Corresponding Author

Yun LING(lingyun@mnnu.edu.cn);
Jing TANG(jingtang@fzu.edu.cn)


P-nitrothiophenol (PNTP) is one of the most common probe molecules studied by surface-enhanced Raman spectroscopy (SERS). The research in electrochemical reduction behavior of PNTP will help understanding the mechanism for the nitrobenzene reduction. In this paper, we used transient electrochemical surface-enhanced Raman spectroscopy (TEC-SERS) to study the SERS of PNTP with cyclic voltammetry and chronoamperometry on gold electrodes. The results show that the TEC-SERS provide a time resolution that equals the transient electrochemical methods, and we concluded that the reaction was so quick that we did not observe the spectral information of intermediate species described in the literatures with a 5-ms temporal resolution. Such studies will assist a deep understanding in the electrochemical reduction of nitrobenzene.

Graphical Abstract


transient electrochemical surface-enhanced Raman spectroscopy, time-resolved electrochemical surface-enhanced Raman spectroscopy, cyclic voltammetry, chronoamperometry, p-nitrothiophenol

Publication Date


Online Available Date


Revised Date


Received Date



[1] Blaser, Hans U. A golden boost to an old reaction[J]. Science, 2006, 313(5785): 312-313.
[2] Corma A, Concepcion P, Serna P. A different reaction pathway for the reduction of aromatic nitro compounds on gold catalysts[J]. Angewandte Chemie International Edition, 2007, 46(38): 7266-7269.
[3] Corma A, Serna P. Chemoselective hydrogenation of nitro compounds with supported gold catalysts[J]. Science, 2006, 313(5785): 332-334.
[4] Gao P, Gosztola D, Weaver M J. Surface-enhanced raman-spectroscopy as a probe of electroorganic reaction pathways.1.processes involving adsorbed nitrobenzene, azoben-
zene, and related species[J]. Journal of Physical Chemistry, 1988, 92(25): 7122-7130.
[5] Shi C T, Wei Z, Birke R L, et al. Detection of short-lived intermediates in electrochemical reactions using time-resolved surface-enhanced Raman-spectroscopy[J]. Journal of Physical Chemistry, 1990, 94(12): 4766-4769.
[6] Shi C T, Zhang W, Birke R L, et al. Time-resolved SERS, cyclic voltammetry, and digital-simulation of the electroreduction of para-nitrobenzoic acid[J]. Journal of Physical Chemistry, 1991, 95(16): 6276-6285.
[7] Sun S C, Birke R L, Lombardi J R, et al. Photolysis of para-nitrobenzoic acid on roughened silver surfaces[J].Journal of Physical Chemistry, 1988, 92(21): 5965-5972.
[8] Haber F. About gradual reduction of the nitrobenzene with limited cathode potential. Z[J]. Elecktrochem, 1898, 4: 506-513.
[9] Haber F, Schmidt C. On the reduction procedure in the electrical reduction of nitrobenzol[J]. Zeitschrift fur phy-sikalische chemie--stochiometrie und verwandtschaftslehre, 1900, 32(2): 271-287.
[10] Zhao L B, Chen J L, Zhang M, et al. Theoretical study on electroreduction of p-nitrothiophenol on silver and gold electrode surfaces[J]. Journal of Physical Chemistry C, 2015, 119(9): 4949-4958.
[11] Medard C, Morin M. Chemisorption of aromatic thiols onto a glassy carbon surface[J]. Journal of Electroanalytical Chemistry, 2009, 632(1/2): 120-126.
[12] Nielsen J U, Esplandiu M J, Kolb D M. 4-nitrothiophenol SAM on Au(111) investigated by in situ STM, electrochemistry, and XPS[J]. Langmuir, 2001, 17(11): 3454-3459.
[13] Tsutsumi H, Furumoto S, Morita M, et al. Electrochemical-behavior of a 4-nitrothiophenol modified electrode prepared by the self-assembly method[J]. Journal of Colloid and Interface Science, 1995, 171(2): 505-511.
[14] Futamata M. Application of attenuated total reflection surface-plasmon-polariton Raman spectroscopy to gold and copper[J]. Applied Optics, 1997, 36(1): 364-375.
[15] Futamata M. Surface-plasmon-polariton-enhanced raman-
scattering from self-assembled monolayers of p-nitrothiophenol and p-aminothiophenol on silver[J]. Journal of Physical Chemistry, 1995, 99(31): 11901-11908.
[16] Matsuda N, Sawaguchi T, Osawa M, et al. Surface-assisted photoinduced reduction of p-nitrothiophenol self-assembled monolayer adsorbed on a smooth silver electrode[J]. Chemistry Letters, 1995, 24(2): 145-146.
[17] Matsuda N, Yoshii K, Ataka K, et al. Surface-enhanced infrared and raman studies of electrochemical reduction of self-assembled monolayers formed from para-nitrohiophenol at silver[J]. Chemistry Letters, 1992, 21(7): 1385-1388.
[18] Kim K, Lee S J, Kim K L. Surface-enhanced Raman scattering of 4-nitrothioanisole in Ag sol[J]. Journal of Physical Chemistry B, 2004, 108(41): 16208-16212.
[19] Zhu T, Yu H Z, Wang Y C, et al. Irreversible adsorption and reduction of p-nitrothio-phenol monolayers on gold: Electrochemical in situ surface enhanced Raman spectroscopy[J]. Molecular Crystals and Liquid Crystals Science and Technology Section A - Molecular Crystals and Liquid Crystals, 1999, 337(1): 241-244.
[20] Futamata M, Nishihara C, Goutev N. Electrochemical reduction of p-nitrothiophenol-self-assembled monolayer films on Au(111) surface and coadsorption of anions and water molecules[J]. Surface Science, 2002, 514(1/3): 241-248.
[21] Zong C, Chen C J, Zhang M, et al. Transient electrochemical surface-enhanced raman spectroscopy: A millisecond time-resolved study of an electrochemical redox process[J]. Journal of the American Chemical Society, 2015, 137(36): 11768-11774.
[22] Hartman T, Wondergem C S, Kumar N, et al. Surface- and tip-enhanced raman spectroscopy in catalysis[J]. Journal of Physical Chemistry Letters, 2016, 7(8): 1570-1584.
[23] Lin T W, Tasi T T, Chang P L, et al. Reversible association of nitro compounds with p-nitrothiophenol modified on Ag nanoparticles/graphene oxide nanocomposites through plasmon mediated photochemical reaction[J]. ACS Applied Materials & Interfaces, 2016, 8(12): 8315-8322.
[24] Kang L L, Han X J, Chu J Y, et al. In situ surface-enhanced raman spectroscopy study of plasmon-driven catalytic reactions of 4-nitrothiophenol under a controlled atmosphere[J]. ChemCatChem, 2015, 7(6): 1004-1010.
[25] Kang L, Xu P, Zhang B, et al. Laser wavelength- and power-dependent plasmon-driven chemical reactions monitored using single particle surface enhanced Raman spectroscopy[J]. Chemical Communications, 2013, 49(33): 3389-3391.
[26] Ling Y, Xie W C, Liu G K, et al. The discovery of the hydrogen bond from p-nitrothiophenol by Raman spectroscopy: Guideline for the thioalcohol molecule recognition tool[J]. Scientific Reports, 2016, 6: 31981.
[27] Ling Y, Xie W C, Wang W L, et al. Direct observation of 4-nitrophenyl disulfide produced from p-nitrothiophenol in air by Raman spectroscopy[J]. Journal of Raman Spectroscopy, 2018, 49(3): 520-525.
[28] Wu Y F(吴元菲), Pang R(庞然), Zhang M(张檬), et al. Theoretical study of photoelectrochemical reactions and EC-SERS on SPR metallic electrodes of silver and gold[J]. Journal of Electrochemistry(电化学), 2016, 22(4): 356-367.
[29] Zhao L B, Zhang M, Huang Y F, et al. Theoretical study of plasmon-enhanced surface catalytic coupling reactions of aromatic amines and nitro compounds[J]. Journal of Physical Chemistry Letters, 2014, 5(7): 1259-1266.
[30] Zhang Z L, Deckert-Gaudig T, Singh P, et al. Single molecule level plasmonic catalysis - a dilution study of p-nitrothiophenol on gold dimers[J]. Chemical Communications, 2015, 51(15): 3069-3072.



To view the content in your browser, please download Adobe Reader or, alternately,
you may Download the file to your hard drive.

NOTE: The latest versions of Adobe Reader do not support viewing PDF files within Firefox on Mac OS and if you are using a modern (Intel) Mac, there is no official plugin for viewing PDF files within the browser window.