麦饭石/ZnO复合材料的吸附及光催化机制研究
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摘要
以尿素、六水硝酸锌为原料,利用水热法制备了麦饭石/ZnO的复合材料。利用X射线衍射仪、扫描电子显微镜、X射线荧光光谱仪、能谱仪、比表面积测定仪对样品的结构、形貌和光学性能进行了表征。在可见光照射下,以酸性品红为降解物,研究麦饭石/ZnO复合材料的吸附及光催化性能,并通过动力学模型来模拟酸性品红被降解的过程。结果表明,麦饭石加入并没有对ZnO的花瓣形貌产生影响,但对其吸附及光催化性能影响很大。随着麦饭石的含量的增大,比表面积、吸附及光催化性能出现先增大后减少的现象。当麦饭石含量为7%时,由于样品的比表面积最大,电子复合几率最低,所以吸附和光催化效率均达到最大值。
The composite materials of medical stone/ZnO were prepared by hydrothermal method using urea and hexahydrate nitrate as raw materials.The structure,morphology and optical properties of the samples were characterized by X-ray diffraction,scanning electron microscopy,X-ray fluorescence spectrometer,energy dispersive spectrometer and specific surface area analyzer.The effect of medical stone on the adsorption and photocatalysis of ZnO was investigated by using acid magenta as the degradation product under visible light irradiation,and the degradation process of the acid fuchsin was simulated by kinetic model.The results show that the addition of medical stone does not affect the petal morphology of ZnO,but has great influence on its adsorption and photocatalytic properties.With the content of the medical stone increasing,the specific surface area,adsorption and photocatalytic properties increased first and then decreased.When the content of medical stone was7%,as the specific surface area of the sample was the largest and the electron recombination probability was the lowest,the adsorption and photocatalytic efficiency were the maximum.
The composite materials of medical stone/ZnO were prepared by hydrothermal method using urea and hexahydrate nitrate as raw materials.The structure,morphology and optical properties of the samples were characterized by X-ray diffraction,scanning electron microscopy,X-ray fluorescence spectrometer,energy dispersive spectrometer and specific surface area analyzer.The effect of medical stone on the adsorption and photocatalysis of ZnO was investigated by using acid magenta as the degradation product under visible light irradiation,and the degradation process of the acid fuchsin was simulated by kinetic model.The results show that the addition of medical stone does not affect the petal morphology of ZnO,but has great influence on its adsorption and photocatalytic properties.With the content of the medical stone increasing,the specific surface area,adsorption and photocatalytic properties increased first and then decreased.When the content of medical stone was7%,as the specific surface area of the sample was the largest and the electron recombination probability was the lowest,the adsorption and photocatalytic efficiency were the maximum.
引文
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[30]ChengYue,Xiao Zhiguo,Yu Hongwei.Preparation and adsorption properties of amino modified mesoporous microsphere Fe3O4@SiO2@mSiO2 magnetic adsorbent[J].Journal of Functional Materials,2017,48(12):12135-12141(in Chinese).成岳,肖治国,余宏伟,等.氨基化修饰介孔Fe3O4@SiO2@mSiO2磁性吸附剂的制备及吸附性能的研究[J].功能材料,2017,48(12):12135-12141.
[31]Chen Zanyu,Chen Yanbo,Li Qiang,et al.Preparation of fluorine and copper co-doping TiO2 hollow microspheres and its visible light photocatalytic performance[J].The Chinese Journal of Nonferrous Metals,2017,27(8):1643-1650(in Chinese).陈赞宇,陈艳波,李强,等.氟铜共掺杂TiO2空心微球的制备及可见光催化性能[J].中国有色金属学报,2017,27(8):1643-1650.
[32]Gao R,Hou X.Preparation and photo-catalytic activity of TiO2-coated medical stone-based porous ceramics[J].International Journal of Minerals,Metallurgy,and Materials,2013,20(6):593-566.
[2]Nekouei F,Nekouei S.Comparative study of photocatalytic activities of Zn5(OH)8Cl2·H2O and ZnO nanostructures in ciprofloxacin degradation:response surface methodology and kinetic studies[J].Science of The Total Environment,2017,601:508-515.
[3]Zhang Mingju,Li Wenming,Zheng Shukai.First-principles calculations on electronic and optical properties of ZnO codoped with Lu-F[J].The Chinese Journal of Nonferrous Metals,2017,27(5):960-966(in Chinese).张明举,李文明,郑树凯.Lu-F共掺杂ZnO光电性质的第一性原理计算[J].中国有色金属学报,2017,27(5):960-966.
[4]LiZiheng,Li Yin,Du Yan.Photovoltaic characteristics of ZnO nanoparticles[J].Chemical Journal of Chinese Universities,2012,33(3):560-570(in Chinese).李子亨,李根,杜艳.纳米ZnO光伏特性分析[J].高等学校化学学报,2012,33(3):560-570.
[5]Omidi A,Habibi-Yangjeh A,Pirhashemi M.Application of ultrasonic irradiation method for preparation of ZnO nanostructures doped with Sb+3 ions as a highly efficient photocatalyst[J].Applied Surface Science,2013,276:468-475.
[6]Sahu D R,Lin S Y,Huang J L.ZnO/Ag/ZnO multilayer films for the application of a very low resistance transparent electrode[J].Applied Surface Science,2006,252(20):7509-7519.
[7]Arslan O,Abali Y.Controlled modulation of 1D ZnO nano/micro structures:evaluation of the various effects on the photocatalytic activity[J].Journal of Physics&Chemistry of Solids,2017,108:88-97.
[8]Wang Jian.Synthesis and photocatalytic properties research of ZnO nanomaterials and core-shell structure[D].Changchun:University of Chinese Academy of Sciences,2016(in Chinese).王健.ZnO纳米材料及核壳结构的制备和光催化性能研究[D].长春:中国科学院大学,2016.
[9]Han X G,He H Z,Kuan G Q.Controlling morphologies and tuning the related properties of nano/microstructured ZnO crystallites[J].Journal of Physical Chemistry C,2008,113(2):584-589.
[10]He S,Zhang S,Lu J,et al.Enhancement of visible light photocatalysis by grafting ZnO nanoplatelets with exposed(001)facets onto a hierarchical substrate[J].Chemical Communications,2011,47(38):10797-10799.
[11]Meng A,Li X,Wang X.Preparation,photocatalytic properties and mechanism of Fe or N-doped Ag/ZnO nanocomposites[J].Ceramics International,2014,40(7):9303-9310.
[12]Shinde S S,Bhosale C H,Rajpure K Y.Photocatalytic degradation of toluene using sprayed N-doped ZnO thin films in aqueous suspension[J].Journal of Photochemistry&Photobiology B Biology,2012,113(8):70-79.
[13]Qin H,Li W,Xia Y.Photocatalytic activity of heterostructures based on ZnO and N-doped ZnO[J].American Chemical Society Applied Materials&Interfaces,2011,3(8):3152-3160.
[14]Zhang Z,Lin H,Zhang H.Synthesis of spindle-like Ag/ZnO heterostructure composites with enhanced photocatalytic performance[J].Superlattices&Microstructures,2014,65(65):134-140.
[15]Faheria P,Gangopadhyay S,Pande S.Synthesis of ZnO/Au and ZnO/Ag nanoparticles and their photocatalytic application using UV and visible light[J].Rsc Advances,2014,4(48):24962-24970.
[16]Shi L,Liang L,Ma J.Highly efficient visible light-driven Ag/AgBr/ZnO composite photocatalyst for degrading rhodamine B[J].Ceramics International,2014,40(2):3495-3506.
[17]Liu P,Guo Y,Xu Q.Enhanced photocatalytic performance of ZnO/multi-walled carbon nanotube nanocomposites for dye degradation[J].Ceramics International,2014,40(4):5629-5638.
[18]Xue J,Ma S,Zhou Y.Facile synthesis of ZnO-C nanocomposites with enhanced photocatalytic activity[J].New Journal of Chemistry,2014,39(3):1852-1862.
[19]Aamad M,Ahmad E,Ahmad W.Enhancing visible light responsive photocatalytic activity by decorating Mndoped ZnO nanoparticles on graphene[J].Ceramics International,2014,40(7):100087-100097.
[20]Liao S,Huang D,Yu D.Preparation and characterization of ZnO/TiO2,SO42-/ZnO/TiO2 photocatalyst and their photocatalysis[J].Journal of Photochemistry&Photobiology A Chemistry,2004,168(1):8-19.
[21]Li D,Huang J F,Cao L Y.Microwave hydrothermal synthesis of Sr2+doped ZnO crystallites with enhanced photocatalytic properties[J].Ceramics International,2014,40(2):2647-2657.
[22]Qiu X,Li G,Sun X.Doping effects of Co2+ions on ZnO nanorods and their photocatalytic properties[J].Nanotechnology,2008,19(21):4656-4666.
[23]Low J,Cao S,Yu J.Two-dimensional layered composite photocatalysts[J].Chemical Communications,2014,50(74):10768-10777.
[24]Yu L,Wang C,Chen F.Investigating the synergistic effects in tourmaline/TiO2-based heterogeneous photocatalysis:underlying mechanism insights[J].Journal of Molecular Catalysis A:Chemical,2016,411:2-11.
[25]Zhou Jiatian,Linghu Wensheng.Characteristics and applied research progress of medical stone[J].Guangdong Chemical Industry,2012,39(13):72-80(in Chinese).周佳甜,令狐文生.麦饭石的特性及其应用研究进展[J].广东化工,2012,39(13):72-80.
[26]Liu S,Tian J,Wang L,et al.One-pot synthesis of CuO nanoflower-decorated reduced graphene oxide and its application to photocatalytic degradation of dyes[J].Catalysis Science&Technology,2012,2(2):339-344.
[27]Rong Xinshan.Preparation of semiconductor(metal oxide,carbon nitride)-based composited material and its research on adsorption/photocatalysis performance[D].Zhenjiang:Jiangsu University,2016(in Chinese).荣新山.半导体(金属氧化物、氮化碳)基复合材料的制备及其吸附/光催化性能研究[D].镇江:江苏大学,2016.
[28]Chen Feitai.Study on adsorption performances and photocatalytic activities of TiO2-based nanostructures[D].Wuhan:Wuhan University,2013(in Chinese).陈飞台.TiO2基纳米结构的吸附与光催化性能研究[D].武汉:武汉大学,2013.
[29]Zheng Wenjing,Lin Jianwei,Zhan Yanhui.Removal of nitrate from aqueous solution using cetylpyridinium chloride(CPC)-modified activated carbon as the adsorbent[J].Environmental Science,2013,34(11):4325-4336(in Chinese).郑雯婧,林建伟,詹艳慧.氯化十六烷基吡啶改性活性炭对水中硝酸盐的吸附作用[J].环境科学,2013,34(11):4325-4336.
[30]ChengYue,Xiao Zhiguo,Yu Hongwei.Preparation and adsorption properties of amino modified mesoporous microsphere Fe3O4@SiO2@mSiO2 magnetic adsorbent[J].Journal of Functional Materials,2017,48(12):12135-12141(in Chinese).成岳,肖治国,余宏伟,等.氨基化修饰介孔Fe3O4@SiO2@mSiO2磁性吸附剂的制备及吸附性能的研究[J].功能材料,2017,48(12):12135-12141.
[31]Chen Zanyu,Chen Yanbo,Li Qiang,et al.Preparation of fluorine and copper co-doping TiO2 hollow microspheres and its visible light photocatalytic performance[J].The Chinese Journal of Nonferrous Metals,2017,27(8):1643-1650(in Chinese).陈赞宇,陈艳波,李强,等.氟铜共掺杂TiO2空心微球的制备及可见光催化性能[J].中国有色金属学报,2017,27(8):1643-1650.
[32]Gao R,Hou X.Preparation and photo-catalytic activity of TiO2-coated medical stone-based porous ceramics[J].International Journal of Minerals,Metallurgy,and Materials,2013,20(6):593-566.