迪美唑在光催化剂TiO_2表面吸附特征及降解机理的理论研究
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摘要
本文采用密度泛函理论研究了迪美唑在锐钛矿TiO_2(101)和(001)晶面的吸附和降解反应机理,分别研究了真空和中性水溶剂条件下,迪美唑在锐钛矿表面吸附的稳定性特征,理论优化了最稳定的吸附构型.研究发现在两种条件下,迪美唑均能吸附在TiO_2表面,吸附过程产生的氢键能增强吸附结构的稳定性,稳定的吸附构型使得迪美唑的C–N键变长,有利于发生开环降解反应.本文还研究了迪美唑在锐钛矿TiO_2两个晶面上的开环降解反应机理.研究发现,在TiO_2(101)晶面迪美唑开环降解所需反应活化能较高,很难发生,而在(001)晶面迪美唑开环可在热反应条件下进行.在水溶剂条件下,迪美唑在锐钛矿TiO_2晶面上的降解反应活化能有所降低,可见溶剂条件能促进降解反应的进行.
In this article,the adsorption and degradation mechanism of dimetridazole(DMZ)on anatase TiO_2(101)and(001)crystal surfaces has been studied by density functional theory.The adsorption stability of DMZ on anatase surface was studied under vacuum and neutral water solvents.The most stable adsorption configuration was optimized by theoretical analysis.It was found that DMZ can be adsorbed on photocatalyst TiO_2 surface under two conditions.The hydrogen bond produced in the adsorption process can enhance the stability of the adsorption structure.The stable adsorption configuration makes the C–N bond length of DMZ longer,which is conducive to the ring opening degradation reaction.We also studied the mechanism of ring opening degradation of DMZ on two crystal planes of anatase TiO_2.It was found that the reaction activation energy of the degrading reaction on TiO_2(101)crystal surface is very high,and the ring opening reaction is difficult to occur.On the(001)crystal surface,the opening of DMZ can be carried out under the condition of thermal reaction.We studied the effect of the water solvation on the degradation reaction.It was found that the activation energies of DMZ on the anatase TiO_2 surface was reduced,indicating that the solvent conditions could promote the degradation reaction.
In this article,the adsorption and degradation mechanism of dimetridazole(DMZ)on anatase TiO_2(101)and(001)crystal surfaces has been studied by density functional theory.The adsorption stability of DMZ on anatase surface was studied under vacuum and neutral water solvents.The most stable adsorption configuration was optimized by theoretical analysis.It was found that DMZ can be adsorbed on photocatalyst TiO_2 surface under two conditions.The hydrogen bond produced in the adsorption process can enhance the stability of the adsorption structure.The stable adsorption configuration makes the C–N bond length of DMZ longer,which is conducive to the ring opening degradation reaction.We also studied the mechanism of ring opening degradation of DMZ on two crystal planes of anatase TiO_2.It was found that the reaction activation energy of the degrading reaction on TiO_2(101)crystal surface is very high,and the ring opening reaction is difficult to occur.On the(001)crystal surface,the opening of DMZ can be carried out under the condition of thermal reaction.We studied the effect of the water solvation on the degradation reaction.It was found that the activation energies of DMZ on the anatase TiO_2 surface was reduced,indicating that the solvent conditions could promote the degradation reaction.
引文
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29 Dolg M,Wedig U,Stoll H,Preuss H.J Chem Phys,1987,86:866-872
30 Bergner A,Dolg M,Küchle W,Stoll H,Preu?H.Mol Phys,1993,80:1431-1441
31 Delley B.J Chem Phys,1990,92:508-517
32 Halgren TA,Lipscomb WN.Chem Phys Lett,1977,49:225-232
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37 Norton DP.Mater Sci Eng-R-Rep,2004,43:139-247
38 Li D,Shi W.Chin J Catal,2016,37:792-799
2 Thompson CS,Traynor IM,Fodey TL,Crooks SRH.Anal Chim Acta,2009,637:259-264
3 Wang JC,Wang DJ,Yang Z,Lin L.Chin J Vet Drug,2007,41:31-33(in Chinese)[汪纪仓,王大菊,杨自军,林霖.中国兽药杂志,2007,41:31-33]
4 Hu C,Deng J,Zhao Y,Xia L,Huang K,Ju S,Xiao N.Food Chem,2014,158:366-373
5 Liu JL,Wong MH.Environ Int,2013,59:208-224
6 Alexy R,Kümpel T,Kümmerer K.Chemosphere,2004,57:505-512
7 Leung HW,Jin L,Wei S,Tsui MMP,Zhou B,Jiao L,Cheung PC,Chun YK,Murphy MB,Lam PKS.Environ Health Perspect,2013,121:839-846
8 Rivera-Utrilla J,Prados-Joya G,Sánchez-Polo M,Ferro-García MA,Bautista-Toledo I.J Hazard Mater,2009,170:298-305
9 Yang SY.Initial processess in TiO2-assissted photodegradation of organic pollutants.Dissertation for the Doctoral Degree.Hangzhou:Zhejiang University,2005(in Chinese)[杨世迎.TiO2光催化降解有机污染物的初始步骤机理研究.博士学位论文.杭州:浙江大学,2005]
10 Van Doorslaer X,Haylamicheal ID,Dewulf J,Van Langenhove H,Janssen CR,Demeestere K.Chemosphere,2015,119:S75-S80
11 Gao NY,Zhang YY,Ma Y.China Environ Sci,2013,33:1958-1964(in Chinese)[高乃云,张晏晏,马艳.中国环境科学,2013,33:1958-1964]
12 Lamine A,Farid M,Hafida L.Int J Chem Environ Eng,2015,6:150-152
13 Sánchez-Polo M,López-Pe?alver J,Prados-Joya G,Ferro-García MA,Rivera-Utrilla J.Water Res,2009,43:4028-4036
14 Chang R,Li CX,Meng H,Lu YZ.J Environ Eng-Asce,2011,5:1950-1954(in Chinese)[常睿,李春喜,孟洪,陆颖舟.环境工程学报,2011,5:1950-1954]
15 Stepnowski P,Zaleska A.J Photochem Photobiol A-Chem,2005,170:45-50
16 Hou RB,Li WW,Shen XC.Acta Phys-Chim Sin,2008,24:269-274(in Chinese)[侯若冰,李伟伟,沈星灿.物理化学学报,2008,24:269-274]
17 O’Rourke C,Bowler DR.J Phys Chem C,2010,114:20240-20248
18 Vittadini A,Selloni A,Rotzinger FP,Gr?tzel M.Phys Rev Lett,1998,81:2954-2957
19 Rahaman O,van Duin ACT,Goddard WA,Doren DJ.J Phys Chem B,2011,115:249-261
20 Plimpton S.J Comput Phys,1995,117:1-19
21 Perdew JP,Burke K,Ernzerhof M.Phys Rev Lett,1996,77:3865-3868
22 Moellmann J,Grimme S.J Phys Chem C,2014,118:7615-7621
23 Risthaus T,Grimme S.J Chem Theor Comput,2013,9:1580-1591
24 Rezá?J,Riley KE,Hobza P.J Chem Theory Comput,2011,7:2427-2438
25 Stampfl C,van de Walle CG.Phys Rev B,1999,59:5521-5535
26 Zhu HX,Liu JM.Appl Phys A,2014,117:831-839
27 Han X,Shao G.J Phys Chem C,2011,115:8274-8282
28 Chen QL,Tang CQ.Acta Phys-Chim Sin,2009,25:915-920(in Chinese)[陈琦丽,唐超群.物理化学学报,2009,25:915-920]
29 Dolg M,Wedig U,Stoll H,Preuss H.J Chem Phys,1987,86:866-872
30 Bergner A,Dolg M,Küchle W,Stoll H,Preu?H.Mol Phys,1993,80:1431-1441
31 Delley B.J Chem Phys,1990,92:508-517
32 Halgren TA,Lipscomb WN.Chem Phys Lett,1977,49:225-232
33 Klamt A,Schüürmann G.J Chem Soc Perkin Trans,1993,2:799-805
34 Delley B.Mol Simul,2006,32:117-123
35 Zhang L,Liu X,Rao W,Li J.Sci Rep,2016,6:35893
36 Li N,Fan X,Tang K,Zheng X,Liu J,Wang B.Colloids Surfs B,2016,140:287-296
37 Norton DP.Mater Sci Eng-R-Rep,2004,43:139-247
38 Li D,Shi W.Chin J Catal,2016,37:792-799