La掺杂TiO_2分子印迹光催化剂的制备及其性能
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摘要
以乙酰氨基苯酚(APAP)为模板剂,钛酸四丁酯为前驱体、硝酸镧为掺杂剂,经溶胶-凝胶法制备了La掺杂分子印迹TiO_2。对La掺杂分子印迹TiO_2光催化剂样品性能进行了表征,以紫外及可见光(λ>400 nm)催化降解APAP模拟废水,考察了La掺杂量、焙烧温度对光催化活性的影响。结果表明:La掺入抑制了锐钛矿晶粒生长,比表面积增加,可见光吸收增强,光催化活性提高:且当n(La):n(Ti)=0.60%,500℃热处理2h,样品的光催化活性最佳,光催化降解10mg/LAPAP模拟废水,紫外光照射70min去除率为85.5%,总有机碳(TOC)去除率达62.5%:可见光照射40h去除率为90.8%。
The molecular imprinting lanthanum doped titanium dioxide(LMT) photocatalysts were fabricated by a sol-gel method with acetaminophen(APAP) as a template, tetrabutyl titanate as a precursor and lanthanum nitrate as a dopant. The properties of the LMT photocatalysts prepared were characterized. The photo-degradation of APAP simulative wastewater under ultraviolet(UV) and visible light(VL, λ>400nm) irradiation as a model reaction was investigated, and the effects of doping dosage and calcination temperature on the photocatalytic activity were analyzed. The results show that the inhibitation of anatase crystal growth, increase of specific surface area, and enhancement of VL absorption are due to lanthanum doping. All the LMT samples exhibit higher photocatalytic activity than that of undoped and non-imprinting Ti0_2. The LMT sample prepared at a molar ratio of n(La):n(Ti) of 0.60% and 500 ℃ for 2h has the maximum photocatalytic activity. When the initial concentration of APAP simulative wastewater is10mg/L, the photo-degradation efficiency and removal of TOC are 85.5% and 62.5%,respectively, under UV irradiation for 70min,and the photo-degradation efficiency is 90.8% under VL irradiation for 40h.
The molecular imprinting lanthanum doped titanium dioxide(LMT) photocatalysts were fabricated by a sol-gel method with acetaminophen(APAP) as a template, tetrabutyl titanate as a precursor and lanthanum nitrate as a dopant. The properties of the LMT photocatalysts prepared were characterized. The photo-degradation of APAP simulative wastewater under ultraviolet(UV) and visible light(VL, λ>400nm) irradiation as a model reaction was investigated, and the effects of doping dosage and calcination temperature on the photocatalytic activity were analyzed. The results show that the inhibitation of anatase crystal growth, increase of specific surface area, and enhancement of VL absorption are due to lanthanum doping. All the LMT samples exhibit higher photocatalytic activity than that of undoped and non-imprinting Ti0_2. The LMT sample prepared at a molar ratio of n(La):n(Ti) of 0.60% and 500 ℃ for 2h has the maximum photocatalytic activity. When the initial concentration of APAP simulative wastewater is10mg/L, the photo-degradation efficiency and removal of TOC are 85.5% and 62.5%,respectively, under UV irradiation for 70min,and the photo-degradation efficiency is 90.8% under VL irradiation for 40h.
引文
[1]CHEN L X,WANG X Y,LU W H,et al.Molecular imprinting:perspectives and applications[J].Chem Soc Rev,2016,45(8):2137-2211.
[2]SHARABI D,PAZ Y.Preferential photodegradation of contaminants by molecular imprinting on titanium dioxide[J].Appl Catal B:Environ,2010,95(1):169-178.
[3]周婉媛,尹佳音,伊玉,等.印迹型TiO_2光催化剂的制备及性能研究[J].武汉理工大学学报,2014,36(2):111-114.ZHOU Wanyuan,YIN Jiayin,YI Yu,et al.J Wuhan Univ Technol(in Chinese),2014,36(2):111-114.
[4]马颖,胡安明.污水中药物和个人护理用品的光降解[J].北京工业大学学报,2016,42(1):60-67.MA Ying,HU Anming.J Beijing Polytech Univ(in Chinese),2016,42(1):60-67.
[5]CARBONARO S,SUGIHARA M N,STRATHMANN T J.Continuous-flow photocatalytic treatment of pharmaceutical micropollutants:Activity,inhibition,and deactivation of TiO2photocatalysts in wastewater effluent[J].Appl Catal B:Environ,2013,129:1-12.
[6]MA R R,WANG X J,HUANG J Y,et al.Photocatalytic degradation of salicylic acid with magnetic activated carbon-supported F-N codoped TiO_2 under visible light[J].Vacuum,2017,141:157-165.
[7]ABA-GUEVARA C G,MEDINA-RAMIREZ I E,HERNANDEZ-RAMIREZ A,et al.Comparison of two synthesis methods on the preparation of Fe,N-Co-doped TiO_2 materials for degradation of pharmaceutical compounds under visible light[J].Ceram Int,2017,43:5068-5079.
[8]LOW J X,CHENG B,YU J G.Surface modification and enhanced photocatalytic CO_2 reduction performance of TiO_2:A review[J].Appl Surf Sci,2017,392:658-686.
[9]刘子传,郑经堂,赵东风,等.金属离子掺杂改性纳米TiO_2的能带结构及其光催化性能[J].硅酸盐学报,2013,41(3):402-408.LIU Zichuan,ZHENG Jingtang,ZHAO Dongfeng,et al.J Chin Ceram Soc,2013,41(3):402-408.
[10]义建军,于鹏,许学翔,等.芳二酚-茂型钛配合物[O,O]CpTiCl的合成及其催化乙烯聚合性能研究[J].高分子学报,2001(3):342-346.YI Jianjun,YU Peng,XU Xuexiang,et al.Acta Polym Sin(in Chinese),2001(3):342-346.
[11]水淼,岳林海,徐铸德.稀土镧掺杂二氧化钛的光催化特性[J].物理化学学报,2000,]6(5):459-464.SHUI Miao,YUE Linhai,XU Zhude.Acta Phys-Chim Sin(in Chinese),2000,16(5):459-464.
[12]LI H R,FENG B.Visible-light-driven composite La_2O_3/TiO_2 nanotube arrays:synthesis and improved photocatalytic activity[J].Mater Sci Semicond Process,2016,43:55-59.
[13]ZHANG Q J,FU Y,WU Y F,et al.Lanthanum-doped TiO_2 nanosheet film with highly reactive{001}facets and its enhanced photocatalytic activity[J].Eur J Inorg Chem,2016,2016(11):1706-1711.
[14]向乾坤,赵秀琴.La掺杂改性TiO_2粉体的制备及其光催化性能研究[J].化工新型材料,2016,44(10):164-165.XIANG Qiankun,ZHAO Xiuqin.New Chem Mater(in Chinese),2016,44(10):164-165.
[15]诸荣,陈航榕,施剑林,等.以嵌段共聚物为结构导向剂的SBA-15和SBA-16的合成及表征[J].无机材料学报,2003,18(4):855-860.ZHU Rong,CHEN Hangrong,SHI Jianlin,et al.J Inorg Mater(in Chinese),2003,18(4):855-860.
[16]朱永飞,顾宜.La203对双酚A和对氯苯酚型聚苯并噁嗪热稳定性的影响[J].高分子材料科学与工程,2014,30(3):43-48.ZHU Yongfei,GU Yi.Polym Mater Sci Eng(in Chinese),2014,30(3):43-48.
[17]唐守强,何菁萍,张昭.铁掺杂介孔二氧化钛的制备及其光催化性能[J].硅酸盐学报,2012,40(7):950-956.TANG Shouqiang,HE Jingping,ZHANG Zhao.J Chin Ceram Soc,2012,40(7):950-956.
[18]PRIYANKA K P,BLAKRISHNA K M,VARGHESE T,et al.Influence of La doping on structural and optical properties of TiO_2nanocrystals[J].Mater Charact,2016,113:144-151.
[19]陈捷,刘延,黄磊,等.焙烧温度对Ti02柱撑膨润土结构,吸附及光催化性能的影响[J].高等学校化学学报,2008,29(7):1406-1411.CHEN Jie,LIU Yan,HUANG Lei,et al.Chem J Chin Univ(in Chinese),2008,29(7):1406-1411.
[20]李葵英,郭静,刘通,等.掺镧多孔TiO_2纳米晶表面电子结构与能量转换机制[J].物理化学学报,2008,24(11):2096-2101.LI Kuiying,GUO Jing,LIU Tong,et al.Acta Phys-Chim Sin(in Chinese),2008,24(11):2096-2101.
[2]SHARABI D,PAZ Y.Preferential photodegradation of contaminants by molecular imprinting on titanium dioxide[J].Appl Catal B:Environ,2010,95(1):169-178.
[3]周婉媛,尹佳音,伊玉,等.印迹型TiO_2光催化剂的制备及性能研究[J].武汉理工大学学报,2014,36(2):111-114.ZHOU Wanyuan,YIN Jiayin,YI Yu,et al.J Wuhan Univ Technol(in Chinese),2014,36(2):111-114.
[4]马颖,胡安明.污水中药物和个人护理用品的光降解[J].北京工业大学学报,2016,42(1):60-67.MA Ying,HU Anming.J Beijing Polytech Univ(in Chinese),2016,42(1):60-67.
[5]CARBONARO S,SUGIHARA M N,STRATHMANN T J.Continuous-flow photocatalytic treatment of pharmaceutical micropollutants:Activity,inhibition,and deactivation of TiO2photocatalysts in wastewater effluent[J].Appl Catal B:Environ,2013,129:1-12.
[6]MA R R,WANG X J,HUANG J Y,et al.Photocatalytic degradation of salicylic acid with magnetic activated carbon-supported F-N codoped TiO_2 under visible light[J].Vacuum,2017,141:157-165.
[7]ABA-GUEVARA C G,MEDINA-RAMIREZ I E,HERNANDEZ-RAMIREZ A,et al.Comparison of two synthesis methods on the preparation of Fe,N-Co-doped TiO_2 materials for degradation of pharmaceutical compounds under visible light[J].Ceram Int,2017,43:5068-5079.
[8]LOW J X,CHENG B,YU J G.Surface modification and enhanced photocatalytic CO_2 reduction performance of TiO_2:A review[J].Appl Surf Sci,2017,392:658-686.
[9]刘子传,郑经堂,赵东风,等.金属离子掺杂改性纳米TiO_2的能带结构及其光催化性能[J].硅酸盐学报,2013,41(3):402-408.LIU Zichuan,ZHENG Jingtang,ZHAO Dongfeng,et al.J Chin Ceram Soc,2013,41(3):402-408.
[10]义建军,于鹏,许学翔,等.芳二酚-茂型钛配合物[O,O]CpTiCl的合成及其催化乙烯聚合性能研究[J].高分子学报,2001(3):342-346.YI Jianjun,YU Peng,XU Xuexiang,et al.Acta Polym Sin(in Chinese),2001(3):342-346.
[11]水淼,岳林海,徐铸德.稀土镧掺杂二氧化钛的光催化特性[J].物理化学学报,2000,]6(5):459-464.SHUI Miao,YUE Linhai,XU Zhude.Acta Phys-Chim Sin(in Chinese),2000,16(5):459-464.
[12]LI H R,FENG B.Visible-light-driven composite La_2O_3/TiO_2 nanotube arrays:synthesis and improved photocatalytic activity[J].Mater Sci Semicond Process,2016,43:55-59.
[13]ZHANG Q J,FU Y,WU Y F,et al.Lanthanum-doped TiO_2 nanosheet film with highly reactive{001}facets and its enhanced photocatalytic activity[J].Eur J Inorg Chem,2016,2016(11):1706-1711.
[14]向乾坤,赵秀琴.La掺杂改性TiO_2粉体的制备及其光催化性能研究[J].化工新型材料,2016,44(10):164-165.XIANG Qiankun,ZHAO Xiuqin.New Chem Mater(in Chinese),2016,44(10):164-165.
[15]诸荣,陈航榕,施剑林,等.以嵌段共聚物为结构导向剂的SBA-15和SBA-16的合成及表征[J].无机材料学报,2003,18(4):855-860.ZHU Rong,CHEN Hangrong,SHI Jianlin,et al.J Inorg Mater(in Chinese),2003,18(4):855-860.
[16]朱永飞,顾宜.La203对双酚A和对氯苯酚型聚苯并噁嗪热稳定性的影响[J].高分子材料科学与工程,2014,30(3):43-48.ZHU Yongfei,GU Yi.Polym Mater Sci Eng(in Chinese),2014,30(3):43-48.
[17]唐守强,何菁萍,张昭.铁掺杂介孔二氧化钛的制备及其光催化性能[J].硅酸盐学报,2012,40(7):950-956.TANG Shouqiang,HE Jingping,ZHANG Zhao.J Chin Ceram Soc,2012,40(7):950-956.
[18]PRIYANKA K P,BLAKRISHNA K M,VARGHESE T,et al.Influence of La doping on structural and optical properties of TiO_2nanocrystals[J].Mater Charact,2016,113:144-151.
[19]陈捷,刘延,黄磊,等.焙烧温度对Ti02柱撑膨润土结构,吸附及光催化性能的影响[J].高等学校化学学报,2008,29(7):1406-1411.CHEN Jie,LIU Yan,HUANG Lei,et al.Chem J Chin Univ(in Chinese),2008,29(7):1406-1411.
[20]李葵英,郭静,刘通,等.掺镧多孔TiO_2纳米晶表面电子结构与能量转换机制[J].物理化学学报,2008,24(11):2096-2101.LI Kuiying,GUO Jing,LIU Tong,et al.Acta Phys-Chim Sin(in Chinese),2008,24(11):2096-2101.