氧化铜/氧化锌/3A分子筛光催化剂的制备及其可见光脱氮性能
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摘要
采用浸渍法合成了氧化铜/氧化锌/3A分子筛(Cu O/Zn O/3A)复合催化剂,并利用X射线粉末衍射(XRD)、紫外-可见漫反射光谱(UV-Vis DRS)、X射线光电子能谱(XPS)等技术手段对催化剂的结构及性能进行了系统的表征;以吡啶-正辛烷体系为模拟油品氮源,系统研究了该催化剂在可见光作用下的光催化脱氮行为,并系统考察了催化剂的制备条件、用量及催化时间对其脱氮性能的影响。结果表明,随着锌源与铜源加入量的增加,Cu O/Zn O/3A复合物的光催化活性,呈现先增大后降低的规律。在400℃煅烧5 h的情况下,当锌源的加入质量分数为9.8%,铜源的加入质量分数为28.6%时,在可见光照射条件下,反应150 min后,Cu O/Zn O/3A复合催化剂对50 m L吡啶质量分数为100μg/g的模拟油品中吡啶的脱氮率达到74.78%。
Copper oxide / zinc oxide /3A molecular sieve( Cu O / Zn O /3A) photocatalyst was prepared by impregnation method and calcined in 450 ℃,and the structure of Cu O / Zn O /3A was characterized by X-ray diffraction( XRD), UV-Vis diffuse reflectance spectroscopy( UV-Vis DRS), and X-ray photoelectron spectroscopy( XPS). Its photocatalytic denitrification behavior was studied by pyridine-n-octane system for simulated oil source of nitrogen under visible light irradiation. The influences of the preparation conditions of the photocatalyst, the amount of photocatalyst and the time of light irradiation on the photocatalytic denitrification performance were investigated. With the increase of the amount of metal oxide,photocatalytic activity of the complex increased at first and then decreased. The Cu O / Zn O /3A composite photocatalyst calcined at 400 ℃ for 5 h with 9. 8% mass fraction of zinc and 28. 6% of copper enabled 74. 78%denitrification of the simulated oil system,after a reaction under visible light of 50 m L solution containing100 μg / g of pyridine for 150 min.
Copper oxide / zinc oxide /3A molecular sieve( Cu O / Zn O /3A) photocatalyst was prepared by impregnation method and calcined in 450 ℃,and the structure of Cu O / Zn O /3A was characterized by X-ray diffraction( XRD), UV-Vis diffuse reflectance spectroscopy( UV-Vis DRS), and X-ray photoelectron spectroscopy( XPS). Its photocatalytic denitrification behavior was studied by pyridine-n-octane system for simulated oil source of nitrogen under visible light irradiation. The influences of the preparation conditions of the photocatalyst, the amount of photocatalyst and the time of light irradiation on the photocatalytic denitrification performance were investigated. With the increase of the amount of metal oxide,photocatalytic activity of the complex increased at first and then decreased. The Cu O / Zn O /3A composite photocatalyst calcined at 400 ℃ for 5 h with 9. 8% mass fraction of zinc and 28. 6% of copper enabled 74. 78%denitrification of the simulated oil system,after a reaction under visible light of 50 m L solution containing100 μg / g of pyridine for 150 min.
引文
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[4]Kim H G,Jeong E D,Borse P H,et al.Photocatalytic Ohmic Layered Nanocomposite for Efficient Utilization of Visible Light Photons[J].Appl Phys Lett,2006,89(6):064103-1-064103-3.
[5]Wang M,Ye C H,Zhang Y,et al.Synthesis of Well-aligned Zn O Nanorod Arrays with High Optical Property via a Lowtemperature Solution Method[J].J Cryst Growth,2006,291(2):334-339.
[6]Lu F,Cai W,Zhang Y.Zn O Hierarchical Micro/nanoarchitectures:Solvothermal Synthesis and Structurally Enhanced Photocatalytic Performance[J].Adv Funct Mater,2008,18(7):1047-1056.
[7]Liu Z L,Deng J C,Deng J J,et al.Fabrication and Photocatalysis of Cu O/Zn O Nano-composites via a New Method[J].Mater Sci Eng B,2008,150(2):99-104.
[8]ZHANG Peipei,XIONG Jie.Preparation and Photocatalytic Properties of Zn O/Cu O Nanofibers[J].J Zhejiang Sci-Tech Univ,2010,27(5):703-709(in Chinese).张培培,熊杰.Zn O/Cu O复合纳米纤维的制备及其光催化性能研究[J].浙江理工大学学报,2010,27(5):703-709.
[9]Alireza Kargar,Yi Jing,Sung Joo Kim,et al.Zn O/Cu O Heterojunction Branched Nanowires for Photoelectrochemical Hydrogen Generation[J].ACS Nano,2013,7(12):11112-11120.
[10]FAN Huitao,ZENG Yi,YANG Haibin,et al.Preparation and Gas Sensitive Properties of Zn O-Cu O Nanocomposites[J].Acta Phys-Chim Sin,2008,24(7):1292-1296(in Chinese).范会涛,曾毅,杨海滨,等.Zn O-Cu O纳米复合氧化物的制备及其气敏性能[J].物理化学学报,2008,24(7):1292-1296.
[11]MA Liming,LI Jinchai.Fabrication of Cu O/Zn O Coaxial Nanowires Heterostructures and Quantum Dot Heterojunctions[J].J Wuhan Univ(Nat Sci Ed),2011,57(3):215-219(in Chinese).马利明,李金钗.Cu O/Zn O量子点异质结及同轴纳米线异质结构的研制[J].武汉大学学报(理学版),2011,57(3):215-219
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[13]Sahay R,Sundaramurthy J,Suresh K P,et al.Synthesis and Characterization of Cu O Nanofibers,and Investigation for Its Suitability as Blocking Layer in Zn O NPs Based Dye Sensitized Solar Cell and as Photocatalyst in Organic Dye Degradation[J].J Solid State Chem,2012,186:261-267.
[14]YAN Guiyang,WANG Xuxu,FU Xianzhi.A Primary Study on Photocatalytic Properties of ZSM-5 Zeolite[J].Chem J Chinese Univ,2004,25(5):942-944(in Chinese).颜桂炀,王绪绪,付贤智.ZSM-5分子筛光催化活性的初步研究[J].高等学校化学学报,2004,25(5):942-944.
[15]Yan G Y,Long J L,Wang X,et al.Insight into Photoactive Sites for the Ethylene Oxidationon Commercial HZSM-5 Zeolites with Iron Impurities by UVRaman,X-ray Absorption Fine Structure,and Electron Paramagnetic Resonance Spectroscopies[J].J Phys Chem C,2007,111(13):5195-5202.
[16]Huang Z W,Cui F,Kang H X,et al.Highly Dispersed Silica-supported Copper Nanoparticles Prepared by Precipitation-gel Method:A Simple but Efficient and Stable Catalyst for Glycerol Hydrogenolysis[J].Chem Mater,2008,20(15):5090-5099.
[17]Myung Y,Jang D M,Sung T K,et al.Composition-Tuned Zn O-Cd SSe Core-Shell Nanowire Arrays[J].ACS Nano,2010,4(7):3789-3800.
[18]Li J,Liu L,Yu Y.Preparation of Highly Photocatalytic Active Nano-size Ti O2-Cu2O Particle Composites with a Novel Electrochemical Method[J].Electrochem Commun,2004,6(9):940-943.
[19]Jung S,Yong K.Fabrication of Cu O Zn O Nanowires on a Stainless Steel Mesh for Highly Efficient Photocatalytic Applications[J].Chem Commun,2011,47(9):2643-2645.
[20]Lu Y C,Lin Y H,Xie T F,et al.Effect of Photogenerated Charge Transfer on the Photocatalysis in High-Performance Hybrid Pt-Co∶Zn O Nanostructure Photocatalyst[J].ACS Appl Mater Interfaces,2013,5(10):4017-4020.