pH值对SnO_2/ZnO形貌及光催化性能的影响
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摘要
为考察酸度对SnO_2/ZnO样品的形貌及光催化活性的影响,以氯化锌和四氯化锡为原料,采用水热反应法在不同酸度条件下制备系列SnO_2/ZnO,并以亚甲基蓝作为目标降解物测试SnO_2/ZnO的光催化活性。采用Fourier红外光谱仪、X射线衍射仪、扫描电子显微镜、紫外可见漫反射光谱仪、X光电子能谱仪、荧光发射光谱及N_2吸附–脱附技术对SnO_2/Zn O进行表征。结果表明:通过调节反应溶液酸度可得到粒状、立方体和球状等不同形貌的SnO_2/ZnO复合材料。光催化实验表明:SnO_2/ZnO系列样品的光催化活性均高于ZnO和SnO_2,在pH值为9的条件下制备的具有立方体结构的样品(Zn-9)光催化效果最好,光照70 min对10 mg/L亚甲基蓝溶液的降解率达97.5%,循环使用5次后依然保持较高的光催化活性。
To investigate the influence of solution pH value on the morphology and photo-catalytic activity of SnO_2/ZnO, zinc chloride and tin tetrachloride were used as raw materials and a series of SnO_2/ZnO materials were synthesized by a hydrothermal method at different solution pH values. Methylene blue(MB), as a photocatalytic degradation target, was used to evaluate the photocatalytic performance of SnO_2/ZnO. The samples were characterized by Fourier transformed infrared spectroscopy, X-ray diffraction, scanning electronic microscopy, ultraviolet-visible diffuse reflectance spectroscopy, X-ray photoelectron spectroscopy, photoluminescence spectroscopy and N2 adsorption–desorption isotherms, respectively. The results show that the various morphologies of SnO_2/ZnO, such as granular, cubic and spherical, can be obtained via changing the acidity of reaction solution. In addition, the photodegradation experiments show that the photocatalytic activity of all SnO_2/ZnO samples is all greater than that of pure ZnO and SnO_2. The sample(Zn-9) prepared at pH value 9 with a cubic-like morphology has the optimum best photocatalytic activity for the degradation MB(10 mg/L) and can reach 97.5% of degradation rate in 70 min, which remains a better photocatalytic activity after five cycles.
To investigate the influence of solution pH value on the morphology and photo-catalytic activity of SnO_2/ZnO, zinc chloride and tin tetrachloride were used as raw materials and a series of SnO_2/ZnO materials were synthesized by a hydrothermal method at different solution pH values. Methylene blue(MB), as a photocatalytic degradation target, was used to evaluate the photocatalytic performance of SnO_2/ZnO. The samples were characterized by Fourier transformed infrared spectroscopy, X-ray diffraction, scanning electronic microscopy, ultraviolet-visible diffuse reflectance spectroscopy, X-ray photoelectron spectroscopy, photoluminescence spectroscopy and N2 adsorption–desorption isotherms, respectively. The results show that the various morphologies of SnO_2/ZnO, such as granular, cubic and spherical, can be obtained via changing the acidity of reaction solution. In addition, the photodegradation experiments show that the photocatalytic activity of all SnO_2/ZnO samples is all greater than that of pure ZnO and SnO_2. The sample(Zn-9) prepared at pH value 9 with a cubic-like morphology has the optimum best photocatalytic activity for the degradation MB(10 mg/L) and can reach 97.5% of degradation rate in 70 min, which remains a better photocatalytic activity after five cycles.
引文
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[25]HUY T H,PHAT B D,KANG F,et a1.SnO2/Ti O2 nanotube heterojunction:The first investigation of NO degradation by visible light driven photocatalysis[J].Chemosphere,2019,215:323-332.
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[27]WANG C,ZHAO J,WANG X,et al.Preparation characterization and photocatalytic activity of nano-sized ZnO/SnO2 coupled photocatalysts[J].Appl Catal B:Environ,2002,39(3):269-279.
[28]CHEN W,QIU Y,ZHONG Y,et al.High efficiency dye-sensitized solar cells based on the composite photoanodes of SnO2nanoparticles/ZnO nanotetrapods[J].J Phys Chem A,2010,114(9):3127-3138.
[29]HAMROUN A,MOUSSA N,PARRINO F,et al.Sol-gel synthesis and photocatalytic activity of ZnO-SnO2 nanocomposites[J].J Mol Catal A:Chem,2014,390:133-141.
[2]周武艺,唐绍裘,张世英,等.制备不同稀土掺杂的纳米氧化钛光催化剂及其光催化活性[J].硅酸盐学报,2004,32(10):1203-1208.ZHOU Wuyi,TANG Shaoqiu,ZHANG Shiying,et al.J Chin Ceram Soc,2004,32(10):1203-1208.
[3]KARUNAKARAN C,VINAYAGAMOORTHY P.Superparamagnetic core/shell Fe2O3/ZnO nanosheets as photocatalyst cum bactericide[J].Catal Today,2017,284:114-120.
[4]HARISH S,ARCHANA J,SABARINATHAN M,et a1.Controlled structural and compositional characteristic of visible light active ZnO/CuO photocatalyst for the degradation of organic pollutant[J].Appl Surf Sci,2017,418:103-112.
[5]汪滨,张广心,郑水林,等.Ce掺杂纳米Ti O2/硅藻土复合材料的光催化性能[J].硅酸盐学报,2016,44(8):1192-1199.WANG Bing,ZHANG Guangxin,ZHENG Shuilin,et al.J Chin Ceram Soc,2016,44(8):1192-1199.
[6]何霞,刘海瑞,董海亮,等.ZnO/In2O3纳米异质结的合成及其光催化性能的研究[J].无机材料学报,2014,3(29):264-268.HE Xia,LIU Hairui,DONG Hailiang,et al.J Inorg Mater(in Chinese),2014,3(29):264-268.
[7]RADZIMSKA A K,JESIONOWSKI T.Zinc oxide-from synthesis to application:A review[J].Materials,2014,7(4):2833-2881.
[8]DAS S,JAYARAMAN V.SnO2:A comprehensive review on structures and gas sensors[J].Prog Mater Sci,2015,46(23):112-255.
[9]KAR A,SAIN S,ROSSOUW D,KNAPPETT B R,et a1.Facile synthesis of SnO2-PbS nanocomposites with controlled structure for applications in photocatalysis[J].Nanoscale,2016,8(5):2727-2739.
[10]CAO L,SPIESS F J,HUANG A A,et al.Heterogeneous photocatalytic oxidation of 1-Butene on SnO2 and TiO2 films[J].J Phys Chem B,1999,103(15):2912-2917.
[11]LIAO X,CHEN J,WANG M,LIU Z,et a1.Enhanced photocatalytic and photoelectrochemical activities of SnO2/Si C nanowire heterostructure photocatalysts[J].J Alloys Compd,2016,658(2):642-648.
[12]LAMBA R,UMAR A,MEHTA S K,et a1.Well-crystalline porous ZnO-SnO2 nanosheets an effective visible-light driven photocatalyst and highly sensitive smart sensor material[J].Talanta,2015,131:490-498.
[13]LAMBA R,UMAR A,MEHTA S K,et a1.ZnO doped SnO2nanoparticles heterojunction photocatalyst for environmental remediation[J].J Alloys Compd,2015,653:327-333.
[14]WANG W W,ZHU Y J,YANG L X.ZnO-SnO2 hollow spheres and hierarchical nanosheets:Hydrothermal preparation,formation mechanism and photocatalytic properties[J].Adv Funct Mater,2010,17(1):59-64.
[15]HAMROUNI A,MOUSSA N,PARRINO F,et a1.Sol-gel synthesis and photocatalytic activity of ZnO-SnO2 nanocomposites[J].J Mol Catal A,2014,390(8):133-141.
[16]JIN C Q,GE C H,JIAN Z G,et al.Facile synthesis and high photocatalytic degradation performance of ZnO-SnO2 hollow spheres[J].Nanoscale Res Lett,2016,11:526-532.
[17]GORDILLO G,MORENO L C,DELACRUZ W,et al.Preparation and characterization of SnO2 thin films deposited by spray pyrolysis from SnCl2 and Sn Cl4 precursors[J].Thin Solid Films,1994,252(1):61-66.
[18]ZHANG B,YUN T,ZHANG J,et a1.The FTIR studies on the structural and electrical properties of SnO2:Films as a function of hydrofluoric acid concentration[J].Optoelectron Adv Mater,2010,4(8):1158-1162.
[19]PUSAWALE S N,DESHMUKH P R,LOKHANDE C D.Chemical synthesis and characterization of hydrous tin oxide thin films[J].Bull Mater Sci,2011,34(6):1179-1183.
[20]RAHMAN M M,GRUNER G,GHAMDI M S,et a1.Chemo-sensors development based on low-dimensional codoped Mn2O3-ZnOnanoparticles using flat-silver electrodes[J].Chem Central J,2013,7(1):60-60.
[21]崔红卫,张富春,邵婷婷.Sn掺杂ZnO电子结构与光学性质的第一性原理研究[J].光学学报,2016,36(7):204-212.CUI Hongwei,ZHANG Fuchun,SHAO Tingting.Acta Opt Sini,2016,36(7):204-212.
[22]SUN B,SIRRINGHAUS H.Surface tension and fluid flow driven self-assembly of ordered ZnO nanorod films for high-performance field effect transistors[J].J Am Chem Soc,2006,128(50):16231-16237.
[23]SING K S W.Reporting physisorption data for gas/solid systems with special reference to the determination of surface area and porosity[J].Pure Appl Chem,1985,57(4):603-619.
[24]JO W K,SELVAM N C.Enhanced visible light driven photocatalytic performance of Zn O-g-C3N4 coupled with graphene oxide as a novel ternary nanocomposite[J].J Hazard Mater,2015,299:462-470.
[25]HUY T H,PHAT B D,KANG F,et a1.SnO2/Ti O2 nanotube heterojunction:The first investigation of NO degradation by visible light driven photocatalysis[J].Chemosphere,2019,215:323-332.
[26]HSIEH P T,CHEN Y C,KAO K S,et a1.Luminescence mechanism of ZnO thin film investigated by XPS measurement[J].Appl Phys A,2008,90:317-321.
[27]WANG C,ZHAO J,WANG X,et al.Preparation characterization and photocatalytic activity of nano-sized ZnO/SnO2 coupled photocatalysts[J].Appl Catal B:Environ,2002,39(3):269-279.
[28]CHEN W,QIU Y,ZHONG Y,et al.High efficiency dye-sensitized solar cells based on the composite photoanodes of SnO2nanoparticles/ZnO nanotetrapods[J].J Phys Chem A,2010,114(9):3127-3138.
[29]HAMROUN A,MOUSSA N,PARRINO F,et al.Sol-gel synthesis and photocatalytic activity of ZnO-SnO2 nanocomposites[J].J Mol Catal A:Chem,2014,390:133-141.