基于不同化学还原法制备的Au/XC-72及其对L-CySH的催化氧化反应研究
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摘要
本文采用乙二醇还原法、抗坏血酸还原法、柠檬酸三钠还原法及硼氢化钠还原法合成胶体金溶液,并将其负载于XC-72上制备Au/XC-72催化剂。X射线衍射(XRD)表明四种方法制备的催化剂均具有明显的Au特征衍射峰,且硼氢化钠还原法制备的Au衍射峰最平缓。透射电子显微镜(TEM)表明硼氢化钠还原法制备的金纳米颗粒(Au NPs)粒径最小,在XC-72表面分布均匀,其他三种方法制备的AuNPs粒径较大,且发生不同程度的团聚。利用制备的催化剂(Au/XC-72)修饰玻碳电极(GCE)并用于L-半胱氨酸(L-CySH)的电催化氧化机制研究,结果显示硼氢化钠还原法制备的Au/XC-72在pH为2时对L-CySH的催化氧化较其它三种方法制备的材料表现出最优的活性,且在1m M～10m M的范围内呈现线性关系,表明L-CySH在Au/XC-72上的氧化反应的速率是受扩散过程控制的。电催化活性高粒径小的Au/XC-72修饰GCE构建的传感器具有广泛的实际应用价值。
A colloidal gold solution was prepared by the methods of ethylene glycol reduction, ascorbic acid reduction, trisodium citrate reduction, and sodium borohydride reduction and supported on XC-72 substrate. Results of X-ray diffraction(XRD) showed that the catalyst prepared by the four methods contained obvious characteristic peak of Au. The Au/XC-72 diffraction peak prepared by sodium borohydride reduction method was the most gradual. Results of transmission electron microscopy(TEM) indicated that the Au NPs prepared by the sodium borohydride reduction method achieved a particle size of less than 5 nm and revealed a uniform distribution on the surface of XC-72. The Au NPs prepared by the other three methods presented larger particle size agglomeration. These catalysts(Au/XC-72) were modified on glassy carbon electrode(GCE) and used for electrochemical oxidation of L-cysteine(L-CySH). The results showed that the preparation of Au/XC-72 modified GCE by sodium borohydride reduction exihibited the best electrocatalytic activity of L-CySH in pH 2 PBS. The L-CySH oxidation was a diffusion-controlled process. It showed a good linear relationship ranging from 1 mM to 10 mM. The sensor constructed by Au/XC-72 modified GCE with high electrocatalytic activity and small particle size has great potential in practical applications.
A colloidal gold solution was prepared by the methods of ethylene glycol reduction, ascorbic acid reduction, trisodium citrate reduction, and sodium borohydride reduction and supported on XC-72 substrate. Results of X-ray diffraction(XRD) showed that the catalyst prepared by the four methods contained obvious characteristic peak of Au. The Au/XC-72 diffraction peak prepared by sodium borohydride reduction method was the most gradual. Results of transmission electron microscopy(TEM) indicated that the Au NPs prepared by the sodium borohydride reduction method achieved a particle size of less than 5 nm and revealed a uniform distribution on the surface of XC-72. The Au NPs prepared by the other three methods presented larger particle size agglomeration. These catalysts(Au/XC-72) were modified on glassy carbon electrode(GCE) and used for electrochemical oxidation of L-cysteine(L-CySH). The results showed that the preparation of Au/XC-72 modified GCE by sodium borohydride reduction exihibited the best electrocatalytic activity of L-CySH in pH 2 PBS. The L-CySH oxidation was a diffusion-controlled process. It showed a good linear relationship ranging from 1 mM to 10 mM. The sensor constructed by Au/XC-72 modified GCE with high electrocatalytic activity and small particle size has great potential in practical applications.
引文
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[3]Zong W,Liu R,Zhao L,et al.Side-chain oxidative damage to cysteine on a glassy carbon electrode[J].Amino Acids,2009,37(4):559-564
[4]Ge S,Yan M,Lu J,et al.Electrochemical biosensor based on graphene oxide-Au nanoclusters composites for L-cysteine analysis[J].Biosensors&Bioelectronics,2012,31(1):49-54
[5]刘忠,杨文博,金永杰,等.5,5′-二硫硝基苯甲酸柱前衍生高效液相色谱法测定酶促反应液中的L-半胱氨酸[J].色谱,2004,22(3):231-233LIU Zhong,YANG Wen-bo,JIN Yong-jie,et al.Determination of L-cysteine in enzymatic reaction mixture with pre-column derivatization by high performance liquid chromatography[J].Chinese Journal of Chromatography,2004,22(3):231-233
[6]黄晓婉,王杉,揭琴丰,等.手性色谱法测定L-硒-甲基硒代半胱氨酸含量的研究[J].现代食品科技,2015,9:309-313HUANG Xiao-wan,WANG Shan,JIE Qin-feng,et al.Determination of L-se-methylselenocysteine content by chiral chromatography[J].Modern Food Science and Technology,2015,9:309-313
[7]Ye Y,Ji J,Pi F,et al.A novel electrochemical biosensor for antioxidant evaluation of phloretin based on cell-alginate/L-cysteine/gold nanoparticle-modified glassy carbon electrode[J].Biosensors&Bioelectronics,2018,119:119-125
[8]Zhang L,Wang Y,Wan K,et al.Effective sulfur-doping in carbon by high-temperature molten salt bath and its electrocatalysis for oxygen reduction reaction[J].Electrochemistry Communications,2018,86:53-56
[9]Jana N R,Gearheart L,Murphy C J.Seeding growth for size control of 5-40 nm diameter gold nanoparticles[J].Langmuir,2001,17(22):6782-6786
[10]Xu F,Wang F,Yang D,et al.Electrochemical sensing platform for L-Cy SH based on nearly uniform Au nanoparticles decorated graphene nanosheets[J].Materials Science&Engineering C-Materials for Biological Applications,2014,38:292-298
[11]Long G-F,Li X-H,Wan K,et al.Pt/CN-doped electrocatalysts:Superior electrocatalytic activity for methanol oxidation reaction and mechanistic insight into interfacial enhancement[J].Applied Catalysis B-Environmental,2017,203:541-548
[12]Harpeness R,Gedanken A.Microwave synthesis of core-shell gold/palladium bimetallic nanoparticles[J].Langmuir,2004,20(8):3431-3434
[13]Huanca D R,Salcedo W J.Physical and electrochemical characterization of crystalline silicon surfaces modified by aluminum[J].Physica Status Solidi a-Applications and Materials Science,2018,215(2):170543
[14]Li L-H,Zhang W-D.Preparation of carbon nanotubes supported platinum nanoparticles by an organic colloidal process for nonenzymatic glucose sensing[J].Microchimica Acta,2008,163(3-4):305-311
[15]杨玉新,叶阳,周有祥,等.四种化学还原法制备胶体金的比较研究[J].湖北农业科学,2011,50(3):476-478YANG Yu-xin,YE Yang,ZHOU You-xiang,et al.Comparative study on four chemical reduction methods for preparing colloidal gold[J].Hubei Agricultural Sciences,2011,50(3):476-478
[16]刘颖沙,李建科,张琳,等.胶体金制备技术的改进与优化[J].食品与发酵工业,2015,41(11):110-114LIU Ying-sha,LI Jian-ke,ZHANG Lin,et al.Improvement and optimization of preparation technology of colloidal gold[J].Food and Fermentation Industries,2015,41(11):110-114
[17]Wu L,Li J,Zhang H-M.One step fabrication of au nanoparticles-ni-al layered double hydroxide composite film for the determination of l-cysteine[J].Electroanalysis,2015,27(5):1195-1201