Abstract
In this manuscript, the potential of zero charge (pzc) of platinum single-crystal electrodes has been determined using the impinging jet system and recording the transient associated with the interphase formation. Initially, the Pt(111), Pt(110), and Pt(100) electrodes covered with CO were used. To demonstrate the validity of the procedure, the values obtained for the pzc of these electrodes were compared with those previously reported in the literature and also with those expected from work function changes. An excellent agreement has been found. After that, the values for the pzc of the stepped surfaces having (111) terraces and (110) steps were determined. For these surfaces, the pzc initially diminishes as the step density increases, in accordance with the expected diminution of the work function due to the Smoluchowski effect on the step site. However, for the shorter terraces, the pzc value increases with the step density, probably because of step dipole-dipole coupling due to the presence of a CO layer on the electrode.
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References
Frumkin AN (1955) Absorption phenomena and electrochemical kinetics. Z Elektrochem Angew Phys Chem 59:807–822
Briega-Martos V, Herrero E, Feliu JM (2019) Pt(hkl) surface charge and reactivity. Curr Opin Electrochem 17:97–105
Ledezma-Yanez I, Wallace WDZ, Sebastian-Pascual P et al (2017) Interfacial water reorganization as a pH-dependent descriptor of the hydrogen evolution rate on platinum electrodes. Nat Energy 2(4). https://doi.org/10.1038/nenergy.2017.31
Prieto A, Hernández J, Herrero E, Feliu JM (2003) The role of anions in oxygen reduction in neutral and basic media on gold single-crystal electrodes. J Solid State Electrochem 7(9):599–606. https://doi.org/10.1007/s10008-003-0362-3
Briega-Martos V, Herrero E, Feliu JMJM (2017) The inhibition of hydrogen peroxide reduction at low potentials on Pt(111): hydrogen adsorption or interfacial charge? Electrochem Commun 85:32–35. https://doi.org/10.1016/j.elecom.2017.10.016
Martínez-Hincapié R, Climent V, Feliu JM (2018) Peroxodisulfate reduction as a probe to interfacial charge. Electrochem Commun 88:43–46. https://doi.org/10.1016/j.elecom.2018.01.012
Martínez-Hincapié R, Climent V, Feliu JM (2019) Peroxodisulfate reduction on platinum stepped surfaces vicinal to the (110) and (100) poles. J Electroanal Chem 847:113226. https://doi.org/10.1016/J.JELECHEM.2019.113226
Briega-Martos V, Herrero E, Feliu JMJM (2017) Effect of pH and water structure on the oxygen reduction reaction on platinum electrodes. Electrochim Acta 241:497–509. https://doi.org/10.1016/j.electacta.2017.04.162
Frumkin AN, Petrii OA (1975) Potentials of zero total charge and zero free charge of platinum group metals. Electrochim Acta 20(5):347–359
Feliu JM, Orts JM, Gómez R, Aldaz A, Clavilier J (1994) New information on the unusual adsorption states of Pt(111) in sulphuric acid solutions from potentiostatic adsorbate replacement by CO. J Electroanal Chem 372(1-2):265–268
Climent V, Gómez R, Feliu JM (1999) Effect of increasing amount of steps on the potential of zero total charge of Pt(111) electrodes. Electrochim Acta 45(4-5):629–637
Rodes A, Gómez R, Feliu JM, Weaver MJ (2000) Sensitivity of compressed carbon monoxide adlayers on platinum(III) electrodes to long-range substrate structure: influence of monoatomic steps. Langmuir 16(2):811–816
Climent V, García-Araez N, Herrero E, Feliu J (2006) Potential of zero total charge of platinum single crystals: a local approach to stepped surfaces vicinal to Pt(111). Russ J Electrochem 42(11):1145–1160. https://doi.org/10.1134/S1023193506110012
Cuesta A (2004) Measurement of the surface charge density of CO-saturated Pt(111) electrodes as a function of potential: the potential of zero charge of Pt(111). Surf Sci 572(1):11–22
Rizo R, Sitta E, Herrero E, Climent V, Feliu JM (2015) Towards the understanding of the interfacial pH scale at Pt(111) electrodes. Electrochim Acta 162:138–145
Garcia-Araez N, Climent V, Herrero E, Feliu JM, Lipkowski J (2006) Thermodynamic approach to the double layer capacity of a Pt(1 1 1) electrode in perchloric acid solutions. Electrochim Acta 51(18):3787–3793. https://doi.org/10.1016/j.electacta.2005.10.043
Trasatti S (1971) Work function, electronegativity, and electrochemical behaviour of metals. II. Potentials of zero charge and “electrochemical” work functions. J Electroanal Chem 33(2):351–378. https://doi.org/10.1016/S0022-0728(71)80123-7
Gómez R, Climent V, Feliu JM, Weaver MJ (2000) Dependence of the potential of zero charge of stepped platinum (111) electrodes on the oriented step-edge density: electrochemical implications and comparison with work function behavior. J Phys Chem B 104(3):597–605
Weaver MJ (1998) Potentials of zero charge for platinum(111)-aqueous interfaces: a combined assessment from in-situ and ultrahigh-vacuum measurements. Langmuir 14(14):3932–3936. https://doi.org/10.1021/La9801054
Jakuszewski B, Kozlowski Z (1962) Determination of zero-charge potential by the immersion method. Rocz Chem 36:1873–1877
Błaszczyk T, Jakuszewski B, Czajkowski JM (1983) Zero charge potential of mercury in the mixtures of formamide and N-methylformamide with ethylene glycol. Electrochim Acta 28(5):675–679. https://doi.org/10.1016/0013-4686(83)85063-4
Hamm UW, Kramer D, Zhai RS, Kolb DM (1996) The pzc of Au(111) and Pt(111) in a perchloric acid solution: an ex situ approach to the immersion technique. J Electroanal Chem 414(1):85–89
Clavilier J, Armand D, Sun SG, Petit M (1986) Electrochemical adsorption behaviour of platinum stepped surfaces in sulphuric acid solutions. J Electroanal Chem 205(1-2):267–277
Herrero E, Orts JM, Aldaz A, Feliu JM (1999) Scanning tunneling microscopy and electrochemical study of the surface structure of Pt(10,10,9) and Pt(11,10,10) electrodes prepared under different cooling conditions. Surf Sci 440(1-2):259–270. https://doi.org/10.1016/S0039-6028(99)00813-4
Clavilier J (1980) The role of anion on the electrochemical behaviour of a {111} platinum surface; an unusual splitting of the voltammogram in the hydrogen region. J Electroanal Chem 107(1):211–216
Rodes A, Clavilier J, Orts JM et al (1992) Electrochemical behavior of platinum (100) in various acidic media. Part II. On the relation between the voltammetric profiles induced by anion specific adsorption studied with a transfer technique preserving surface cleanliness and structure. J Electroanal Chem 338:317–338
Gómez R, Clavilier J (1993) Electrochemical behaviour of platinum surfaces containing (110) sites and the problem of the third oxidation peak. J Electroanal Chem 354(1-2):189–208
Attard GA, Hunter K, Wright E, Sharman J, Martínez-Hincapié R, Feliu JM (2017) The voltammetry of surfaces vicinal to Pt{110}: structural complexity simplified by CO cooling. J Electroanal Chem 793:137–146. https://doi.org/10.1016/j.jelechem.2016.10.005
Nieuwenhuys BE, Sachtler WMH (1973) Crystal face specificity of nitrogen adsorption on a platinum field emission tip. Surf Sci 34(2):317–336. https://doi.org/10.1016/0039-6028(73)90121-0
Rotermund HH, Jakubith S, Kubala S, von Oertzen A, Ertl G (1990) Investigation of surfaces by scanning photoemission microscopy. J Electron Spectrosc Relat Phenom 52:811–819
Herrero E, Álvarez B, Feliu JM, Blais S, Radovic-Hrapovic Z, Jerkiewicz G (2004) Temperature dependence of the CO<inf>ads</inf> oxidation process on Pt(1 1 1), Pt(1 0 0), and Pt(1 1 0) electrodes. J Electroanal Chem 567(1):139–149. https://doi.org/10.1016/j.jelechem.2003.12.019
Angelucci CACA, Herrero E, Feliu JMJM (2010) Modeling CO oxidation on Pt(111) electrodes. J Phys Chem C 114(33):14154–14163. https://doi.org/10.1021/jp103597w
Attard GA, Souza-Garcia J, Martínez-Hincapié R, Feliu JM (2019) Nitrate anion reduction in aqueous perchloric acid as an electrochemical probe of Pt{1 1 0}-(1 × 1) terrace sites. J Catal 378:238–247. https://doi.org/10.1016/j.jcat.2019.09.002
Trasatti S (1995) Surface science and electrochemistry: concepts and problems. Surf Sci 335:1–9
Trasatti S (1990) The “absolute” electrode potential-the end of the story. Electrochim Acta 35(1):269–271. https://doi.org/10.1016/0013-4686(90)85069-Y
Lang B, Joyner RW, Somorjai GA (1972) Low energy electron diffraction studies of high index crystal surfaces of platinum. Surf Sci 30(2):440–453. https://doi.org/10.1016/0039-6028(72)90011-8
Lebedeva NP, Rodes A, Feliu JM, Koper MTM, van Santen RA (2002) Role of crystalline defects in electrocatalysis: CO adsorption and oxidation on stepped platinum electrodes as studied by in situ infrared spectroscopy. J Phys Chem B 106(38):9863–9872. https://doi.org/10.1021/jp0203806
Bergelin M, Herrero E, Feliu JMM, Wasberg M (1999) Oxidation of CO adlayers on Pt(111) at low potentials: an impinging jet study in H2SO4 electrolyte with mathematical modeling of the current transients. J Electroanal Chem 467(1-2):74–84. https://doi.org/10.1016/S0022-0728(99)00046-7
Lebedeva NP, Koper MTM, Feliu JM, van Santen RA (2002) Role of crystalline defects in electrocatalysis: mechanism and kinetics of CO adlayer oxidation on stepped platinum electrodes. J Phys Chem B 106(50):12938–12947. https://doi.org/10.1021/jp0204105
Smoluchowski R (1941) Anisotropy of the electronic work function of metals. Phys Rev 60(9):661–674. https://doi.org/10.1103/Physrev.60.661
Busó-Rogero C, Herrero E, Bandlow J, Comas-Vives A, Jacob T (2013) CO oxidation on stepped-Pt(111) under electrochemical conditions: insights from theory and experiment. Phys Chem Chem Phys 15(42):18671–18677. https://doi.org/10.1039/c3cp53282h
Ferre-Vilaplana A, Gisbert R, Herrero E (2014) On the electrochemical properties of platinum stepped surfaces vicinal to the (100) pole. A computational study. Electrochim Acta 125:666–673. https://doi.org/10.1016/j.electacta.2014.01.138
Gómez R, Feliu JM, Aldaz A, Weaver MJ (1998) Validity of double-layer charge-corrected voltammetry for assaying carbon monoxide coverages on ordered transition metals: comparisons with adlayer structures in electrochemical and ultrahigh vacuum environments. Surf Sci 410(1):48–61
Climent V, Feliu JM, Alkire RC, et al (2017) Surface electrochemistry with Pt single-crystal electrodes Nanopatterned and Nanoparticle-Modified Electrodes 17
Villegas I, Weaver MJ (1994) Carbon monoxide adlayer structures on platinum (111) electrodes: a synergy between in-situ scanning tunneling microscopy and infrared spectroscopy. J Chem Phys 101(2):1648–1660. https://doi.org/10.1063/1.467786
Kiskinova M, Szab A, Yates JT (1988) Compressed CO overlayers on Pt(111) — evidence for tilted CO species at high coverages by digital ESDIAD. Surf Sci 205(1-2):215–229. https://doi.org/10.1016/0039-6028(88)90173-2
Rhee CK, Feliu JM, Herrero E, Mrozek P, Wieckowski A (1993) Auger electron spectroscopy, low-energy electron diffraction, and electrochemistry of carbon monoxide on a Pt( 100) electrode. J Phys Chem 97(38):9730–9735
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This work has been financially supported by MINECO-FEDER (Spain) through project CTQ2016-76221-P.
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Boronat-González, A., Herrero, E. & Feliu, J.M. Determination of the potential of zero charge of Pt/CO electrodes using an impinging jet system. J Solid State Electrochem 24, 2871–2881 (2020). https://doi.org/10.1007/s10008-020-04654-7
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DOI: https://doi.org/10.1007/s10008-020-04654-7