUN Cun. Experimental and simulation study on morphological transformation of trace elements under oxygen combustion[J]. J Eng Thermophys, 2006, 27(s2):199-202. http://d.old.wanfangdata.com.cn/Periodical/gcrwlxb2006z2052
[4]	DING Z H, ZHENG B S, ZHUANG M. Mode of occurrence of arsenic in high-As coals from endemic arsenicosis areas in southwestern Guizhou Province, China[J]. J Coal Sci Eng, 2007, 13(2):194-198. http://www.cqvip.com/Main/Detail.aspx?id=24615571
[5]	董静兰, 马凯.富氧气氛下煤与生物质掺烧时砷的释放研究[J].动力工程学报, 2017, 37(3):237-241. http://d.old.wanfangdata.com.cn/Periodical/dlgc201703011 DONG Jing-lan, MA Kai. Study on arsenic release from coal-biomass combustion under oxygen-enriched atmosphere[J]. Chin J Power Eng, 2017, 37(3):237-241. http://d.old.wanfangdata.com.cn/Periodical/dlgc201703011
[6]	高正阳, 吕少昆, 吉硕.碳基表面吸附铅的机理[J].环境工程学报, 2016, 10(7):3848-3852. http://d.old.wanfangdata.com.cn/Periodical/hjwrzljsysb201607076 GAO Zheng-yang, LÜ Shao-kun, JI Shuo. Mechanism of lead adsorption on carbon-based surfaces[J]. J Chin Environ Eng, 2016, 10(7):3848-3852. http://d.old.wanfangdata.com.cn/Periodical/hjwrzljsysb201607076
[7]	高正阳, 吕少昆.二氧化锰改性活性炭吸附汞的机理研究[J].动力工程学报, 2015, 35(11):923-928. doi: 10.3969/j.issn.1674-7607.2015.11.010 GAO Zheng-yang, LÜ Shao-kun. Mechanism of adsorption of mercury by manganese dioxide modified activated carbon[J]. Chin J Power Eng, 2015, 35(11):923-928. doi: 10.3969/j.issn.1674-7607.2015.11.010
[8]	郭欣, 郑楚光, 吕乃霞.簇模型CaO(001)面上吸附汞与氯化汞的密度泛函理论研究[J].中国电机工程学报, 2005, 25(13):101-104. doi: 10.3321/j.issn:0258-8013.2005.13.019 GUO Xin, ZHENG Chu-guang, LÜ Nai-xia. Density functional theory study of adsorption of mercury and mercury over the CaO(001) Surface of cluster model[J]. Proc CSEE, 2005, 25(13):101-104. doi: 10.3321/j.issn:0258-8013.2005.13.019
[9]	王鹏, 吴江, 任建兴.飞灰未燃尽碳对吸附烟气汞影响的试验研究[J].动力工程学报, 2012, 32(4):332-337. doi: 10.3969/j.issn.1674-7607.2012.04.012 WANG Peng, WU Jiang, REN Jian-xing. Experimental study on the effect of unburned carbon from fly ash on mercury adsorption in flue gas[J]. Chin J Power Eng, 2012, 32(4):332-337. doi: 10.3969/j.issn.1674-7607.2012.04.012
[10]	王军, 蒋建国, 隋继超.垃圾焚烧飞灰基本性质的研究[J].环境科学学报, 2006, 27(11):141-145. http://d.old.wanfangdata.com.cn/Periodical/hjkx200611026 WANG Jun, JIANG Jian-guo, SUI Ji-chao. Study on the basic properties of waste incineration fly ash[J]. J Environ Sci-China, 2006, 27(11):141-145. http://d.old.wanfangdata.com.cn/Periodical/hjkx200611026
[11]	孙俊民, 韩德馨, 姚强.燃煤飞灰的显微颗粒类型与显微结构特征[J].电子显微学报, 2001, 20(2):140-147. doi: 10.3969/j.issn.1000-6281.2001.02.012 SUN Jun-min, HAN De-xin, YAO Qiang. Microscopic particle types and microstructure characteristics of coal-fired fly ash[J]. J Electron Micro, 2001, 20(2):140-147. doi: 10.3969/j.issn.1000-6281.2001.02.012
[12]	WILLIAMS R P, RIESSEN A V. Determination of the reactive component of fly ashes for geopolymer production using XRF and XRD[J]. Fuel, 2010, 89(12):3683-3692. doi: 10.1016/j.fuel.2010.07.031
[13]	NURIA L, FRANCESC I, GIANFRANCO P. Adsorption of Cu, Pd, and Cs Atoms on Regular and Defect Sites of the SiO₂ Surface[J]. J Am Chem Soc, 2017, 121(4):813-821. doi: 10.1021/ja981753c
[14]	FERULLO R M, GARDA G R, BELELLI P G. Deposition of small Cu, Ag and Au particles on reduced SiO₂[J]. J Mol Struct (Theochem), 2006, (769):217-223. http://www.sciencedirect.com/science/article/pii/S0166128006002478
[15]	吕鑫.簇-表面类比: 金属氧化物簇模型探讨[D].厦门: 厦门大学, 2004. LÜ Xin. Cluster-Surface Analogy: Discussion on Metal Oxide Cluster Model[D]. Xiamen: Xiamen University, 2004.
[16]	MUKHOPADHYAY S, SUSHKO P V. Correlation between the atomic structure, formation energies, and optical absorption of neutral oxygen vacancies in amorphous silica[J]. Phys Rev B, 2005, 71(23):5204. http://scitation.aip.org/getabs/servlet/GetabsServlet?prog=normal&id=PRBMDO000071000023235204000001&idtype=cvips&gifs=Yes
[17]	KRISHNAN R, BINKLEY J S, SEEGER R. Self-consistent molecular-orbital methods-A basis set for correlated wave functions[J]. Chem Phys, 1980, 72(1):650-654. http://www.tandfonline.com/servlet/linkout?suffix=CIT0112&dbid=16&doi=10.1080%2F00268970701757875&key=10.1063%2F1.438955
[18]	WEIGEND F, AHLRICHS R. Balanced basis sets of split valence, triple zeta valence and quadruple zeta valence quality for H to Rn:Design and assessment of accuracy[J], Phys Chem Chem Phys, 2005, (7):3297-3305. http://www.tandfonline.com/servlet/linkout?suffix=CIT0030&dbid=16&doi=10.1080%2F01932691.2017.1298040&key=10.1039%2Fb508541a
[19]	GAUSSIAN 09, REVISIOND.01, FRISCH M J, TRUCKS G W, SCHLEGEL H B. Gaussian, Inc., Wallingford CT, 2016.
[20]	LU T. Multiwfn:A multifunctional wavefunction analyzer[J]. J Comput Chem, 2012, 33(5):580-592. doi: 10.1002/jcc.v33.5
[21]	TANG T H, CUI Y P. A theoretical study of some X-H-π hydrogen-bonded complexes using the theory of atoms in molecules[J]. Can J Chem, 2011, 74(6):1162-1170. doi: 10.1139/v96-130#.W-OmfPkfR8Q
[22]	BADER R F. A quantum theory of molecular structure and its applications[J]. Chem Rev, 1991, 91(5):893-928. doi: 10.1021/cr00005a013
[23]	CREMER D, KRAKA E. Chemical bonds without bonding electron density-Does the difference electron density analysis suffice for a description of the chemical bond[J]. Angew Chem, 1984, 23(23):627-628. doi: 10.1002/anie.198406271/pdf
[24]	ESPINOSA E, ALKORTA I, ELGUERO J. From weak to strong interactions:A comprehensive analysis of the topological and energetic properties of the electron density distribution involving X-H F-Y systems[J]. J Chem Phys, 2002, 117(12):5529-5542. doi: 10.1063/1.1501133
[25]	董兰, 蒋树斌, 郑申声. Be_n(n=1~6)团簇吸附H₂的密度泛函研究[J].原子能科学技术, 2010, 44(12):1414-1419. http://d.old.wanfangdata.com.cn/Periodical/yznkxjs201012002 DONG Lan, JIANG Shu-bin, ZHENG Shen-sheng. Density functional theory for hydrogen molecule adsorption of Be_n(n=1~6) clusters[J]. Atomic Energy Sci Technol, 2010, 44(12):1414-1419. http://d.old.wanfangdata.com.cn/Periodical/yznkxjs201012002
[26]	叶天旭, 徐永强, 张予辉. Co/MoS₂催化剂加氢脱硫活性的量子化学研究[J].中国石油大学学报(自然科学版), 2005, 29(4):119-121. doi: 10.3321/j.issn:1000-5870.2005.04.028 YE Tian-xu, XU Yong-qiang, ZHANG Yu-hui. Quantum chemistry study on hydrogenation desulfurization activity of Co/MoS₂ catalyst[J]. J Chin Univ Pet(Nat Sci Ed), 2005, 29(4):119-121. doi: 10.3321/j.issn:1000-5870.2005.04.028
[27]	JACOBSEN H J. Localized-orbital locator (LOL) profiles of transition-metal hydride a[J]. Can J Chem, 2009, 87(7):965-973. doi: 10.1139/V09-060