Yb掺杂量对混晶相TiO_2可见光催化活性的影响
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摘要
采用简单的溶胶-凝胶法制备稀土Yb掺杂混合晶相TiO_2纳米粉体,通过XRD、XPS、TEM、FT-IR、UV-Vis-DRS、PL和Nano-sizer纳米粒度仪等对样品进行表征,以可见光辐照下催化降解亚甲基蓝(MB)为模型,研究了Yb掺杂对纳米TiO_2的结构和可见光催化活性的影响.结果表明,Yb掺入TiO_2后在表面存在Yb~(3+)和Yb~(2+)两种形态,Yb掺杂抑制了TiO_2从锐钛矿向金红石的相转变,阻碍晶粒生长,增加了纳米TiO_2表面-OH数量;适量的Yb掺杂可促使合适比例的金红石与锐钛矿的混晶相形成,有效降低TiO_2光生e~-/h~+对的复合率,扩大吸收光谱的波长范围,提高TiO_2光催化活性.当热处理温度500℃、掺杂量n(Yb):n(Ti)=0.009时Yb-TiO_2样品在普通日光灯下对MB在6 h内的光催化降解效率达95.2%,明显高于同等条件下纯TiO_2样品的降解率56.4%.
The TiO_2 nanopowders with different Yb doping amount were prepared by a facile sol-gel method.The samples were characterized by XRD,XPS,TEM,FT-IR,UV-Vis,PL and Nano-sizer nano particle size analyzer,etc.The influence of Yb-doping on structure and visible photocatalytic activity of mixed phase TiO_2 was evaluated by photocatalytic degradation of methylene blue( MB) under the irradiation of fluorescent lamp.The results show that ytterbium appeared two kinds of Yb~(3+) and Yb~(2+) valence state on the surface of TiO_2.Ytterbium doping can restrain the phase transfer from anatase to rutile,prevent the grain growth,and increase the surface hydroxyl content.Appropriate amount of Yb doping and the proportions of rutile and anatase mixed phase can effectively inhibit the recombination of photogenerated electron and hole,expand the wavelength range of absorption spectrum,and improve the photocatalytic performance of TiO_2. Meanwhile,the photocatalytic activity of the Yb-TiO_2 samples was the best under the irradiation of fluorescent light when the sintered temperature t = 500 ℃ and n( Yb) ∶ n( Ti) = 0.009,it was 95.2% within 6 h and significantly higher than 56.4% of pure TiO_2 under the same experimental conditions.
The TiO_2 nanopowders with different Yb doping amount were prepared by a facile sol-gel method.The samples were characterized by XRD,XPS,TEM,FT-IR,UV-Vis,PL and Nano-sizer nano particle size analyzer,etc.The influence of Yb-doping on structure and visible photocatalytic activity of mixed phase TiO_2 was evaluated by photocatalytic degradation of methylene blue( MB) under the irradiation of fluorescent lamp.The results show that ytterbium appeared two kinds of Yb~(3+) and Yb~(2+) valence state on the surface of TiO_2.Ytterbium doping can restrain the phase transfer from anatase to rutile,prevent the grain growth,and increase the surface hydroxyl content.Appropriate amount of Yb doping and the proportions of rutile and anatase mixed phase can effectively inhibit the recombination of photogenerated electron and hole,expand the wavelength range of absorption spectrum,and improve the photocatalytic performance of TiO_2. Meanwhile,the photocatalytic activity of the Yb-TiO_2 samples was the best under the irradiation of fluorescent light when the sintered temperature t = 500 ℃ and n( Yb) ∶ n( Ti) = 0.009,it was 95.2% within 6 h and significantly higher than 56.4% of pure TiO_2 under the same experimental conditions.
引文
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[22] CHAO X Y,ZHANG N,JIAN L J.Sm3+/TiO_2catalyzed photo-synthesis of methanol from carbon dioxide and water[J].Environmental Chemistry,2010,29(3):481-485.
[23]刘月,余林,魏志钢,等.稀土金属掺杂对锐钛矿型TiO_2光催化活性影响的理论和实验研究[J].高等学校化学学报,2013,34(2):434-440.LIU Y,YU L,WEI Z G,et al. Theoretical and experimental studies on photocatalytic potential of rare earth doped anatase TiO_2[J].Chemical Journal of Cinese Universities,2013,34(2):434-440.
[24] MYILSAMY M,MURUGESAN V,MAHALAKSHMI M.The effect of synthesis conditions on mesoporous structure and the photocatalytic activity of TiO_2nanoparticls[J]. Journal of Nanoscience and Nanotechnology,2015,15(6):4 664-4 675.
[25]伍勇华,兰子君,杜伟良,等.高孔隙率Ce-TiO_2微粉的制备及其光催化性能研究[J].硅酸盐通报,2016,35(9):2 772-2 776.WU Y H,LAN Z J,DU W L,et al.Preparation of highporosity Ce-TiO_2micropowder and its photocatalytic Performance[J].Bulletin of The Chinese Ceramic Society,2016,35(9):2 772-2 776.
[26] KRALOVA M,LEVCHUK I,KASPAREK V,et al.Influence of synthesis conditions on physical properties of lanthanide-doped titania for photocatalytic decomposition of metazachlor[J]. Chinese Journal of Catalysis,2015,36(10):1 679-1 684.
[27] LIU Z,GUO B,HONG L,et al.Preparation and characterization of cerium oxide doped TiO_2nanoparticles[J].Journal of Physics&Chemistry of Solids,2005,66(1):161-167.
[28]牛微,王刚,刘旭东,等.稀土掺杂TiO_2光阳极的制备及其光解水制氢性能研究[J].功能材料,2015,46(20):20 123-20 127.NIU W,WANG G,LIU X D,et al. Preparation of rare earth doped TiO_2photoanode and performance of photocatalytic hydrogen evolution[J]. Journal of Functional Materials,2015,46(20):20 123-20 127.
[2]曹雪娟,刘誉贵,刘晓凤,等.La掺杂TiO_2光催化材料制备工艺优化与催化性能[J].科学技术与工程,2017,17(14):166-172.CAO X J,LIU Y G,LIU X F,et al.Preparation process optimization and catalytic performance of La doped TiO_2photocatalytic materials[J].Science Technology and Engineering,2017,17(14):166-172.
[3] JOSE C,CONESAL.Band structures and nitrogen doping effects in zinc titanate photocatalysts[J]. Catalysis Today,2013,208(6):11-18.
[4] SCHNEIDER J,MATSUOKA M,TAKEUCHI M,et al.Understanding TiO_2,photocatalysis:mechanisms and materials[J].Chemical Reviews,2014,114(19):9 919-9 986.
[5]王竹梅,刘波,谢志翔,等.B掺杂量对TiO_2纳米粉体的结构与光催化性能影响研究[J].人工晶体学报,2016,45(1):229-236.WANG Z M,LIU B,XIE Z X,et al.Effect of B doping on the structure and photocatalytic properties of TiO_2nano powders[J].Journal of Synthetic Crystals,2016,45(1):229-236.
[6]黄凤萍,张双,王帅,等.稀土Dy掺杂对纳米TiO_2相变及光催化性能的影响[J].材料导报,2015,29(11):6-10.HUANG F P,ZHANG S,WANG S,et al.Effects of Dydoping on phase transition and photocatalytic properties of nano TiO_2[J].Materials Review,2015,29(11):6-10.
[7] JOANNA R,TOMASZ G,JANUSZ W S,et al.Lanthanide co-doped TiO_2:The effect of metal type and amount on surface properties and photocatalytic activity[J].Applied Surface Science,2014,307(15):333-345.
[8] EL-BAHY Z M,ISMAIL A A,MOHAMED R M. Enhancement of titania by doping rare earth for photodegradation of organic dye(Direct Blue)[J].Journal of Hazardous Materials,2009,166(1):138-143.
[9] STENGL V,BAKARDJIEVA S,MURAFA N.Preparation and photocatalytic activity of rare earth doped TiO_2nanoparticles[J]. Materials Chemistry and Physics,2009,114(1):217-226.
[10] XIAO Q,SI Z C,ZHANG J,et al.Photoinduced hydroxyl radical and photocatalytic activity of samariumdoped TiO_2nanocrystalline[J]. Journal of Hazardous Materials,2008,150(1):62-69.
[11]李玲.Ce3+掺杂纳米TiO_2自清洁玻璃光催化性能研究[J].云南大学学报:自然科学版,2005,27(3A):77-80.LI L. The research of the photocatalytic properties of nano-TiO_2self-cleaning glass doped by Ce3+[J].Journal of Yunnan University:Natural Sciences Edition,2005,27(3A):77-80.
[12]徐刘君,燕宁宁,朱中其,等.Yb-TiO_2光催化剂的制备及性能研究[J].功能材料,2012,43(6):71-75.XU L J,YAN N N,ZHU Z Q,et al. Preparation and properties of Yb-TiO_2photocatalysts[J]. Journal of Functional Materials,2012,43(6):71-75.
[13] HAMED E,ALIREZA B,MOHAMMAD A B,et al.Ultrasonic-assisted sol-gel synthesis of samarium,cerium co-doped TiO_2nanoparticles with enhanced sonocatalytic efficiency[J].Ultrasonics Sonochemistry,2015,26(2):281-292.
[14]井立强,孙晓君,蔡伟民,等.掺杂Ce的TiO_2纳米粒子的光致发光及其光催化活性[J].化学学报,2003,61(8):1 241-1 245.JING L Q,SUN X J,CAI W M,et al. Photoluminescence of Ce doped TiO_2nanoparticles and their photocatalytic activity[J]. Acta Chimica Sinica,2003,61(8):1 241-1 245.
[15]张瑾,徐刘君,朱忠其,等.Yb,N共掺杂TiO_2光催化剂的制备及可见光下降解亚甲基蓝的研究[J].功能材料,2015,46(4):4 118-4 122.ZHANG J,XU L J,ZHU Z Q,et al.Synthesis and properties of(Yb,N)-TiO_2photocatalyst for degradation of methylene blue(MB)under visible light irradiation[J]. Journal of Functional Materials,2015,46(4):4 118-4 122.
[16] ACIKA I O,KIISKB V,KRUNKSA M,et al.Characterisation of samarium and nitrogen co-doped TiO_2films prepared by chemical spray pyrolysis[J]. Applied Surface Science,2012,261(11):735-741.
[17] MA Y F,XING M Y,ZHANG J L,et al.Synthesis of well ordered mesoporous Yb,N co-doped TO2with superior vissible photocatalytic activity[J]. Microporous and Mesoporous Materials,2012,152:145-152.
[18] HUANG D G,LIAO S J,ZHOU W B,et al.Synthesis of samarium and nitrogen co-doped TiO_2by modified hydrothermal method and its photocatalytic performance fo rthe degradation of 4-chlorophenol[J]. Journal of Physics and Chemistry of Solids,2009,70(5):853-859.
[19] TANG J T,CHEN X M,LIU Y,et al.Samarium-doped mesoporous TiO_2nanoparticles with improved photocatalytic performance for elimination of gaseous organic pollutants[J].Solid State Sciences,2013,15:129-136.
[20]谢桂香,张著森,周云龙.ZnO/Sm-TiO_2纳米粉体制备及光催化性能[J].厦门理工学院学报,2015,23(3):31-34.XIE G X,ZHANG Z S,ZHOU Y L. Preparation and photocatalytic performance of Zn O/Sm-TiO_2nanopowders[J]. Journal of Xiamen University of Technology,2015,23(3):31-34.
[21]黄晶晶.N/Y掺杂对二氧化钛薄膜性能影响的研究[D].南昌:南昌大学,2013.HUANG J J. Properties of N/Y doped titanium dioxide thin films[D].Nanchang:Nanchang University,2013.
[22] CHAO X Y,ZHANG N,JIAN L J.Sm3+/TiO_2catalyzed photo-synthesis of methanol from carbon dioxide and water[J].Environmental Chemistry,2010,29(3):481-485.
[23]刘月,余林,魏志钢,等.稀土金属掺杂对锐钛矿型TiO_2光催化活性影响的理论和实验研究[J].高等学校化学学报,2013,34(2):434-440.LIU Y,YU L,WEI Z G,et al. Theoretical and experimental studies on photocatalytic potential of rare earth doped anatase TiO_2[J].Chemical Journal of Cinese Universities,2013,34(2):434-440.
[24] MYILSAMY M,MURUGESAN V,MAHALAKSHMI M.The effect of synthesis conditions on mesoporous structure and the photocatalytic activity of TiO_2nanoparticls[J]. Journal of Nanoscience and Nanotechnology,2015,15(6):4 664-4 675.
[25]伍勇华,兰子君,杜伟良,等.高孔隙率Ce-TiO_2微粉的制备及其光催化性能研究[J].硅酸盐通报,2016,35(9):2 772-2 776.WU Y H,LAN Z J,DU W L,et al.Preparation of highporosity Ce-TiO_2micropowder and its photocatalytic Performance[J].Bulletin of The Chinese Ceramic Society,2016,35(9):2 772-2 776.
[26] KRALOVA M,LEVCHUK I,KASPAREK V,et al.Influence of synthesis conditions on physical properties of lanthanide-doped titania for photocatalytic decomposition of metazachlor[J]. Chinese Journal of Catalysis,2015,36(10):1 679-1 684.
[27] LIU Z,GUO B,HONG L,et al.Preparation and characterization of cerium oxide doped TiO_2nanoparticles[J].Journal of Physics&Chemistry of Solids,2005,66(1):161-167.
[28]牛微,王刚,刘旭东,等.稀土掺杂TiO_2光阳极的制备及其光解水制氢性能研究[J].功能材料,2015,46(20):20 123-20 127.NIU W,WANG G,LIU X D,et al. Preparation of rare earth doped TiO_2photoanode and performance of photocatalytic hydrogen evolution[J]. Journal of Functional Materials,2015,46(20):20 123-20 127.