Stability of substituted phenyl groups electrochemically grafted at carbon electrode surface

被引:152
作者
D'Amours, M [1 ]
Bélanger, D [1 ]
机构
[1] Univ Quebec, Dept Chim, Montreal, PQ H3C 3P8, Canada
关键词
D O I
10.1021/jp027223r
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
The electrochemical reduction of an aryl diazonium tetrafluoroborate salt, dissolved in acetonitrile, at a carbon electrode surface allowed the grafting of aryl groups with the formation of a carbon-carbon bond. Groups such as 4-carboxyphenyl, 4-nitrophenyl, 4-diethylaniline (DEA), and 4-bromophenyl were grafted at a glassy carbon electrode surface. The stability of these grafted groups, present at the glassy carbon electrode surface, was studied at various electrode potentials in aqueous media. In appropriate experimental conditions, the as-grafted groups severely inhibit the cyclic voltammetry response of selected redox probes. Thus, the reappearance and/or increase of an electrochemical response, after polarization, was taken as an indication that a modification of the grafted layer occurred. Our results demonstrated that polarization at very positive (ca. 1.8 V) and negative (ca. -2 V) potentials is needed to observe an electrochemical response. Electrochemical impedance and X-ray photoelectron spectroscopies were also used to investigate the stability of the grafted layers. The impedance data usually tracks fairly well the cyclic voltammetry results, although the former appears to be more sensitive to changes that are occurring upon polarization of the modified electrode. Interestingly, the XPS data indicate clearly that the grafted layer is not always completely removed at the extreme positive and negative potentials investigated. A mechanism was proposed to explain the transformation occurring during polarization of the modified electrode and involves desorption of the substituted aryl groups during the concomitant hydrogen, oxygen, or chlorine evolution and finally leaving close to a covalently bonded monolayer of the grafted species at the electrode surface.
引用
收藏
页码:4811 / 4817
页数:7
相关论文
共 31 条
  • [1] Covalent modification of iron surfaces by electrochemical reduction of aryldiazonium salts
    Adenier, A
    Bernard, MC
    Chehimi, MM
    Cabet-Deliry, E
    Desbat, B
    Fagebaume, O
    Pinson, J
    Podvorica, F
    [J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2001, 123 (19) : 4541 - 4549
  • [2] Covalent modification of carbon surfaces by aryl radicals generated from the electrochemical reduction of diazonium salts
    Allongue, P
    Delamar, M
    Desbat, B
    Fagebaume, O
    Hitmi, R
    Pinson, J
    Saveant, JM
    [J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1997, 119 (01) : 201 - 207
  • [3] Derivatization of carbon surfaces by anodic oxidation of arylacetates. Electrochemical manipulation of the grafted films
    Andrieux, CP
    Gonzalez, F
    Saveant, JM
    [J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1997, 119 (18) : 4292 - 4300
  • [4] Baizer M., 1983, ORGANIC ELECTROCHEMI, V2nd
  • [5] Anodic oxidation of porous carbon
    Barton, SS
    Evans, MJB
    Halliop, E
    MacDonald, JAF
    [J]. LANGMUIR, 1997, 13 (05) : 1332 - 1336
  • [6] Electrochemical stability of self-assembled monolayers on gold
    Beulen, MWJ
    Kastenberg, MI
    van Veggel, FCJM
    Reinhoudt, DN
    [J]. LANGMUIR, 1998, 14 (26) : 7463 - 7467
  • [7] ACTIVATION OF GLASSY-CARBON ELECTRODE IN AQUEOUS AND NONAQUEOUS MEDIA
    BJELICA, LJ
    JOVANOVIC, LS
    [J]. ELECTROCHIMICA ACTA, 1992, 37 (02) : 371 - 372
  • [8] Stability of ω-functionalized self-assembled monolayers as a function of applied potential
    Boubour, E
    Lennox, RB
    [J]. LANGMUIR, 2000, 16 (19) : 7464 - 7470
  • [9] The electrochemical reduction of diazonium salts on iron electrodes.: The formation of covalently bonded organic layers and their effect on corrosion
    Chaussé, A
    Chehimi, MM
    Karsi, N
    Pinson, J
    Podvorica, F
    Vautrin-Ul, C
    [J]. CHEMISTRY OF MATERIALS, 2002, 14 (01) : 392 - 400
  • [10] COVALENT MODIFICATION OF CARBON SURFACES BY GRAFTING OF FUNCTIONALIZED ARYL RADICALS PRODUCED FROM ELECTROCHEMICAL REDUCTION OF DIAZONIUM SALTS
    DELAMAR, M
    HITMI, R
    PINSON, J
    SAVEANT, JM
    [J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1992, 114 (14) : 5883 - 5884