不同尺寸金纳米颗粒的制备及其SERS性能
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摘要
为了研究不同尺寸的金纳米颗粒作为表面增强喇曼散射(SERS)活性基底对表面增强喇曼光谱的影响,采用氯金酸作为金源,柠檬酸三钠作为还原剂及保护剂,通过控制柠檬酸三钠的加入量合成了不同尺寸的金纳米颗粒。通过扫描电子显微镜(SEM)和紫外可见分光光度计(UV-vis)等技术对金纳米颗粒进行了性质表征。利用喇曼光谱仪,以罗丹明B作为被检测探针,研究了三种不同尺寸的金纳米颗粒(20、50和100 nm)喇曼增强效果。通过喇曼光谱图发现20和50 nm的金纳米颗粒具有较好的SERS效果。随后以20 nm的金纳米颗粒为SERS活性基底,对表面增强喇曼光谱检测罗丹明B的检测限进行了研究,可以使罗丹明检测限灵敏度达到10-9 mol/L。
In order to study the effects of Au nano-particles of different sizes as surface-enhanced Raman scattering(SERS)active substrates on SERS,the Au nano-particles of different sizes were synthesized by using chloroauric acid as Au sources and sodium citrate as reductants and protectants,and by controlling the added amounts of sodium citrate.The properties of the Au nano-particles were characterized by the scanning electron microscopy(SEM),ultraviolet-visible spectrophotometer(UV-vis)and so on.With rhodamine B as the test probe,the Raman enhancement effects of the Au nano-particles with three different sizes(i.e.20,50 and 100 nm)were studied by Raman spectroscopy.Through the Raman spectra,it is found that the Au nano-particles of 20 nm and 50 nm exhibit better SERS effects.Then the detection limit of rhodamine B of SERS was studied with20 nm Au nano-particles as the SERS active substrate,and the sensitivity of the detection limit of rhodamine B can reach 10-9 mol/L.
In order to study the effects of Au nano-particles of different sizes as surface-enhanced Raman scattering(SERS)active substrates on SERS,the Au nano-particles of different sizes were synthesized by using chloroauric acid as Au sources and sodium citrate as reductants and protectants,and by controlling the added amounts of sodium citrate.The properties of the Au nano-particles were characterized by the scanning electron microscopy(SEM),ultraviolet-visible spectrophotometer(UV-vis)and so on.With rhodamine B as the test probe,the Raman enhancement effects of the Au nano-particles with three different sizes(i.e.20,50 and 100 nm)were studied by Raman spectroscopy.Through the Raman spectra,it is found that the Au nano-particles of 20 nm and 50 nm exhibit better SERS effects.Then the detection limit of rhodamine B of SERS was studied with20 nm Au nano-particles as the SERS active substrate,and the sensitivity of the detection limit of rhodamine B can reach 10-9 mol/L.
引文
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[23] ZHANG T,SUN Y,HANG L,et al.Periodic porous alloyed Au-Ag nanosphere arrays and their highly sensitive SERS performance with good reproducibility and high density of hotspots[J].ACS Applied Materials&Interfaces,2018,10(11):9792-9801.
[24] WANG M,SHI G,ZHU Y,et al.Au-decorated dragonfly wing bioscaffold arrays as flexible surface-enhanced Raman scattering(SERS)substrate for simultaneous determination of pesticide residues[J].Nanomaterials,2018,8(5):1-16.
[25]潘龙飞.金纳米颗粒的制备及暗场观测系统[D].合肥:中国科学技术大学,2017.
[26]高丽珍.金纳米颗粒的制备、表面改性及其光学特性的研究[D].开封:河南大学,2004.
[27] KREIBIG U,VOLLMER M.Optical properties of metal clusters[M].Berlin:Springer-Verlag,1995:278-279.
[2]周全.罗丹明荧光探针的设计、合成及应用的研究[D].长沙:湖南大学,2015.
[3]王传现,韩丽,方晓明,等.食品中罗丹明B的高效液相色谱荧光检测[J].分析仪器,2008(1):27-30.
[4]张贞理,张平,申大忠.超高效液相色谱-串联质谱法同时测定水产调味品中的罗丹明B、结晶紫和孔雀石绿[J].分析化学,2012,40(3):487-488.
[5]叶佳明,汪庆旗,应寒松,等.食品中罗丹明B的高效液相色谱串联质谱法检测[J].农产品加工,2017(2):52-54.
[6]赵珊,张晶,丁晓静,等.凝胶净化/超高效液相色谱电喷雾质谱法检测调味油中11种禁用偶氮染料及罗丹明B[J].分析测试学报,2012,31(4):448-452.
[7]胡小钟,储晓刚,余建新,等.基质固相分散和气相色谱-质谱法测定浓缩苹果汁中22种有机氯农药和15种拟除虫菊酯农药的残留量[J].分析测试学报,2004,23(5):38-42.
[8]胡贝贞,宋伟华,谢丽萍,等.加速溶剂萃取/凝胶渗透色谱-固相萃取净化/气相色谱-质谱法测定茶叶中残留的33种农药[J].色谱,2008,26(1):22-28.
[9] RAJALAKSHMI S,PITCHAIMUTHU S,KANNAN N,et al.Enhanced photocatalytic activity of metal oxides/β-cyclodextrin nanocomposites for decoloration of rhodamine B dye under solar light irradiation[J].Applied Water Science,2017,7(1):115-127.
[10] LOU X Y,GUO Y G,XIAO D X,et al.Rapid dye degradation with reactive oxidants generated by chloride-induced peroxymonosulfate activation[J].Environmental Science&Pollution Research International,2013,20(9):6317-6323.
[11] KNEIPP J,KNEIPP H,KNEIPP K.SERS—a single-molecule and nanoscale tool for bioanalytics[J].Chemical Society Reviews,2008,37(5):1052-1060.
[12] KNEIPP K,WANG Y,KNEIPP H,et al.Single molecule detection using surface-enhanced Raman scattering(SERS)[J].Physical Review Letters,1997,78(9):1667-1670.
[13] LIU H,ZHANG L,LANG X,et al.Single molecule detection from a large-scale SERS-active Au79Ag21substrate[J].Scientific Reports,2011,1(112):1-6.
[14] KANG T,YOO S M,YOON I,et al.Patterned multiplex pathogen DNA detection by Au particle-on-wire SERS sensor[J].Nano Letters,2010,10(4):1189-1193.
[15] SHARMA S K,KUMAR P,BARTHWAL S,et al.Highly sensitive surface-enhanced raman scattering(SERS)-based multi gas sensor:Au nanoparticles decorated on partially embedded 2D colloidal crystals into elastomer[J].Chemistry Select,2017,2(24):6961-6969.
[16] QUYEN T T B,CHANG C C,SU W N,et al.Self-focusing Au@SiO2 nanorods with rhodamine 6G as highly sensitive SERS substrate for carcinoembryonic antigen detection[J].Journal of Materials Chemistry:B,2014,2(6):629-636.
[17] ZHANG M,LING Y,YU S,et al.Au@SiO2nanoparticles sheathed W nano-tips for local electrochemical and SERS applications[C]//Proceedings of the 232nd ECS meeting.Washington DC,USA,2017:1-3.
[18] TONG R,HU X,FANG G,et al.Rapid detection of hexamethylenetetramine based on the substrate UC@SiO2@Au@Ag using SERS[J].RSC Advances,2017,7(79):49969-69974.
[19]曹瑶.基于纳米金整体柱表面增强喇曼光谱研究及其在生物分析中的应用[D].北京:北京化工大学,2016.
[20]陶文玉.贵金属微纳米结构的设计与制备及其SERS性质研究[D].合肥:中国科学技术大学,2014.
[21] ANKUDZE B,PAKKANEN T T.Gold nanoparticle decorated Au-Ag alloy tubes:a bifunctional substrate for label free and in situ,surface-enhanced Raman scattering based reaction monitoring[J].Applied Surface Science,2018,453:341-349.
[22] SUN M,ZHAO A,WANG D,et al.Cube-like Fe3O4@SiO2@Au@Ag magnetic nanoparticles:a highly efficient SERS substrate for detection of pesticide[J].Nanotechnology,2018,29(16):1-6.
[23] ZHANG T,SUN Y,HANG L,et al.Periodic porous alloyed Au-Ag nanosphere arrays and their highly sensitive SERS performance with good reproducibility and high density of hotspots[J].ACS Applied Materials&Interfaces,2018,10(11):9792-9801.
[24] WANG M,SHI G,ZHU Y,et al.Au-decorated dragonfly wing bioscaffold arrays as flexible surface-enhanced Raman scattering(SERS)substrate for simultaneous determination of pesticide residues[J].Nanomaterials,2018,8(5):1-16.
[25]潘龙飞.金纳米颗粒的制备及暗场观测系统[D].合肥:中国科学技术大学,2017.
[26]高丽珍.金纳米颗粒的制备、表面改性及其光学特性的研究[D].开封:河南大学,2004.
[27] KREIBIG U,VOLLMER M.Optical properties of metal clusters[M].Berlin:Springer-Verlag,1995:278-279.
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