. (SERS),,. ( 1.2~ 0.9 V),

Transcript

1 200 B 2005, 35 (3): 200~205 * ** ** (, ;, ). (SERS),,. ( 1.2~ 0.9 V),,, N C2=N3 ; ( 0.8~ 0.7 V),, ; ( 0.6 V).,,.,. 1,., [1,2] ;,, [3,4] ;,,.,,,..,.,,, , * ( : , ) ** bren@xmu.edu.cn, ragu@suda.edu.cn SCIENCE IN CHINA Ser. B Chemistry

2 , (Raman) (IR) (SFG) [5~10]., (SERS),,. SERS,. SERS, [11~14]., [15] [16], SERS, SERS, SERS, SERS., (IMH) ( 1),, SERS (CV), (0.05 mol L 1 IMH mol L 1 NaClO 4 ) Dilor LabRam I, nm He-Ne. CHI 606B, XHD-. (SCE),.,. 2.2 (ORC) [17], SERS. 6 #, 3 µm, 0.3 µm Al 2 O 3,. 0.5 mol L 1 NaClO 4, 1.0 V 20 s,, 1.4 V 15 s, 1.2 V 20 s. ORC 1.0 V, 0.2 V s 1, 0.1 V s 1, 1.25 V , (0.1 mol L 1 KCl) (0.1 mol L 1 KCl mol L 1 IMH) (CV) ( 2). CV,, CV,,., V V.., ( 3),. (0.1 mol L 1 KCl), E 0 corr 0.83 V, I 0 corr A mol L 1 15 min,

3 202 B 35 V A, 85.5%,,.,, 15 min,,.,,,., SERS,. 2 1, 0.1 mol L 1 KCl; 2, 0.1 mol L 1 KCl mol L 1 IMH mol L 1 KCl 1, IMH; 2, 0.05 mol L 1 IMH 15 min; 3, 0.05 mol L 1 IMH 30 min E corr 0.76 V, I corr A,. : r = (I 0 corr I corr )/I 0 corr, 83.8%. 30 min, E corr I corr SERS, SERS.,, cm 1,. SERS, ( 1.2 V), ( 0.6 V), SERS.,, cm 1., 0.7 V,,, SERS 4.,. ph, : (neutral) (ylide) (cationic) (anionic). 4 N-H (1158 cm -1 ), : [12], N-H,., SCIENCE IN CHINA Ser. B Chemistry

4 3 203, 4, mol L 1 KCl mol L 1 IMH SERS,. 5 [20] : 1385 cm 1 C2=N3 C2-H, 1570 cm 1 N1-C2 C4-H, N1-H,,. SERS :. ( 1.2 V), 1385 cm 1, C2=N3 C2-H, N3 ( 5(a)),., 1385 cm 1, C2=N3 ( 5(b)). N1-C2 C4-H N1-H, N1-H, 1570 cm 1. [18] : N(N3), ; N(N1), ;. [19] :,,, ; N, N-Metal cm 1 N-H C-H [18], ; 270 cm 1 N-Co [12,19] ; (1142, 1489 cm 1 ) (1322 cm 1 ) [12,18] ;. SERS,.,, cm 1 : 5,,,. 0.7 V,, SERS ( 6),.,,,,. 6 (1168, cm 1 ) N1-H (δ N1-H +δ ring ), C2-H

5 204 B 35 (δ C2-H ), C2-H (δ C2-H +δ ring ) [21,22], (IMH) cm 1 [23].,,,. SERS 0.7 V, 0.7 V, SERS. 0.6 V,, 520 cm 1 ( 6)., 150~700 cm 1 (197, 485, 527, 619, 690 cm 1 ), CoO, Co(OH) 2, Co 3 O 4 [24].,,,. CV 0.6 V. 6 SERS 4 SERS, SERS.,., ;,. ( 1.2 V) 0.9 V,, N,, C2=N3 ; 0.8 ~ 0.7 V,,, ; ( 0.6 V),,.,,,. 1 Chia R W J, Edwards J, Geisler M, et al. Effect of disk roughness and carbon impact energy on corrosion protection of magnetic recording films. Tribol Inter, 2000, 33(5-6): 323~327 2 Kuk S T, Song Y S, Suh S, et al. The formation of LiCoO 2 on a NiO cathode for a molten carbonate fuel cell using electroplating. J Mater Chem, 2001, 11(2): 630~635 3 Tiernan M J, Fesenko E A, Barnes P A, et al. The application of CRTA and linear heating thermoanalytical techniques to the study of supported cobalt oxide methane combustion catalysts. Thermochim Acta, 2001, 379(1-2): 163~175 4 Shibanova M D, Golub'ev A V, Maksimov Y V, et al. Effect of thermal treatment on the structuring of an iron-cobalt-chromium oxide catalyst for the complete oxidation of fuel. Kinet Catal, 2001, 42(1): 112~116 5 Chen Y X, Miki A, Ye S, et al. Formate, an active intermediate for direct oxidation of methanol on Pt electrode. J Am Chem Soc, 2003, 125(13): 3680~ Yajima T, Uchida H, Watanabe M. In-situ ATR-FTIR spectroscopic study of electro-oxidation of methanol and adsorbed CO at Pt-Ru alloy. J Phys Chem B, 2004, 108(8): 2654~ Xue Q, Dai Q P, Jiang S G. Chemical reactions of imidazole with metallic silver studied by the use of SERS and XPS techniques. J Am Chem Soc, 1988, 110(8): 2393~ Musiani M M, Mengoli G, Fleischmann M, et al. An electrochemical and SERS investigation of the influence of ph on the effectiveness of some corrosion inhibitions of copper. J Electroanal Chem, 1987, 217(1): 187~202 SCIENCE IN CHINA Ser. B Chemistry

6 Chou K C, Markovic N M, Kim J. et al. An in situ time-dependent study of CO oxidation on Pt(111) in aqueous solution by voltammetry and sum frequency generation. J Phys Chem B, 2003, 107(8): 1840~ Wang J, Even M A, Chen X. et al. Detection of amide I signals of interfacial proteins in situ using SFG. J Am Chem Soc, 2003, 125(33): 9914~ Cao P G, Yao J L, Zheng J W, et al. Comparative study of inhibition effects of benzotriazole for metals in neutral solutions as observed with surface-enhanced Raman spectroscopy. Langmuir, 2002, 18(1): 100~ Wang G, Shi J, Yang H, et al. Surface-enhanced Raman scattering of imidazole adsorbed on an iron surface. J Raman Spectrosc, 2002, 33(2): 125~ Aramaki K, Fujioka E. Spectroscopic investigations on the inhibition mechanism of propargyl alcohol for iron corrosion in hydrochloric acid at elevated temperatures. Corrosion, 1997, 53(4): 319~ Cao P G, Yao J L, Ren B, et al. Surface-enhanced Raman scattering spectra of thiourea adsorbed at an iron electrode in NaClO 4 solution. J Phys Chem B, 2002, 106(39): 10150~ 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 Phys Chem B, 2002, 106(37): 9463~ Cao P G, Yao J L, Ren B, et al. Surface-enhanced Raman scattering from bare Fe electrode surface. Chem Phys Lett, 2000, 316(1-2): 1~ :, ~46 18 David A C, Jeanne E P. Surface-enhanced Raman scattering of the acid-base forms of imidazole on silver. Langmuir, 1992, 8(4): 1218~ Cao P G, Gu R A, Tian Z Q. Surface-enhanced Raman spectroscopy studies on the interaction of imidazole with a silver electrode in acetonitrile solution. J Phys Chem B, 2003, 107(3): 769~ Sadlej J, Jaworski A, Miaskiewicz K. A theoretical study of the vibrational spectra of imidazole and its different forms. J Mol Struct, 1992, 274: 247~ Salama S, Spiro T G. Resonance Raman spectra of cobalt( )-imidazole complexes: analogues of the binding site of cobalt-substituted zinc proteins. J Am Chem Soc, 1978, 100(4): 1105~ Caswell D S, Spiro T G. Ultraviolet resonance Raman spectroscopy of imidazole, histidine, and Cu(imidazole) 2+ 4 : implications for protein studies. J Am Chem Soc, 1986, 108(21): 6470~ Cornilsen B, Nakamoto K. Metal isotope effect on metal-ligand vibrations- imidazole complexes with Co( ), Ni( ), Cu( ), and Zn( ). J Inorg Nucl Chem, 1974, 36(11): 2467~ :, ~95