摘要
作为一类新兴的光催化材料,钼酸盐纳米材料具有高表面能、多活性位点和高选择性等优点,在可见光催化降解污染物方面有着重要应用,近年来受到广泛关注.作为钼酸盐家族重要的一员,钼酸银在杀菌、表面增强拉曼光谱、气敏材料等方面均有重要应用,但其光催化性能却鲜见报道.这是由于它的光谱响应范围窄和广生载流子分离效率低所致.虽然近来有少量基于钼酸银的复合材料的光催化研究,但催化效果不佳.众所周知,作为自由电子体系,诸多金属纳米粒子,如贵金属、碱金属等,存在表面等离子体共振效应(SPR),使得贵金属,特别是Ag,Au等纳米粒子在可见区域有较强的吸收.利用这一特性,Awazu等将Ag纳米颗粒沉积在TiO_2表面,创造性地将SPR应用于光催化反应,开发出在可见光谱区具有宽光谱吸收特征的Ag/TiO_2.随后陆续合成出基于SPR效应的Ag@AgCl,Ag/Ag_3PO_4材料均具有良好的光催化性能.基于此,本文在十二烷基硫酸钠(SDS)的存在下,采用水热法一步合成了具有SPR效应的Ag/Ag_2MoO_4可见光催化材料,并利用X射线粉末衍射(XRD)、紫外可见漫反射(DRS)、X射线光电子能谱(XPS)和扫描电子显微镜(SEM)等技术对材料进行了表征.系统地探讨了体系pH值、反应时间、表面活性剂用量对产物的晶相和微观形貌等的影响.此外,还利用罗丹明B降解实验考察了上述合成条件对材料可见光催化活性的影响,并通过捕获剂实验深入地研究了起催化作用的活性物种.XRD结果表明,体系的pH值对材料的晶型有极大影响,随着pH由酸性变至中性、碱性,最终得到的钼酸银也由Ag_2Mo_2O_7过渡到Ag_2MoO_4.SEM图显示在最优条件(pH为7,加入0.5g SDS,160℃下水热14 h)下制得的钼酸银为八面体的Ag_2MoO_4,且其表面均匀地分布着Ag纳米颗粒,与XPS图谱结果一致.另外表面活性剂SDS的用量对所合成材料的形貌影响很大.本文可一步得到以八面体Ag_2MoO_4为主的Ag/Ag_2MoO_4复合材料,是因为SDS的疏水长链可以诱导Ag_2MoO_4的各向异性生长.DRS结果表明,Ag_2MoO_4八面体上Ag颗粒的引入使其在可见光区的吸收明显加强,因而它在可见光下催化降解罗丹明B降解反应活性增加.捕获剂实验结果表明,起决定性作用的活性物种是光生空穴,另外·OH也起了一定作用.
Novel silver/silver molybdate（Ag/Ag2MoO4） composites with surface plasmon resonance（SPR）-enhanced photocatalytic performance were successfully fabricated via a facile one-pot hydrothermal route with the presence of sodium dodecyl sulfate（SDS） in this study.The as prepared silver/silver molybdate（Ag/Ag2MoO4） composites were systematically characterized by X-ray diffraction（XRD）,scanning electron microscopy（SEM） and ultraviolet-visible diffuse reflectance absorption spectroscopy（DRS） in order to investigate their crystal structure,morphology and optical property as well.The photocatalytic activities of the composites were subsequently evaluated by their ability to degrade rhodamine B（RhB） under visible-light irradiation.Varies of controlled experiments were then carefully operated to gain a deep insight into the assembling of Ag/Ag2MoO4composites.It was found that preparation conditions such as pH,reaction time,and the amount of surfactant played important roles in the formation of composites with octahedral microstructures.And the composite obtained at 160 ℃ using 0.5 g of sodium dodecyl sulfate exhibited the highest photocatalytic performance under visible-light irradiation.Capture experiments were also conducted to clarify the function of different active species generated on the surface of Ag/Ag2MoO4during the photocatalytic process,in which both holes and ·OH radicals were found to play crucial role in photocatalytic removal of RhB under visible light irradiation.A possible photocatalytic mechanism of Ag/Ag2MoO4 was finally proposed on the basis of all the results to explain the higher photocatalytic activity of the octahedral Ag/Ag2MoO4 composites.It was inferred that the photoinduced ＂hot＂ electrons can quickly transfer from the Ag NPs to the conduction band of Ag2MoO4 and react with oxygen and H2O to generate a large quality of active radicals such as ·OH and ·O2^- because of the SPR effects.Besides,this SPR effects of Ag nanoparticles deposited on the surface of Ag2MoO4 can not only dramatically amplify its light absorption,especially in the visible region,but also promote the separation of photoexcited electron-hole pairs and effectively decrease electron-hole recombination.
基金
supported by Fundamental Research Funds for the Central Universities (2662014BQ061, 2015PY120, 2015PY047, 2016PY088)
the National Natural Science Foundation of China (51572101, 21502059, 21607047)~~
