Mn,N共掺杂对锐钛矿相TiO2微观结构和性能的影响

张学军; 柳清菊; 邓曙光; 陈娟; 高攀

doi:10.7498/aps.60.087103

摘要

采用第一性原理平面波超软赝势方法,系统研究了Mn,N共掺杂对锐钛矿相TiO2的晶体结构、缺陷形成能、电子结构、光学性质以及氧化还原能力的影响.研究表明:Mn,N共掺杂锐钛矿相TiO2后,TiO2晶格发生了畸变,导致晶体八面体偶极矩增加,有利于光生电子-空穴对的有效分离;在TiO2带隙中出现了杂质能级,使锐钛矿相TiO2的光学吸收带边红移,可见光区的吸收系数明显增大,有利于光催化效率的提高;在不考虑

关键词:

Abstract

The effects of Mn and N codoping on the crystal structure, defect formation energy, electronic structure, optical property and redox ability of anatase TiO2 are investigated by first-principles calculations of plane-wave ultrasoft pseudopotential. The calculation results show that the octahedral dipole moment of anatase TiO2 increases due to its lattice distortion after Mn, N codoping, which is favorable for effective separation of photogenerated electron-hole pairs. Some impurity bands appear in the band gap, which leads to the red-shift of optical absorption edge and to the increase in coefficient of light absorption, thereby facilitating the enhancement of the photocatalytic efficiency. If the impurity band is not taken into account, the band edge redox potential of codoped TiO2 is only slightly changed compared with that of pure TiO2 . All of these results can explain the better photocatalytic performances of Mn, N codoped anatase TiO2 under visible-light irradiation.

Keywords:

作者及机构信息

1.
湖南城市学院物理与电信工程系,益阳 413000;

2.
云南大学物理科学与技术学院,云南省纳米材料与技术重点实验室,昆明 650091;

3.
湖南工程职业技术学院信息工程系,长沙 410151

基金项目: 国家自然科学基金 (批准号:50862009,51062017)资助的课题.

Authors and contacts

1.
Department of Physics and Electron Information Engineering, Hunan City University, Yiyang 413000, China;

2.
Key Laboratory of Nanomaterials and Nanotechnology of Yunnan Province, College of Physics Science and Technology, Yunnan University, Kunming 650091, China;

3.
Department of Information Engineering, Hunan Vocational and Technical College of Engineering, Changsha 410151, China

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施引文献

[1]	Arconada N, Castro Y, Durn A 2010 Appl. Catal. A 385 101
[2]	Fujishima A, Zhang X T, Tryk D A 2008 Surf. Sci. Rep. 63(12) 515
[3]
[4]
[5]	Fujishima A, Zhang X T, Tryk D A 2007 Int. J. Hydrogen Energy 32 2664
[6]
[7]	Vougioukalakis G, Stergiopoulos T, Kantonis G, Kontos A, Papadopoulos K, Stublla A, Potvin P, Falaras P 2010 J. Photochem. Photobiol. A 214 22
[8]
[9]	Yamashita H, Harada M, Misaka J, Takeuchi M, Ikeue K, Anpo M 2002 J. Photochem. Photobiol. A 148 257
[10]	Yu H Z, Pen J B, Liu J C 2009 Acta Phys. Sin. 58 669 (in Chinese) [於黄忠、彭俊彪、刘金成 2009 物理学报 58 669]
[11]
[12]
[13]	Yu J X, Fu M, Ji G F, Chen X R 2009 Chin. Phys. B 18 269
[14]	Lin F, Zheng F W, Ouyang F P 2009 Acta Phys. Sin. 58 193 (in Chinese) [林峰、郑法伟、欧阳方平 2009 物理学报 58 193]
[15]
[16]	Zhu J, Yu J X, Wang Y J, Chen X R, Jing F Q 2008 Chin. Phys. B 17 2216
[17]
[18]
[19]	Xu L, Tang C Q, Qian J 2010 Acta Phys. Sin. 59 2721(in Chinese)[徐凌、唐超群、钱俊 2010 物理学报 59 2721]
[20]	Zhu L, Xie J S, Cui X L, Shen J, Yang X L, Zhang Z J 2010 Vacuum 84 797
[21]
[22]
[23]	Choi W, Termin A, Hoffmann M R 1994 J. Phys. Chem. 98 13669
[24]	Liu Y, Wang H Q, Wu Z B 2007 J. Environ. Sci. 19 1505
[25]
[26]
[27]	Asahi R, Morikawa T, Ohwaki T, Aoki K O, Taga Y 2001 Science 293 269
[28]
[29]	Kang I C, Zhang Q W, Yin S, Sato T, Saito F 2008 Environ. Sci. Technol. 42 3622
[30]
[31]	Di Valentin C, Finazzi E, Pacchioni G, Selloni A, Livraghi S, Paganini M C, Giamello E 2007 Chem. Phys. 339 44
[32]
[33]	Zhang X, Hu Y, Gong Q, Wei C H 2010 Chem. Ind. Eng. Prog. 29 1071(in Chinese)[张霞、胡芸、龚倩、韦朝海 2010 化工进展 29 1071]
[34]	Chen S F, Liu W, Zhang S J, Chen Y H 2010 J. Sol-Gel Sci. Technol. 54 258
[35]
[36]	Hu Y, Zhang X, Wei C H 2010 Res. Chem. Intermed. 36 95
[37]
[38]
[39]	Zhao Z Y, Liu Q J 2008 J. Phys. D 41 025105
[40]
[41]	Ceperley D M, Alder B J 1980 Phys. Rev. Lett. 45 566
[42]
[43]	Perdew J P, Zunger A 1981 Phys. Rev. B 23 5048
[44]
[45]	Monkhorst H J, Pack J D 1976 Phys. Rev. B 13 5188
[46]	Zhang X J, Gao P, Liu Q J 2010 Acta Phys. Sin. 59 4930 (in Chinese)[张学军、高攀、柳清菊 2010 物理学报 59 4930]
[47]
[48]	Gao P, Wu J, Liu Q J, Zhou W F 2010 Chin. Phys. B 19 087103
[49]
[50]
[51]	Gai Y Q, Li J B, Li A S, Xia J B, Wei S H 2009 Phys. Rev. Lett. 102 036402
[52]	Segall M D, Lindan P J D, Probert M J, Pickard C J, Hasnip P J, Clark S J, Payne M C 2002 J. Phys.:Condens. Matter 14 2717
[53]
[54]	Long R, Niall J 2009 Appl. Phys. Lett. 94 132102
[55]
[56]
[57]	Ma X, Miao L, Bie S W, Jiang J J 2010 Solid State Commun. 150 689
[58]
[59]	Ma X G, Jiang J J, Liang P 2008 Acta Phys. Sin. 57 3120 (in Chinese) [马新国、江建军、梁培 2008 物理学报 57 3120]
[60]	Valentin C D, Pacchioni G, Selloni A 2005 Chem. Matter 17 6656
[61]
[62]	Van de Walle C G, Neugebauer J 2004 J. Appl. Phys. 95 3851
[63]
[64]	Knauth P, Tutter H L 1999 J. Appl. Phys. 85 897
[65]
[66]	Yang K, Dai Y, Huang B 2007 J. Phys. Chem. C 111 12086
[67]
[68]	Zhu W G, Qiu X F, Iancu V, Chen X Q, Pan H, Wang W, Dimitrijevic N M, Rajh T, Meyer H M, Paranthaman M P, Stocks G M, Weitering H H, Gu B H, Eres G, Zhang Z Y 2009 Phys. Rev. Lett. 103 226401
[69]
[70]
[71]	Mulliken R S 1934 Chem. Phys. 2 782
[72]
[73]	Mulliken R S 1955 Chem. Phys. 23 1833
[74]
[75]	Chen K, Fan G H, Zhang Y, Ding S F 2008 Acta Phys. Sin. 57 3138 (in Chinese) [陈琨、范广涵、章勇、丁少锋 2008 物理学报 57 3138]
[76]
[77]	Sato J, Kobayashi H, Inoue Y 2003 Phys. Chem. B 107 7970
[78]	Zhao Z Y, Liu Q J 2008 Catal. Lett. 124 111
[79]
[80]	Le L C, Ma X G, Tang H, Wang Y, Li X, Jiang J J 2010 Acta Phys. Sin. 59 1314 (in Chinese) [乐伶聪、马新国、唐豪、王扬、李翔、江建军 2010 物理学报 59 1314]
[81]
[82]
[83]	Okato T, Sakano T, Obara M 2005 Phys. Rev. B 72 115124
[84]
[85]	Kim Y I, Atherton S J, Brigham E S, Mallouk T E 1993 Phys. Chem. 97 11802
[86]	Yu H F, Zhang Z W, Hu F C 2008 J. Alloys Compd. 465 484
[87]
[88]
[89]	Tang J W, Ye J H 2005 Chem. Phys. Lett. 410 104

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