纳米TiO_2/聚氯乙烯共轭衍生物复合材料的制备及可见光催化性能
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摘要
聚氯乙烯(PVC)在270℃真空环境中经热处理脱除HCl得到具有共轭结构的PVC衍生物(CDPVC)。纳米TiO_2与CDPVC(质量比为2∶1)经高能球磨复合得到纳米TiO_2/CDPVC复合材料。采用TEM、XRD、XPS、FTIR、SEM和Raman等对纳米TiO_2/CDPVC复合材料进行了分析表征,并采用罗丹明B(RhB)的光催化降解反应和K_2Cr_2O_7的光催化还原反应评价其可见光催化活性及稳定性。结果表明,TiO_2与CDPVC经高能球磨复合后形成了Ti—O—C结构,该结构有利于提高纳米TiO_2/CDPVC复合材料的可见光吸收能力和光生电子/空穴分离效率。与纳米TiO_2和普通研磨的TiO_2-CDPVC相比,纳米TiO_2/CDPVC复合材料具有较高的可见光催化活性和良好的可见光催化稳定性。其可见光催化机制是CDPVC吸收光子产生光生电子-空穴对,并容易将光生电子注入到TiO_2的导带中,CDPVC内光生电子和TiO_2导带上的光生电子(e_(CB)~-)被吸附在材料表面上的氧捕获产生·O_2~-自由基,·O_2~-自由基可以直接降解RhB分子,直至最后降解生成H_2O和CO_2。
Polyvinyl chloride(PVC)was heat-treated in a vacuum at 270℃to prepare a partly conjugated derivative(CDPVC)through a reaction of remove HCl.The nano TiO_2/CDPVC composite was prepared by compounding commercial TiO_2 and CDPVC with the mass ratio of 2∶1 in a high-energy ball-miller,and was characterized by TEM,XRD,XPS,FTIR,SEM and Raman,et al.The photocatalytic degradation of rhodamine B(RhB)and the photocatalytic reduction of K_2Cr_2O_7 were used to evaluate the visible photocatalytic activity and stability of the nano TiO_2/CDPVC composite.The results show that the structure of Ti—O—C formed by compounding TiO_2 and CDPVC in a high-energy ball-miller,which is advantageous to the improvement in both visible-light absorption capacity of the nano TiO_2/CDPVC composite and separation efficiency of photogenerated electron/hole pairs.Compared to nano TiO_2 and TiO_2-CDPVC(an ordinary product after grinding TiO_2 and CDPVC),nano TiO_2/CDPVC composite exhibits the higher visible-light photocatalytic activity and excellent stability.The visible-light photocatalytic mechanism can be proposed that CDPVC adsorbs photos to produce photogenerated electron-hole pairs,and the photogenerated electrons can be easily injected into the conduction band of TiO_2.The photogenerated electrons(e_(CB)~-)in CDPVC and conduction band of TiO_2 can be captured by oxygen on the surface of the TiO_2/CDPVC composite to form·O_2~-radicals,and·O_2~-radicals can directly degrade rhodamine B molecules even to produce H_2O and CO_2.
Polyvinyl chloride(PVC)was heat-treated in a vacuum at 270℃to prepare a partly conjugated derivative(CDPVC)through a reaction of remove HCl.The nano TiO_2/CDPVC composite was prepared by compounding commercial TiO_2 and CDPVC with the mass ratio of 2∶1 in a high-energy ball-miller,and was characterized by TEM,XRD,XPS,FTIR,SEM and Raman,et al.The photocatalytic degradation of rhodamine B(RhB)and the photocatalytic reduction of K_2Cr_2O_7 were used to evaluate the visible photocatalytic activity and stability of the nano TiO_2/CDPVC composite.The results show that the structure of Ti—O—C formed by compounding TiO_2 and CDPVC in a high-energy ball-miller,which is advantageous to the improvement in both visible-light absorption capacity of the nano TiO_2/CDPVC composite and separation efficiency of photogenerated electron/hole pairs.Compared to nano TiO_2 and TiO_2-CDPVC(an ordinary product after grinding TiO_2 and CDPVC),nano TiO_2/CDPVC composite exhibits the higher visible-light photocatalytic activity and excellent stability.The visible-light photocatalytic mechanism can be proposed that CDPVC adsorbs photos to produce photogenerated electron-hole pairs,and the photogenerated electrons can be easily injected into the conduction band of TiO_2.The photogenerated electrons(e_(CB)~-)in CDPVC and conduction band of TiO_2 can be captured by oxygen on the surface of the TiO_2/CDPVC composite to form·O_2~-radicals,and·O_2~-radicals can directly degrade rhodamine B molecules even to produce H_2O and CO_2.
引文
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[34]ZHANG F J,XIE F Z,LIU J,et al.Rapid sonochemical synthesis of irregular nanolaminar-like Bi2WO6 as efficient visible-light-active photocatalysts[J].Ultrasonics Sonochemistry,2013,20(1):209-215.
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[36]ZHUANG J D,DAI W X,TIAN Q F,et al.Photocatalytic degradation of Rh B over TiO2bilayer films:Effect of defects and their location[J].Langmuir,2010,26(12):9686-9694.
[37]YU K,YANG S G,HE H,et al.Visible light-driven photocatalytic degradation of rhodamine B over NaBiO3:Pathways and mechanism[J].Journal of Physical Chemistry A,2009,113(37):10024-10032.
[38]WANG D S,BAO C,LUO Q Z,et al.Improved visible-light photocatalytic activity and anti-photocorrosion of CdS nanoparticles surface-modified by conjugated derivatives from polyvinyl chloride[J].Journal of Environmental Chemical Engineering,2015,3(3):1578-1585.
[2]TIAN G H,FU H G,JING L Q,et al.Preparation and characterization of stable biphase TiO2 photocatalyst with high crystallinity,large surface area,and enhanced photoactivity[J].Journal of Physical Chemistry C,2008,112(8):3083-3089.
[3]MURUGANANDHAM M,SWAMINATHAN M.TiO2-UV photocatalytic oxidation of reactive yellow 14:Effect of operational parameters[J].Journal of Hazardous Materials,2006,135(1-3):78-86.
[4]PILLAI S C,PERIYAT P,GEORGE H,et al.Synthesis of high-temperature stable anatase TiO2photocatalyst[J].Journal of Physical Chemistry C,2007,111(4):1605-1611.
[5]管盘铭,夏亚穆,李德宏,等.掺杂TiO2纳米粉的合成、表征及催化性能研究[J].催化学报,2001,22(2):161-164.GUAN P M,XIA Y M,LI D H,et al.Synthesis,characterization and catalytic performance of doped TiO2nanopowder[J].Chinese Journal of Catalysis,2001,22(2):161-164(in Chinese).
[6]敏世雄,王芳.TiO2共轭高分子纳米复合材料的制备及光催化性能研究[J].化学通报,2008,75(4):297-298.MIN S X,WANG F.Preparation and photocatalytic properties of TiO2conjugated polymer nanocomposites[J].Chemical Bulletin,2008,75(4):297-298(in Chinese).
[7]HOFFMANN M R,MARTIN S T,CHOI W,et al.Environmental applications of semiconductor photocatalysis[J].Chemical Reviews,1995,95(1):69-96.
[8]郭勤,黄冬根,熊伟,等.电化学制备石墨烯/纳米TiO2复合材料及光催化性能[J].复合材料学报,2018,35(1):142-149.GUO Q,HUANG D G,XIONG W,et al.Electrochemical preparation of graphene/nano-TiO2composites and their photocatalytic properties[J].Acta Materiae Compositae Sinica,2018,35(1):142-149(in Chinese).
[9]ELMAAZAWI M,FINKEN A N,NAIR A B,et al.Adsorption and photocatalytic oxidation of acetone on TiO2:An in situ transmission FTIR study[J].Journal of Catalysis,2000,191(1):138-146.
[10]KUMAR A,JAIN A K.Photophysics and photochemistry of colloidal CdS-TiO2coupled semiconductors-photocatalytic oxidation of indole[J].Journal of Molecular Catalysis A:Chemical,2001,165(1-2):265-273.
[11]PILKENTON S,RAFTERY D.Solid-state NMR studies of the adsorption and photooxidation of ethanolon mixed TiO2/SnO2photo-catalysts[J].Solid State Nuclear Magnetic Resonance,2003,24(4):236-253.
[12]HU C,TANG Y C,YU J C,et al.Photocatalytic degradation of cationic blue X-GRL adsorbed on TiO2/SiO2photocatalyst[J].Applied Catalysis B:Environmental,2003,40(2):131-140.
[13]TATSUMA T,TAKEDA S,SAITOH S,et al.Bactericidal effect of an energy storage TiO2/WO3photocatalyst in dark[J].Electrochemistry Communications,2003,5(9):793-796.
[14]YUKINA T,PAILIN N,TETSU T.Energy storage TiO2-MoO3 photocatalysts[J].Electrochimical Acta,2004,49(12):2025-2029.
[15]MAEDA K,ISHIMAKI K,TOKUNAGA Y,et al.Modification of wide-band-gap oxide semiconductors with cobalt hydroxide nanoclusters for visible-light water oxidation[J].Angewandte Chemie,2016,55(29):8309-8313.
[16]SHANG J,LI W,ZHU Y F.Structure and photocatalytic characteristics of TiO2film photocatalyst coated on stainless steel webnet[J].Journal of Molecular Catalysis A:Chemical,2003,202(1-2):187-195.
[17]LU W W,GAO S Y,WANG J J.One-pot synthesis of Ag/ZnO self-as-sembled 3Dhollow microspheres with enhanced photocatalytic performance[J].Journal of Physical Chemistry C,2008,112(43):16792-16800.
[18]HWANG D W,KIM H G,KIM J,et al.Photocatalytic water splitting over highly donor-doped(110)layered perovskites[J].Journal of Catalysis,2000,193(1):40-48.
[19]ZONG X,WU G P,YAN H J,et al.Photocatalytic H2evolution on MoS2/CdS catalysts under visible light irradiation[J].Journal of Physical Chemistry C,2010,114(4):1963-1968.
[20]铁伟伟,张艳鸽,郑直,等.含共轭结构的ZnO/聚乙烯醇复合光催化材料的制备与性能[J].复合材料学报,2016,33(7):1423-1428.TIE W W,ZHANG Y G,ZHENG Z,et al.Preparation and properties of ZnO/polyvinyl alcohol composite photocatalytic materials with conjugated structure[J].Acta Materiae Compositae Sinica,2016,33(7):1423-1428(in Chinese).
[21]LI X Y,WANG D S,CHENG G X,et al.Preparation of polyaniline-modified TiO2nanoparticles and their photocatalytic activity under visible light illumination[J].Applied Catalysis B:Environmental,2008,81(3):267-273.
[22]WANG D S,XU Z X,LUO Q Z,et al.Preparation and visible-light photocatalytic performances of g-C3N4surface hybridized with a small amount of CdS nanoparticles[J].Journal of Materials Science,2016,51(2):893-902.
[23]LI X Y,SHI L,WANG D S,et al.Visible light photocatalytic activity of TiO2/heat-treated PVC film[J].Journal of Chemical Technology&Biotechnology,2012,87(8):1187-1193.
[24]NARITA S,ICHINOHE S,ENOMOTO S,et al.Infrared spectrum of polyvinyl chlorideⅠ[J].Journal of Polymer Science Part A:Polymer Chemistry,1959,37(131):273-280.
[25]DOEUFF S,HENRY M,SANCHEZ C,et al.Hydrolysis of titanium alkoxides:Modification of the molecular precursor by acetic acid[J].Journal of Non-Crystalline Solids,1987,89(1-2):206-216.
[26]KANG I C,ZHANG Q,YIN S,et al.Preparation of a visible sensitive carbon doped TiO2 photo-catalyst by grinding TiO2with ethanol and heating treatment[J].Applied Catalysis B:Environmental,2008,80(1):81-87.
[27]WANG W,ZHOU Y J,LU C H,et al.The effect of hydrothermal temperature on the structure and photocatalytic activity of{001}faceted anatase TiO2[J].Materials Letters,2015,160:231-234.
[28]NISHANTHI S T,IYYAPUSHPAM S,SUNDARAKAN-NAN B,et al.Inter-relationship between extent of anatase crystalline phase and photocatalytic activity of TiO2 nanotubes prepared by anodization and annealing method[J].Separation&Purification Technology,2014,131(2):102-107.
[29]ELLAHI S,HESTER R E,WILLIAMS K P J,et al.Waveguide resonance raman spectroscopy of degraded PVC[J].Spectrochimica Acta Part A:Molecular&Biomolecular Spectroscopy,1995,51(4):549-553.
[30]FUYUHIKO I,ISSEI H,TAKEHIKO S,et al.The resonance Raman spectrum of thermally degraded poly(vinyl chloride)-iodine complex[J].Macromolecules,1975,8(1):1221-1224.
[31]GUPTA K K,MISHRA P K,SRIVASTAVA P,et al.Hydrothermal in situ preparation of TiO2particles onto poly(lactic acid)electrospun nanofibres[J].Applied Surface Science,2013,264:375-382.
[32]REN W J,AI Z H,JIA F L,et al.Low temperature preparation and visible light photocatalytic activity of mesoporous carbon-doped crystalline TiO2[J].Applied Catalysis B:Environmental,2007,69(3):138-144.
[33]JIANG Z F,JIANG D L,YAN Z X,et al.A new visible light active multifunctional ternary composite based on TiO2-In2O3nanocrystals heterojunction decorated porous graphitic carbon nitride for photocatalytic treatment of hazardous pollutant and H2evolution[J].Applied Catalysis B:Environmental,2015,170-171:195-205.
[34]ZHANG F J,XIE F Z,LIU J,et al.Rapid sonochemical synthesis of irregular nanolaminar-like Bi2WO6 as efficient visible-light-active photocatalysts[J].Ultrasonics Sonochemistry,2013,20(1):209-215.
[35]SHANG M,WANG W Z,XU H L,et al.New Bi2WO6nanocages with high visible-light-driven photocatalytic activities prepared in refluxing EG[J].Crystal Growth&Design,2008,9(2):991-996.
[36]ZHUANG J D,DAI W X,TIAN Q F,et al.Photocatalytic degradation of Rh B over TiO2bilayer films:Effect of defects and their location[J].Langmuir,2010,26(12):9686-9694.
[37]YU K,YANG S G,HE H,et al.Visible light-driven photocatalytic degradation of rhodamine B over NaBiO3:Pathways and mechanism[J].Journal of Physical Chemistry A,2009,113(37):10024-10032.
[38]WANG D S,BAO C,LUO Q Z,et al.Improved visible-light photocatalytic activity and anti-photocorrosion of CdS nanoparticles surface-modified by conjugated derivatives from polyvinyl chloride[J].Journal of Environmental Chemical Engineering,2015,3(3):1578-1585.
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