罗丹明B表面分子印迹N-TiO_2的制备及其在可见光下的选择性光催化研究
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摘要
以溶胶-凝胶法制备的氮掺杂二氧化钛(TiO_2)为基质,以罗丹明B(RhB)为模板分子,以邻苯二胺为交联剂和功能单体,在紫外光下引发聚合,制备了RhB表面分子印迹N-TiO_2-MIP。采用傅立叶红外光谱(FT-IR)、X射线衍射(XRD)、紫外-可见光漫反射吸收光谱(UV-Vis)等对样品进行了表征。结果表明:样品为纳米级锐钛矿相;氮(N)掺杂因N2p与O2p混合引起禁带窄化,表面包覆及分子印迹均有效改善了TiO_2孔型和孔隙结构,增大了比表面积,N-TiO_2-MIP对目标污染物RhB的降解率高达93.2%,并具有良好的选择性。
Rhodamine B surface molecular imprinted N-TiO_2 was synthesized by surface molecular imprinting technique using nitrogen-doped TiO_2 as the substrate prepared by sol-gel technique,rhodamine B as the template molecule,o-phenylenediamine as cross linking agent and the functional monomer,polymerized under UV irradiation.The samples were characterized by FT-IR,XRD,UV-Vis diffuse reflectance spectrophotometer and N_2 adsorptiondesorption.The results indicated that titania all were anatase with nanometer size.The red-shift of absorption edge was caused by both narrowed energy gap by mixed of N_2 pand O_2 pinduced by nitrogen doped to TiO_2 andπ-π*transition from the domain of conjugate structure with poly(o-phenylenediamine).The pass and pore structure were improved effectively by nitrogen-doping,surface coating and molecular imprinting,the specific surface area was increased.Compared with four kinds of pollutant degradation,due to specific recognition sites caused by molecular imprinting,it showed that a good selectivity for the target pollutants rhodamine B under visible-light,the degradation was 93.2%.
Rhodamine B surface molecular imprinted N-TiO_2 was synthesized by surface molecular imprinting technique using nitrogen-doped TiO_2 as the substrate prepared by sol-gel technique,rhodamine B as the template molecule,o-phenylenediamine as cross linking agent and the functional monomer,polymerized under UV irradiation.The samples were characterized by FT-IR,XRD,UV-Vis diffuse reflectance spectrophotometer and N_2 adsorptiondesorption.The results indicated that titania all were anatase with nanometer size.The red-shift of absorption edge was caused by both narrowed energy gap by mixed of N_2 pand O_2 pinduced by nitrogen doped to TiO_2 andπ-π*transition from the domain of conjugate structure with poly(o-phenylenediamine).The pass and pore structure were improved effectively by nitrogen-doping,surface coating and molecular imprinting,the specific surface area was increased.Compared with four kinds of pollutant degradation,due to specific recognition sites caused by molecular imprinting,it showed that a good selectivity for the target pollutants rhodamine B under visible-light,the degradation was 93.2%.
引文
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[2]Joglekar H S,Samant S D,Joshi J B,et al.Kinetics of wet air oxidation of phenol and substitute phenols[J].Water Research,1991,25(2):135-145.
[3]Erdemoglu S,Aksu S K,Sayilkan F,et al.Photocatalytic degradation of congo Red by hydrothermally synthesized nanocrystalline TiO2and identification of degradation products by LC-MS[J].Journal of Hazardous Materials,2008,155(3):469-476.
[4]冯玉杰.电化学技术在环境工程中的应用[M].北京:化学工业出版社,2002,26-98.
[5]Rauf M A,Meetani M A,Khaleel A,et al.Photocatalytic degradation of methylene blue using a mixed catalyst and product analysis by LC-MS[J].Chemical Engineering Journal,2010,157(2/3):373-378.
[6]雷乐成,汪大翚.水处理高级氧化技术[M].北京:化学工业出版社,2001,33-68.
[7]Tomkiewicz M.Scaling properties in photocatalysis[J].Catalysis Today,2000,58(2/3):115-123.
[8]Li X Z,Li F B,Yang C L,et al.Photocatalytic activity of WOx-TiO2under visible light irradiation[J].Journal of Photochemistry and Photobiology A(Chemistry),2001,141:209-217.
[9]康巧梅,洪臣熙.La2O3-TiO2的制备及其光催化性能[J].化工环保,2015,35(4):432-437.
[10]Tian Fei,Wu Zhansheng,Yan Yujun,et al.Synthesis of visible-light-responsive Cu and N-codoped AC/TiO2 photocatalyst through microwave irradiation[J].Nanoscale Research Letters,2016,10(11):292-296.
[11]艾翠玲,郭锐敏,邵享文.CdS-TiO2复合光催化剂可见光下降解黄连素[J].环境化学,2013,32(3):366-373.
[12]Pan Lun,Zou Jijun,Liu Xinyu,et al.Visible-light-induced photodegradation of Rhodamine B over hierarchical TiO2:effects of storage period and water-mediated adsorption switch[J].Industrial and Engineering Chemistry Research,2012,51(39):12782-12786.
[13]Yaron P.Preferential photodegradation-why and how?[J].Comptes Rendus Chimie,2006,9(5/6):774-787.
[14]Chen Lingxin,Xu Shoufang,Li Jinhua,et al.Recent advances in molecular imprinting technology:current status,challenges and highlighted applications[J].Chemical Society Reviews,2011,40(5):2922-2942.
[15]罗利军,王娟,潘学军,等.二氧化钛选择性光催化降解有机污染物研究进展[J].化学通报,2013,76(4):332-337.
[16]Tang Heqing,Zhu Lihua,Yu Chen,et al.Selective photocatalysis mediated by magnetic molecularly imprinted polymers[J].Separation and Purification Technology,2012,95:165-171.
[17]Shiraishi Y,Suzuki T,Hirai T,et al.Selective photooxidation of chlorophenols with molecularly imprinted polymers containing aphotosensitizer[J].New Journal of Chemistry,2010,34(4):714-717.
[18]Mishraa K P,Gogate P R,et al.Intensification of degradation of aqueous solutions of Rhodamine B using sonochemical reactors at operating capacity of 7L[J].Journal of Environmental Management,2011,92(8):1972-1977.
[19]Qin H L,Gu G B,Liu S,et al.Preparation of nitrogen-doped titania with visible-light activity and its application[J].Comptes Rendus Chimie,2008,11(1/2):95-100.
[20]Qin H L,Gu G B,Liu S,et al.Preparation of nitrogen-doped titania using sol-gel technique and its photocatalytic activity[J].Materials Chemistry and Physics,2008,112(2):346-352.
[21]索丹霞,刘桂超,彭婷婷,等.N掺杂锐钛矿结构TiO2光催化性能研究[J].上海工程技术大学学报,2015,29(1):27-31.
[22]阿孜古丽·木尔赛力木,茹仙古丽·加马力,吐尔逊·阿不都热依木,等.界面聚合法合成聚邻苯二胺及其表征[J].化学研究与应用,2007,19(4):409-412.
[23]辛勤,罗孟飞.现代催化研究方向[M].北京:科学出版社,2009,15-22.
[24]景文珩,王韦岗,邢卫红.大孔-介孔氮掺杂二氧化钛的制备及其光催化性能测试[J].催化学报,2009,30(5):426-432.
[25]Xu P P,Xu W Z,Zhang X J,et al.Molecularly-imprinted material for dibenzothiophene recognition prepared by surface imprinting methods[J].Adsorption Science and Technology,2009,27(10):975-987.
[26]Asahi R,Morikawa T,Irie H,et al.Nitrogen-doped titanium as visible-light-sensitive photocatalyst:designs,developments,and prospects[J].Chemical Reviews,2014,114(19):9824-9852.
[27]Yu G,Gao J,Hummelen J C,et al.Polymer photovoltaic cell:enhanced efficiencies via a network of internal donor acceptor heterojunctions[J].Science,1995,270(5243):1789-1791.
[28]张华.表面改性、分子印迹型TiO2的制备及其性能[D].太原:中北大学,2014.
[29]Deng F,Li Y X,Luo X B,et al.Preparation of conductive polypyrole/TiO2 nanocomposite via surface molecular imprinting technique and its photocatalytic activity under simulated solar light irradiation[J].Colloids and Surfaces A,2012(395):183-189.
[30]魏声培,安娅,秦好丽.水杨酸分子印迹掺氮TiO2粉末的制备及其在可见光下的选择性光催化研究[J].华南农业大学学报,2016,37(4):134-140.
[31]苗智颖.溶胶-凝胶分子印迹聚合物和金属纳米材料的制备及其在传感器的应用研究[D].天津:南开大学,2014.