二苯并噻吩结构和性质的理论研究
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摘要
为了探究煤中噻吩类有机硫化合物降解规律,采用密度泛函理论来对煤的一种含硫模型化合物进行量子化学方面的计算与研究。采用Materials Studio中的Dmol~3程序分析了与煤有关的含硫模型化合物二苯并噻吩(DBT)的结构和相关性质(键角键长、电荷、振动频率、热力学性质、分子反应活性及稳定性)。计算结果显示处于噻吩环结构中的C—S键键能和C—C键键能相等,噻吩环中的C—S键键能大于非环中的C—S键键能;预测噻吩中C—S键更难断裂;模型化合物中的S原子处HOMO伸展较大,是给电子的位置,S原子易失去电子发生反应。
In order to explore the degradation rule of thiophene organic sulfur compounds in coal, density functional theory was used to calculate and study the quantum chemistry of a sulfur model compound in coal. The structure and related properties(bond length, charge, vibration frequency, thermodynamic properties, molecular reactivity and stability) of dibenzothiophene(DBT), a sulfur model compound related to coal, were analyzed by using Dmol~3 program in Materials Studio. The results show that the C—S bond energy in thiophene ring structure is equal to that of C—C bond, and the C—S bond energy in thiophene ring is higher than that in non-loop. It is more difficult to cut the C—S bond in thiophene. The HOMO of the S atom in the model compound is larger, which is where the electron is given.
In order to explore the degradation rule of thiophene organic sulfur compounds in coal, density functional theory was used to calculate and study the quantum chemistry of a sulfur model compound in coal. The structure and related properties(bond length, charge, vibration frequency, thermodynamic properties, molecular reactivity and stability) of dibenzothiophene(DBT), a sulfur model compound related to coal, were analyzed by using Dmol~3 program in Materials Studio. The results show that the C—S bond energy in thiophene ring structure is equal to that of C—C bond, and the C—S bond energy in thiophene ring is higher than that in non-loop. It is more difficult to cut the C—S bond in thiophene. The HOMO of the S atom in the model compound is larger, which is where the electron is given.
引文
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[13] Huang P.Study on the Network of Dibenzothiophene Hydrogenation Using Phosphide Catalyst [J].Clean Coal Technol,2017,23(3):66-70 (in Chinese).(黄澎.磷化物催化剂体系下二苯并噻吩加氢反应网络研究[J].洁净煤技术,2017,23(3):66-70.)
[14] Yang X R,Zhu L,Ma X G,et al.Study of 4,6-Dimethyldibenzothiophene Oxidated by Ultrasounda-ssisted Tertiary Butyl Hydrogen Peroxide [J].Chem Res Appl,2017,29(12):1 872-1 876 (in Chinese).(杨孝容,祝莉,马旭光,等.超声辅助叔丁基过氧化氢氧化4,6-二甲基二苯并噻吩的研究[J].化学研究与应用,2017,29(12):1 872-1 876.)
[15] Du C M,Hu G S,Zh M X,et al.The Investigation on the Degradation Mechanism of the Thiophene Sulfur Model Compound [J].J Atom Mol Phys,2017,34(3):419-426 (in Chinese).(杜传梅,胡国帅,张明旭等.噻吩类含硫模型化合物的降解机理研究[J].原子与分子物理学报,2017,34(3):419-426.)
[2] Jin W,Tian Y S,Zeng L D.Preparation of F127-MoO3/Al2O3 and Its Catalytic Oxidation Removal of Dibenzothiophene [J].Pet Process Petrochem,2017,48(10):11-16 (in Chinese).(金伟,田永胜,曾丹林等.F127-MoO3/Al2O3的制备及其催化氧化脱除二苯并噻吩的研究[J].石油炼制与化工,2017,48(10):11-16.)
[3] Zhang X W,Dong X Z,Fan Y P,et al.Study on Desulfurization Effect and Mechanism of High Sulfur Anthracite by Microwave Combined with Acid Fertilizer [J].China Coal,2018,44(2):95-99 (in Chinese).(张秀文,董宪姝,樊玉萍等.微波联合酸性助剂对高硫无烟煤脱硫效果及机理的研究[J].中国煤炭,2018,44(2):95-99.)
[4] Ma R X,Liu C C,Zhang Y S,et al.Experimental Study on Desulphurization of Pingshuo High Sulfursteam Coal with Microwave Irradiation [J].Coal Technol,2017,36(3):302-304 (in Chinese).(马瑞欣,刘常春,张亚松等.平朔高硫动力煤微波脱硫试验研究[J].煤炭技术,2017,36(3):302-304.)
[5] Tao X X,Tang L F,Xie M H,et al.Dielectric Response Characteristics of Coal’s Sulfur-containing Model Compounds and Their Effects on the Microwave Desulfurization[J].J China Coal Soc,2017,42(3):760-767 (in Chinese).(陶秀祥,唐龙飞,谢茂华,等.煤含硫模型化合物的介电响应特性及其对微波脱硫的影响[J].煤炭学报,2017,42(3):760-767.)
[6] Fujiki J,Furuya E.Density Functional Theory Study of Adsorption of Benzothiophene and Naphthalene on Silica [J].Fuel,2016,164:180-185.
[7] Charanya C,Sampathkrishnan S,Balamurugan N.Natural Bond Orbital (NBO),Natural Population Analysis (NPA) and Non Linear Optical Properties of (1S,2R)-2-Amino-1-phenylpropan-1-ol Using DFT Method [J].Spectrosc Spectral Anal,2017,37(9):2 984-2 988 (in Chinese).(Charanya C,Sampathkrishnan S,Balamurugan N.Natural Bond Orbital (NBO),Natural Population Analysis (NPA) and Non Linear Optical Properties of (1S,2R)-2-Amino-1-phenylpropan-1-ol Using DFT Method [J].光谱学与光谱分析,2017,37(9):2 984-2 988.)
[8] Türker L.Effect of Magnesium Atom on CL-20——A DFT Treatment [J].Chin Explos Propellants,2017,40(6):17-21 (in Chinese).(Türker L.Effect of Magnesium Atom on CL-20——A DFT Treatment [J].火炸药学报,2017,40(6):17-21.)
[9] Elhorri A M,Zouaoui-Rabah M.NLO Response of Derivatives of Benzene,Stilbene and Dipheny-lacetylene:MP2 and DFT Calculations [J].Chin J Chem Eng,2017,25(6):800-808 (in Chinese).(Elhorri A M,Zouaoui-Rabah M.NLO Response of Derivatives of Benzene,Stilbene and Dipheny- lacetylene:MP2 and DFT Calculations [J].中国化学工程学报,2017,25(6):800-808.)
[10] Xue J L,Xia S J,Zhang L Y,et al.Adsorption and Hydrogenation Process of p-Chloronitrobenzene on Au20 Cluster:a DFT Study [J].Chin J Structural Chem ,2018,37(1):7-14 (in Chinese).(Xue J L,Xia S J,Zhang L Y,et al.Adsorption and Hydrogenation Process of p-Chloronitrobenzene on Au20 Cluster:a DFT Study [J].结构化学,2018,37(1):7-14.)
[11] Zheng H Y,Zhagn J L,Liu W F.Porous Carbon Microspheres Modified by Molecularly Imprinted Polymer for Selectively Adsorbing Dibenzothiophene [J].J Taiyuan Univo Technol,2016,47(2):151-155 (in Chinese).(郑海燕,张军利,刘伟峰.分子印迹功能化多孔碳微球选择性吸附二苯并噻吩[J],太原理工大学学报,2016,47(2):151-155.)
[12] Du C M.Study on Density Functional of Organic Sulfur Removal Mechanism in Coal [D].Anhui:Doctoral Dissertation of Anhui University of Science and Technology,2014 (in Chinese).(杜传梅.煤中有机硫脱除机理的密度泛函研究[D].安徽:安徽理工大学博士学位论文,2014.)
[13] Huang P.Study on the Network of Dibenzothiophene Hydrogenation Using Phosphide Catalyst [J].Clean Coal Technol,2017,23(3):66-70 (in Chinese).(黄澎.磷化物催化剂体系下二苯并噻吩加氢反应网络研究[J].洁净煤技术,2017,23(3):66-70.)
[14] Yang X R,Zhu L,Ma X G,et al.Study of 4,6-Dimethyldibenzothiophene Oxidated by Ultrasounda-ssisted Tertiary Butyl Hydrogen Peroxide [J].Chem Res Appl,2017,29(12):1 872-1 876 (in Chinese).(杨孝容,祝莉,马旭光,等.超声辅助叔丁基过氧化氢氧化4,6-二甲基二苯并噻吩的研究[J].化学研究与应用,2017,29(12):1 872-1 876.)
[15] Du C M,Hu G S,Zh M X,et al.The Investigation on the Degradation Mechanism of the Thiophene Sulfur Model Compound [J].J Atom Mol Phys,2017,34(3):419-426 (in Chinese).(杜传梅,胡国帅,张明旭等.噻吩类含硫模型化合物的降解机理研究[J].原子与分子物理学报,2017,34(3):419-426.)