欢迎访问《电化学(中英文)》期刊官方网站,今天是
论文

纳米结构金电极上对氨基苯硫酚的电化学反应过程研究

  • 彭辉远 ,
  • 王家正 ,
  • 刘佳 ,
  • 于欢欢 ,
  • 林建德 ,
  • 吴德印 ,
  • 田中群
展开
  • 厦门大学化学化工学院,固体表面物理化学国家重点实验室,福建 厦门 361005

收稿日期: 2021-06-28

  修回日期: 2021-07-15

  网络出版日期: 2021-08-05

基金资助

国家自然科学基金项目(22032004);国家自然科学基金项目(21533066);国家自然科学基金项目(21773197)

Investigation on Electrochemical Processes of p-Aminothiophenol on Gold Electrode of Nanostructures

  • Hui-Yuan Peng ,
  • Jia-Zheng Wang ,
  • Jia Liu ,
  • Huan-Huan Yu ,
  • Jian-De Lin ,
  • De-Yin Wu ,
  • Zhong-Qun Tian
Expand
  • State Key Laboratory of Physical Chemistry of Solid Surfaces, Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, Fujian, China

Received date: 2021-06-28

  Revised date: 2021-07-15

  Online published: 2021-08-05

摘要

本文研究了金电极上吸附对氨基苯硫酚(PATP)的电化学行为。在0.05 mol·L-1的硫酸溶液(pH = 1)中,从循环伏安图中可观察到PATP的不可逆电氧化峰。基于吸附PATP电化学氧化为4′-巯基-N-苯基醌二亚胺(NPQD)的反应机理,计算了电极表面PATP的覆盖度, 并在低激光功率下通过电化学表面增强拉曼光谱进行了氧化产物表征。通过电化学线性扫描伏安法及理论模拟计算,确定了PATP电化学氧化的动力学参数,即表观反应速率常数k及传递系数α,确定了生成阳离子自由基的步骤为速率控制步骤。

本文引用格式

彭辉远 , 王家正 , 刘佳 , 于欢欢 , 林建德 , 吴德印 , 田中群 . 纳米结构金电极上对氨基苯硫酚的电化学反应过程研究[J]. 电化学, 2022 , 28(4) : 2106281 . DOI: 10.13208/j.electrochem.210628

Abstract

Electrochemical reactions on nanostructured noble electrodes have received much attention, however, the reaction mechanism and reaction kinetics are still difficult to be studied. Probe molecule can give an insight to the investigation of electrochemical reactions on noble electrodes with nanostructures. In this paper, the electrochemical process of p-aminothiophenol (PATP) adsorbed on the gold electrode was studied by electrochemical cyclic voltammetry and surface-enhanced Raman spectroscopy (SERS). Here, we used one-step sodium citrate reduction method (Frens method) to synthesize gold nanoparticles, which are used to construct the nanostructured gold electrode. The Raman electrolytic cell used was based on the traditional three-electrode electrolytic cell. The gold electrode was used as the working electrode (WE), the saturated calomel electrode (SCE) as the reference electrode (RE), and the platinum wire (Pt) as the counter electrode (CE). After the careful pretreatment of the gold electrode surface, the cell was assembled and placed on the platform of the XploRa instrument to get started. With the assistance of potentiostat, the SERS spectra at different potentials were acquired and combined together, a so-call electrochemical surface-enhanced Raman spectroscopic (EC-SERS) experiment. In a 0.05 mol·L-1 sulfuric acid solution (pH = 1), an irreversible oxidation peak was found in the cyclic voltammogram, which is considered to correspond to the oxidation of the PATP molecule. The oxidation mechanism is proposed by combination of previous work in literature, and it is pointed out that the PATP molecule was initially transformed into cationic radical. Then, this cationic radical coupled with the PATP molecule to an intermediate NPQDH2 , and finally electrochemically oxidized to 4'-mercapto-N-phenylquinone diamine (NPQD). On the basis of this mechanism, the surface coverage of PATP on the electrode surface was calculated and the coverage value was found to be larger at the nanostructured electrode due to the modification of gold nanoparticles than that of general gold electrodes. In the following, the electrochemical oxidation product was characterized by the EC-SERS spectra. Finally, we experimentally and theoretically studied the electrochemical oxidation kinetics of PATP on the gold nanoparticle-modified gold electrode (Au NPs@Au). The apparent reaction rate constant k and transfer coefficient α of PATP were calculated by electrochemical linear sweeping voltammetry and theoretical simulation, respectively, finding that the cationic radical formation step is the rate-limiting step. We believe that this work will no doubt stimulate the basic research of PATP on gold electrodes consisting of nanostructures and provide a guide to electrochemical kinetic research in other metal-adsorbate systems.

参考文献

[1] Bryant M A, Joa S L, Pemberton J E. Raman-scattering from monolayer films of thiophenol and 4-mercaptopyridine at Pt surfaces[J]. Langmuir, 1992, 8(3): 753-756.
[2] Diem T, Czajka B, Weber B, Regen S L. Spontaneous assembly of phospholipid monolayers via adsorption onto gold[J]. J. Am. Chem. Soc., 1986, 108(19): 6094-6095.
[3] Finklea H O, Avery S, Lynch M, Furtsch T. Blocking oriented monolayers of alkyl mercaptans on gold electrodes[J]. Langmuir, 1987, 3(3): 409-413.
[4] Hubbard A T. Electrochemistry at well-characterized surfaces[J]. Chem. Rev., 1988, 88(4): 633-656.
[5] Nuzzo R G, Zegarski B R, Dubois L H. Fundamental-studies of the chemisorption of organosulfur compounds on Au(111)- Implications for molecular self-assembly on gold surfaces[J]. J. Am. Chem. Soc., 1987, 109(3): 733-740.
[6] Porter M D, Bright T B, Allara D L, Chidsey C E D. Spontaneously organized molecular assemblies. 4. Structural characterization of normal-alkyl thiol monolayers on gold by optical ellipsometry, infrared-spectroscopy, and electrochemistry[J]. J. Am. Chem. Soc., 1987, 109(12): 3559-3568.
[7] Campion A, Kambhampati P. Surface-enhanced Raman scattering[J]. Chem. Soc. Rev., 1998, 27(4): 241-250.
[8] Kneipp K, Wang Y, Kneipp H, Perelman L T, Itzkan I, Dasari R, Feld M S. Single molecule detection using surface-enhanced Raman scattering (SERS)[J]. Phys. Rev. Lett., 1997, 78(9): 1667-1670.
[9] Li J F, Huang Y F, Ding Y, Yang Z L, Li S B, Zhou X S, Fan F R, Zhang W, Zhou Z Y, Wu D Y, Ren B, Wang Z L, Tian Z Q. Shell-isolated nanoparticle-enhanced Raman spectroscopy[J]. Nature, 2010, 464(7287): 392-395.
[10] Otto A, Mrozek I, Grabhorn H, Akemann W. Surface-enhanced Raman-scattering[J]. J. Phys. Condens. Matter., 1992, 4(5): 1143-1212.
[11] Schlucker S. Surface-enhanced Raman spectroscopy: Concepts and chemical applications[J]. Angew. Chem. Int. Ed., 2014, 53(19): 4756-4795.
[12] Tian Z Q, Ren B, Wu D Y. Surface-enhanced Raman scattering: From noble to transition metals and from rough surfaces to ordered nanostructures[J]. J. Phys. Chem. B., 2002, 106(37): 9463-9483.
[13] Huang Y F, Wu D Y, Zhu H P, Zhao L B, Liu G K, Ren B, Tian Z Q. Surface-enhanced Raman spectroscopic study of p-aminothiophenol[J]. Phys. Chem. Chem. Phys., 2012, 14(24): 8485-8497.
[14] Hutchison J A, Centeno S P, Odaka H, Fukumura H, Hofkens J, Uji-I H. Subdiffraction limited, remote excitation of surface enhanced Raman scattering[J]. Nano Lett., 2009, 9(3): 995-1001.
[15] Villarreal E, Li G F G, Zhang Q F, Fu X Q, Wang H. Nanoscale surface curvature effects on ligand-nanoparticle interactions: A plasmon-enhanced spectroscopic study of thiolated ligand adsorption, desorption, and exchange on gold nanoparticles[J]. Nano Lett., 2017, 17(7): 4443-4452.
[16] Ward D R, Halas N J, Ciszek J W, Tour J M, Wu Y, Nordlander P, Natelson D. Simultaneous measurements of electronic conduction and Raman response in molecular junctions[J]. Nano Lett., 2008, 8(3): 919-924.
[17] Wu D Y, Zhang M, Zhao L B, Huang Y F, Ren B, Tian Z Q. Surface plasmon-enhanced photochemical reactions on noble metal nanostructures[J]. Sci. China Chem., 2015, 58(4): 574-585.
[18] Huang Y F, Zhang M, Zhao L B, Feng J M, Wu D Y, Ren B, Tian Z Q. Activation of oxygen on gold and silver nanoparticles assisted by surface plasmon resonances[J]. Angew. Chem. Int. Ed., 2014, 53(9): 2353-2357.
[19] Jiang R, Zhang M, Qian S L, Yan F, Pei L Q, Jin S, Zhao L B, Wu D Y, Tian Z Q. Photoinduced surface catalytic coupling reactions of aminothiophenol derivatives investigated by SERS and DFT[J]. J. Phys. Chem. C., 2016, 120(30): 16427-16436.
[20] Wu D Y, Zhao L B, Liu X M, Huang R, Huang Y F, Ren B, Tian Z Q. Photon-driven charge transfer and photocatalysis of p-aminothiophenol in metal nanogaps: a DFT study of SERS[J]. Chem. Commun., 2011, 47(9): 2520-2522.
[21] Zhan C, Wang Z Y, Zhang X G, Chen X J, Huang Y F, Hu S, Li J F, Wu D Y, Moskovits M, Tian Z Q. Interfacial construction of plasmonic nanostructures for the utilization of the plasmon-excited electrons and holes[J]. J. Am. Chem. Soc., 2019, 141(20): 8053-8057.
[22] Patrito E M, Cometto F P, Paredes-Olivera P. Quantum mechanical investigation of thiourea adsorption on Ag(111) considering electric field and solvent effects[J]. J. Phys. Chem. B., 2004, 108(40): 15755-15769.
[23] Lukkari J, Kleemola K, Meretoja M, Ollonqvist T, Kankare J. Electrochemical post-self-assembly transformation of 4-aminothiophenol monolayers on gold electrodes[J]. Langmuir, 1998, 14(7): 1705-1715.
[24] Raj C R, Kitamura F, Ohsaka T. Electrochemical and in situ FTIR spectroscopic investigation on the electrochemical transformation of 4-aminothiophenol on a gold electrode in neutral solution[J]. Langmuir, 2001, 17(23): 7378-7386.
[25] Wu D Y, Li J F, Ren B, Tian Z Q. Electrochemical surface-enhanced Raman spectroscopy of nanostructures[J]. Chem. Soc. Rev., 2008, 37(5): 1025-1041.
[26] Ling Y(凌云), Tang J(汤儆), Liu G K(刘国坤), Zong C(宗铖). Transient electrochemical surface-enhanced Raman spectroscopic study in electrochemical reduction of p-nitrothiophenol[J]. J. Electrochem.(电化学), 2019, 25(6): 731-739.
[27] Yuan Y X(袁亚仙), Yang F Z(杨凤珠), Liu W(刘伟), Wei P J(韦萍洁), Yao J L(姚建林), Gu R A(顾仁敖). Electrochemical SERS studies on the adsorption of benzoimidazole and derivative in nonaqueous solution[J]. J. Electrochem.(电化学), 2010, 16(3): 343-349.
[28] Frens G. Controlled nucleation for the regulation of the particle size in monodisperse gold suspensions[J]. Nat. Phys. Sci., 1973, 241(105): 20-22.
[29] Carvalhal R T, Freire R S, Kubota L T. Polycrystalline gold electrodes: A comparative study of pretreatment procedures used for cleaning and thiol self-assembly monolayer formation[J]. Electroanalysis, 2005, 17(14): 1251-1259.
[30] Sun R(孙如), Li S J(李淑瑾), Yao J L(姚建林), Gu R A(顾仁敖). Surface enhanced Raman spectroscopy and theoretical studies on the electrochemical transformation processes of 4-aminothiophenol on Au electrode[J]. Acta Chim. Sinica.(化学学报), 2007, 65(17): 1741-1745.
[31] Zhang P(张普), Wei Y(卫怡), Cai J(蔡俊), Chen Y X(陈艳霞), Tian Z Q(田中群). Nonlinear Stark effect observed for carbon monoxide chemisorbed on gold core/palladium shell nanoparticle film electrodes, using in situ surface-enhanced Raman spectroscopy[J]. Chin. J. Catal.(催化学报), 2016, 37(7): 1156-1165.
[32] Laviron E. General expression of the linear potential sweep voltammogram in the case of diffusionless electrochemical systems[J]. J. Electroanal. Chem., 1979, 101(1): 19-28.
[33] Andrieux C P, Legorande A, Saveant J M. Electron-Transfer and bond breaking - Examples of passage from a sequential to a concerted mechanism in the electrochemical reductive cleavage of Arylmethyl halides[J]. J. Am. Chem. Soc., 1992, 114(17): 6892-6904.
文章导航

/