Abstract:Various roughening methods for the bare Ti electrode such as mechanical roughening, electrochemical oxidation-reduction method and chemical etching were tried to obtain surface-enhanced Raman spectra (SERS) successfully for the first time. The results of the experiments proved that mechanical roughening and electrochemical oxidation-reduction method could be successfully employed in roughening titanium electrode, however, surfaces roughened in such ways showed no SERS-activity in Raman detection. Finally, chemical etching with hydrofluoric acid was proved to be an effective way to get SERS-active titanium surface, and surface-enhanced Raman spectra of pyridine adsorbed on a titanium surface was observed for the first time. In order to get the most effective titanium surface, roughening conditions, including concentration of the acid, the time of etching and the external potential, were investigated. As illustrated, Raman activity varies with conditions changing in roughening processes and the most reasonable condition for roughening was indicated. The result showed that at the concentration of hydrofluoric acid 0.33% (Wt) and 5 min for etching, the most SERS-active rough titanium surface could be obtained. In addition, with an external potential to speed up corrosion, the surface of titanium electrode tended to form a thin film of oxide, which prevented further corrosion and caused SERS-activity decrease. Thus, in this paper, the surface-enhanced Raman spectra of pyridine (pyridine 0.01 mol·L-1, and electrolyte KCl 0.1 mol·L-1) adsorbed on bare roughed Ti electrode were observed at open circuit potential. Referring to the calculations of enhancement factor of pyridine on electrode, the enhancement factor is about 102 on the roughened titanium electrode.
秦 维,姚建林*, 顾仁敖*. 纯钛电极上的表面增强拉曼光谱研究[J]. 光谱学与光谱分析, 2009, 29(12): 3300-3303.
QIN Wei, YAO Jian-lin*, GU Ren-ao*. Studies of Surface-Enhanced Raman Spectroscopy on Bare Ti Electrode. SPECTROSCOPY AND SPECTRAL ANALYSIS, 2009, 29(12): 3300-3303.
[1] SHAO Juan(邵 娟). Rare Metals and Cemented Carbides(稀有金属与硬质合金), 2007, 35; 4. [2] TANG Yu-xin, TAO Jie, ZHANG Yan-yan, et al(汤育欣, 陶 杰, 张焱焱). Acta Physico-Chimica Sinica(物理化学学报), 2008, 24(12): 2191. [3] CHENG Xue-qun, LI Xiao-gang, DU Cui-wei(程学群, 李晓刚, 杜翠薇). Petro-Chemical Equipment(石油化工设备), 2008, 37: 5. [4] Lawrence K. Titanium Etching Solution, US, 4314876[P], 1982-02-09. [5] Moskovits M. Rev. Mod. Phys., 1985, 57(3): 783. [6] Otto A, Mrozek I, Grabhorn H, et al. J. Phys: Condensed Matter., 1992, 4: 1143. [7] Tian Z Q, Ren B, Mao B W. Journal of Phys. Chem. B., 1997, 101: 1338. [8] Ren B, Li X Q, She C X, et al. Electrochimica Acta, 2000, 46: 193. [9] Tian Z Q, Ren, B, Wu D Y. Journal of Phys. Chem. B, 2002, 106: 9463. [10] Vogel E, Meuer P, Kiefer W, et al. Journal of Molecular Structure, 1999, 482, 241. [11] Aletha M N, Richard L M. Anal. Chem., 2004, 76: 1089. [12] Wu D Y, Xie Y, Ren B- et al. Chem. Phys. Chem. Commun., 2001, 18: 1. [13] Huang Q J, Yao J L, Gu R A, et al. Chem. Phys. Lett., 1997, 271: 101. [14] Cai W B, Ren B, Li X Q, et al. Surf. Sci., 1998, 406(1-3): 9. [15] ZHAO Li-cheng, et al(赵力成, 等). Corrosion and Protection Technology(腐蚀科学与防护技术), 2007, 19(1): 27. [16] Kenichi T. Etching Method for Titanium or Titanium Alloy, JP, 2004043850[P]. 2004-02-12. [17] LIU Zheng, CUI Li, YANG Zhi-lin, et al(刘 郑, 崔 丽, 杨志林, 等). The Journal of Light Scattering(光散射学报), 2006, 18: 4. [18] GU Wei, CUI Yan, LIU Guo-kun, et al(顾 伟, 崔 颜, 刘国坤,等). Chemical Journal of Chinese Universities(高等学校化学学报), 2006, 27(11): 2132. [19] Ren Bin, Len Xu-feng, Tian Zhong-qun. Electrochemistry, 2001, 7: 1. [20] CAO Pei-gen, YAO Jian-lin, XU Hao-yuan, et al(曹佩根, 姚建林, 徐浩元,等). The Journal of Light Scattering(光散射学报), 2000, 12: 2. [21] YANG Chang-jiang, LIANG Cheng-hao, WANG Hua(杨长江, 梁成浩, 王 华). Corrosion Science And Protection Technology(腐蚀科学与防护技术), 2006, 18: 2.