N掺杂对TiO_2电子结构与光催化活性影响的理论研究Theoretical Study on the Electronic Structure and Visible-light Photocatalytic Activity of N-doped TiO_2
赵冬秋;
摘要(Abstract)：
采用第一性原理超软赝势平面波方法对N掺杂TiO2的基态电子结构进行了计算研究。计算结果显示N取代O掺杂不仅把TiO2的价带位置升高了0.27 eV,而且在带隙中诱导了有N 2p、O 2p和Ti 3d构成的未占据电子态。这三态的相互作用使带隙态具有了展宽和离域化的特性。N掺杂TiO2电子结构改变的原因是由于形成了相对较强的N-Ti共价键。价带上移和扩展带隙态共同促进了N掺杂TiO2可见光催化活性的提高。
关键词(KeyWords)： N掺杂TiO2;电子结构;第一性原理计算;可见光催化活性;带隙态
基金项目(Foundation):
作者(Authors): 赵冬秋;
参考文献(References)：
- [1]R.Asahi,T.Morikawa,T.Ohwaki,K.Aoki,and Y.Taga.Visible-light photocatalysis in nitrogen-dopedtitanium oxides[J].Science,2001,293:269.
- [2]C.Di Valentin,G.Pacchioni,and A.Selloni.Origin ofthe different photoactivity of N-doped anatase and rutileTiO2[J].Phys.Rev.B,2004,70:085116.
- [3]Z.Lin,A.Orlov,R.M.Lambert,and M.C.Payne.New insights into the origin of visible light photocatalyticactivity of nitrogen-doped and oxygen-deficient anataseTiO2[J].J.Phys.Chem.B,2005,109:20948.
- [4]T.Lindgren,J.M.Mwabora,E.Avendan珘o,J.Jons-son,A.Hoel,C.-G.Granqvist,and S.-E.Lindquist.Photoelectrochemical and optical properties ofnitrogen doped titanium dioxide films prepared by reac-tive DC magnetron sputtering[J].J.Phys.Chem.B,2003,107:5709.
- [5]H.Irie,Y.Watanabe,and K.Hashimoto.Nitrogen-Concentration Dependence on Photocatalytic Activity ofTiO2-x Nx Powders[J].J.Phys.Chem.B,2003,107:5483.
- [6]Y.Nakano,T.Morikawa,T.Ohwaki,and Y.Taga.Deep-level optical spectroscopy investigation of N-doped TiO2 films[J].Appl.Phys.Lett.,2005,86:132104.
- [7]D.N.Tafen,J.Wang,N.Wu,and J.P.Lewis.Visi-ble light photocatalytic activity in nitrogen-doped TiO2nanobelts[J].Appl.Phys.Lett.,2009,94:093101.
- [8]J.Wang,D.N.Tafen,J.P.Lewis,Z.Hong,A.Manivannan,M.Zhi,and N.Wu.Origin of photocata-lytic activity of nitrogen-doped TiO2 nanobelts[J].J.Am.Chem.Soc.,2009,131:12290.
- [9]C.Di Valentin,G.Pacchioni,A.Selloni,S.Livraghi,and E.Giamello.Characterization of paramagnetic spe-cies in N-doped TiO2 powders by EPR spectroscopy andDFT calculations[J].J.Phys.Chem.B,2005,109:11414.
- [10]A.K.Rumaiz,J.Woicik,E.Cockayne,H.Y.Lin,G.H.Jaffari,and S.I.Shah.Oxygen vacancies in Ndoped anatase TiO2:Experiment and first-principlescalculations[J].Appl.Phys.Lett.,2009,95:262111.
- [11]L.Mi,P.Xu,H.Shen,and P.-N.Wang.First-principles calculation of N:H codoping effect on energygap narrowing of TiO2[J].Appl.Phys.Lett.,2007,90:171909.
- [12]R.Long,and N.J.English.First-principles calcula-tion of nitrogen-tungsten codoping effects on the bandstructure of anatase-titania[J].Appl.Phys.Lett.,2009,94:132102.
- [13]W.G.Zhu,X.F.Qiu,V.Iancu,X.-Q.Chen,H.Pan,W.Wang,N.M.Dimitrijevic,T.Rajh,H.M.Meyer III,M.P.Paranthaman,G.M.Stocks,H.H.Weitering,B.H.Gu,G.Eres,and Z.Y.Zhang.Band Gap Narrowing of Titanium Oxide Semiconductorsby Noncompensated Anion-Cation Codoping for En-hanced Visible-Light Photoactivity[J].Phys.Rev.Lett.,2009,103:226401.
- [14]M.D.Segall,P.J.D.Lindan,M.J.Probert,C.J.Pickard,P.J.Hasnip,S.J.Clark,and M.C.Pay-ne.First-principles simulation:Ideas,illustrationsand the CASP code[J].J.Phys.:Condens.Matter,2002,14:2717.
- [15]H.J.Monkhorst,and J.D.Pack.Special points forBrillouin-zone integrations[J].Phys.Rev.B,1976,13:5188.
- [16]J.K.Burdett,T.Hughbanks,G.J.Miller,J.W.R.Jr,and J.V.Smith.Structural-electronic rela-tionships in inorganic solids:powder neutron diffractionstudies of the rutile and anatase polymorphs of titaniumdioxide at 15 and 295 K[J].J.Am.Chem.Soc.1987,109:3639.
- [17]R.Sanjinés,H.Tang,H.Berger,F.Gozzo,G.Mar-garitondo,and F.Lévy.Electronic structure of anataseTiO2 oxide[J].J.Appl.Phys.,1994,75:2945.
- [18]M.Sathish,B.Viswanathan,R.P.Viswanath,andC.S.Gopinath.Synthesis,characterization,electronicstructure,and photocatalytic activity of nitrogen-dopedTiO2 nanocatalyst[J].Chem.Mater.,2005,17:6349.