Abstract
The electrooxidation of d- and l-glucose at chiral Pt{321}r/s single crystal electrodes modified with Au, Ag and Bi adatoms up to a coverage of one monolayer (ML) is reported. All adatoms investigated are found to selectively decorate kink and step sites. Only at higher coverages is adsorption onto the narrow {111} terrace sites observed for Bi, Ag and Au, consistent with previously reported adsorption behaviour on stepped surfaces vicinal to the {111} plane for chemisorbates exhibiting a lower work function than platinum. However, silver is found to block {111} terrace sites even when Pt step sites are still available on Pt{321}. This behaviour is ascribed to the propensity of silver to undergo place-exchange to form a surface alloy. The selective decoration of chiral kink sites has a profound influence on the voltammetric response of Pt{321} towards glucose electrooxidation. For bismuth adsorption, the electrooxidation current density initially increases and reaches a maximum when bismuth adsorption at {111} terraces commences. This is because the reaction pathways at step/kink sites leading to the formation of adsorbed CO (a surface poison for the clean surface reaction) and other strongly adsorbed intermediates, are either blocked by adsorbed bismuth or their electrooxidation and subsequent removal promoted. Once all step/kink sites are blocked by bismuth, hardly any chiral discrimination can be discerned between r-/s-electrodes towards d-/l-glucose. Silver adsorption does not cause any increase in glucose electrooxidation current density but rather induces a continual attenuation in glucose electrooxidation activity, particular (in contrast to bismuth) electrooxidation current at potentials in excess of 0.35 V. Therefore, unlike for bismuth, the initial glucose adsorption and electrooxidation processes associated with chiral kink sites appear to be preserved even though silver adsorbs at these sites. It is speculated that spontaneous place-exchange of silver with platinum to form a PtAg surface alloy at steps is responsible for this difference in behaviour between silver and bismuth. Finally, gold neither promotes reaction rate nor preserves chiral discrimination and is therefore deduced to act as an inert site blocker (no alloying, no promotion of CO electrooxidation) leading to complete attenuation of glucose electrooxidation current at a coverage of one ML.
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Naohara H, Ye S, Uosaki K (1999) J Electroanal Chem 473:2
Kibler LA, Kleinert M, Kolb DM (2000) Surf Sci 461:155
Kibler LA, Kleinert M, Lazarescu V, Kolb DM (2002) Surf Sci 498:175
Kibler LA, Kleinert M, Randler R, Kolb DM (1999) Surf Sci 443:19
Waibel H-F, Kleinert M, Kibler LA, Kolb DM (2002) Electrochim Acta 47:1461
Sung Y-E, Chrzanowski W, Wieckowski A, Zolfaghari A, Blais S, Jerkiewicz G (1998) Electrochim Acta 44:1019
Rhee CK, Wakisaka M, Tolmachev YV, Johnston CM, Haasch R, Attenkofer K, Lu GQ, You H, Wieckowski A (2003) J Electroanal Chem 554:367
Buller LJ, Herrero E, Gomez R, Feliu JM, Abruña HD (1996) J Chem Soc Faraday Trans 92:3757
Massong H, Tillmann S, Langkau T, Abd El Meguid EA, Baltruschat H (1998) J Electrochem Acta 44:1379
Maciá MD, Herrero E, Feliu JM (2002) Electrochim Acta 47:3653
Clavilier J, Feliu JM, Aldaz A (1988) J Electroanal Chem 243:419
Herrero E, Climent V, Feliu JM (2000) Electrochem Commun 2:636
Michaelson HB (1977) J Appl Phys 48:4729
Garcia-Araez N, Climent V, Feliu JM (2008) J Am Chem Soc 130:3824
Morgenstern M, Michely T, Comsa G (1996) Phys Rev Lett 77:703
Gutiérrez De Dios FJ, Gómez R, Feliu JM (2001) Electrochem Commun 3:659
Lei H-W, Hattori H, Kita H (1996) Electrochim Acta 41:1619
Yang Y-Y, Sun S-G, Gu Y-J, Zhou Z-Y, Zhen C-H (2001) Electrochim Acta 46:4339
Herrero E, Fernández-Vega A, Feliu JM, Aldaz A (1993) J Electroanal Chem 350:73
Janssen MMP, Moolhuysen J (1976) Electrochim Acta 21:861
Clavilier J, Llorca MJ, Feliu JM, Aldaz A (1991) J Electroanal Chem 310:429
Hazzazi OA, Attard GA, Wells PB (2004) J Mol Catal A Chem 216:247
Attard GA, Harris C, Herrero E, Feliu J (2002) Faraday Discuss 121:253
Watson DJ, Attard GA (2001) Electrochim Acta 46:3157
Attard GA (2001) J Phys Chem B 105:3158
Popovic KD, Tripkovic AV, Adzic RR (1992) J Electroanal Chem 339:227
Beden B, Largeaud F, Kokoh KB, Lamy C (1996) Electrochim Acta 41:701
Ahmadi A, Attard G, Feliu J, Rodes A (1999) Langmuir 15:2420
Kokkiniois G, Leger JM, Lamy C (1988) J Electroanal Chem 242:221
Rodes A, Llorca MJ, Feliu JM, Clavilier J (1996) Anal Quim Int Ed 92:118
Marinkovic NS, Popovic KD, Tripkovic AV, Markovic NM, Adzic RR (1992) Proc Electrochem Soc 92:353
Llorca MJ, Feliu JM, Aldaz A, Clavilier J, Rodes A (1991) J Electroanal Chem 316:175
Martins A, Ferreira V, Queiros A, Aroso I, Silva F, Feliu J (2003) Electrochem Commun 5:741
Pratt SJ, Jenkins SJ, King DA (2005) Surf Sci 585:L159
McFadden CF, Gremer PS, Gellman AJ (1996) Langmuir 12:2483
Sholl DS (1998) Langmuir 14:862
Attard GA, Ahmadi A, Feliu J, Rodes A, Herrero E, Blais S, Jerkiewicz G (1999) J Phys Chem B 103:1381
Clavilier J, Armand D, Sun SG, Petit M (1986) J Electroanal Chem 205:267
Rodes A, Zamakhchari MA, El Achi K, Clavilier J (1991) J Electroanal Chem 305:115
Al-Akl A, Attard G, Price R, Timothy B (2001) Phys Chem Chem Phys 3:3261
Morrison RT, Boyd RN (1973) Organic chemistry, 3rd edn. Allyn and Bacon, M. A., Boston, p 1095
Evans RW, Attard GA (1993) J Electroanal Chem 345:337
Domke KF, Xiao XY, Baltruschat H (2009) Electrochim Acta 54:4829
Hazzazi OA (2002) Doctoral Thesis, Cardiff University, UK
Attard GA, Al-Akl A (2003) J Electroanal Chem 554:439
Aberdam D, Salem C, Durand R, Faure R (1990) Surf Sci 239:71
Batzill M, Koel BE (2004) Surf Sci 553:50
Batzill M, Koel BE (2003) Europhys Lett 64:70
Tsay JS, Yao YD, Shern CS (1998) Phys Rev B 58:3609
Casalis L, Gunther S, Kovac J, Marsi M, Kiskinova M, Bifone A (1998) Chem Phys Lett 290:245
Tsay JS, Shern CS (1996) Chin J Phys 34:130
Vaskevich A, Rosenblum M, Gileadi E (1995) J Electroanal Chem 383:167
Hazzazi OA, Attard GA, Wells PB, Vidal-Iglesias FJ, Casadesus M (2009) J Electroanal Chem 625:123
Clavilier J, Orts JM, Gomez R, Feliu JM, Aldaz A (1996) J Electroanal Chem 404:281
Acknowledgment
The authors would like to thank the EPSRC for financial support. Omar A. Hazzazi expresses his thanks to the Saudi Arabian Government for financial support. GAA acknowledges the help of Sharon Huxter in the preparation of the figures.
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Hazzazi, O.A., Harris, C.A., Wells, P.B. et al. Electrooxidation of d- and l-Glucose at Well-Defined Chiral Bimetallic Electrodes. Top Catal 54, 1392–1402 (2011). https://doi.org/10.1007/s11244-011-9766-y
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DOI: https://doi.org/10.1007/s11244-011-9766-y