Tools and Electrochemical In Situ and On-Line Characterization Techniques for Nanomaterials

  • Têko W. Napporn
  • Laetitia Dubau
  • Claudia Morais
  • Mariana R. Camilo
  • Julien Durst
  • Fabio H. B. Lima
  • Frédéric Maillard
  • K. Boniface Kokoh
Chapter

Abstract

In the last century, progress in electrochemistry and electrocatalysis was very spectacular due to the remarkable evolution in surface science, chemistry, and physics. Electrochemical study of perfect smooth or bulk materials was the usual way to understand the interaction between the surfaces of such materials with their close environment. Therefore, any modification of the surface structure or composition provides change in the material behavior and the nature of the adsorbed species or near. Usually, the modification of smooth surface consists in the increase of its roughness factor through the deposition of sublayer or layer of metal particles. The deposition can be done on a well-defined surface (model electrode with a known crystallographic structure) [1]. Then, surface modification becomes a way of creating new active sites to enhance the reactivity of molecules. The development of nanoscale materials has changed the approach of studying and identifying active sites in heterogeneous catalysis, and particularly in electrocatalysis. Indeed, electrocatalysis uses the surface of a material, which is submitted to an electrode potential, as the reaction site. Therefore, the material structure, morphology and its composition are the key parameters to control the electrochemical process [2]. The nature of the active site depends on these parameters. Furthermore, the assessment of the nature of the active site before, during, and after the electrocatalytic reaction becomes a huge challenge. Thereby, electrochemical tools like cyclic voltammetry, underpotential deposition of a monolayer of a species [3–5], the specific adsorption of species or molecule, and CO stripping [6] were the first approaches. It is the basic measurement of the electrons flow through the surface per unit of time during the reaction at the surface. Therefore, the electric current per area unit represents the charge transfer reaction that occurs at a metal-solution interface. Since the middle of the last century, an increase in the development of several in situ spectroscopic techniques was observed due to the need of understanding the structure of the interface between electrodes and solutions. Indeed, coupling the electrochemistry measurements to other techniques such as Fourier Transform Infrared Spectroscopy (FTIRS), X-Ray Diffraction (XRD) [7, 8], Transmission Electron Microscopy (TEM) [9], Scanning Tunneling Microscopy (STM) [10], Surface-Enhanced Raman Scattering (SERS) [11] becomes a suitable approach to assess in real time at the electrified interface electrode-solution; some relevant data on electrocatalysts structure, morphology, composition, and stability of materials; and on the reaction intermediates and products. The identification of the surface state in addition to that of adsorbed species, intermediates, and products of the reaction process have permitted to determine a mechanistic pathway which is essential for enhancing the material performance and selectivity. It appears obvious that the identification of surface state of a nanomaterial under realistic electrochemical reaction conditions represents a noble scientific breakthrough. In the present chapter, for the first time some techniques coupled with electrochemistry able to characterize nanomaterials as electrodes will be extensively addressed. This chapter will also show the progress in in situ electrochemical approaches. One motivated approach is to be able to characterize electrochemically and experimentally the surface of the nanoparticle. Therefore, in the first part of the chapter, an example of a pure electrochemical tool, which permits to probe the nanoelectrocatalyst surface, is discussed. Although the progress in nanotechnology increases rapidly, various tools have been developed in electrochemistry for understanding the reaction pathway, intermediates, and products formation.

Notes

Acknowledgments

T.W. Napporn (IC2MP) thanks Region Poitou Charentes for its financial support for investigating Electrocatalysis of gold nanoparticles. L. Dubau, J. Durst, and F. Maillard (LEPMI) thank Dr. Jean-Louis Hazemann, Dr. Olivier Proux, and all the members of the FAME team for their kind help to the realization of the EXAFS measurements on the beamline BM30B of the European Synchrotron Radiation Facility. F.H.B. Lima and M.R. Camilo (IQSC) acknowledge financial support from FAPESP (Fundação de Amparo à Pesquisa do Estado de São Paulo – Sao Paulo Research Foundation), grants 2016/13323-0, 2013/16930-7, and 2014/26699-3, and CNPq (Conselho Nacional de Desenvolvimento Científico e Tecnológico), grant 306469/2016-2.

References

  1. 1.
    Wadayama T, Todoroki N, Yamada Y, Sugawara T et al (2010) Oxygen reduction reaction activities of Ni/Pt(111) model catalysts fabricated by molecular beam epitaxy. Electrochem Commun 12(8):1112–1115Google Scholar
  2. 2.
    Kang Y, Yang P, Markovic NM, Stamenkovic VR (2016) Shaping electrocatalysis through tailored nanomaterials. Nano Today 11(5):587–600Google Scholar
  3. 3.
    Coutanceau C, Urchaga P, Brimaud S, Baranton S (2012) Colloidal syntheses of shape- and size-controlled Pt nanoparticles for electrocatalysis. Electrocatalysis 3(2):75–87Google Scholar
  4. 4.
    Hernandez J, Solla-Gullon J, Herrero E, Feliu JM et al (2009) In situ surface characterization and oxygen reduction reaction on shape-controlled gold nanoparticles. J Nanosci Nanotechnol 9(4):2256–2273Google Scholar
  5. 5.
    Hebié S, Cornu L, Napporn TW, Rousseau J et al (2013) Insight on the surface structure effect of free gold nanorods on glucose electrooxidation. J Phys Chem C 117(19):9872–9880Google Scholar
  6. 6.
    Urchaga P, Baranton S, Coutanceau C, Jerkiewicz G (2012) Evidence of an eley-rideal mechanism in the stripping of a saturation layer of chemisorbed CO on platinum nanoparticles. Langmuir 28(36):13094–13104Google Scholar
  7. 7.
    Sibert E, Wang L, De Santis M, Soldo-Olivier Y (2014) Mechanisms of the initial steps in the Pd electro-deposition onto Au(111). Electrochim Acta 135(594–603Google Scholar
  8. 8.
    Oliveira VL, Sibert E, Soldo-Olivier Y, Ticianelli EA et al (2016) Borohydride electrooxidation reaction on Pt(111) and Pt(111) modified by a pseudomorphic Pd monolayer. Electrochim Acta 190:790–796Google Scholar
  9. 9.
    Lopez-Haro M, Guétaz L, Printemps T, Morin A et al (2014) Three-dimensional analysis of Nafion layers in fuel cell electrodes. Nat Commun 5:5229. 1–6Google Scholar
  10. 10.
    Wakisaka M, Asizawa S, Yoneyama T, Uchida H et al (2010) In situ STM observation of the CO Adlayer on a Pt(110) electrode in 0.1 M HClO4 solution. Langmuir 26(12):9191–9194Google Scholar
  11. 11.
    Li D, Jia SJ, Fodjo EK, Xu H et al (2016) In situ SERS and X-ray photoelectron spectroscopy studies on the pH-dependant adsorption of anthraquinone-2-carboxylic acid on silver electrode. Appl Surf Sci 367:153–159Google Scholar
  12. 12.
    Sánchez-Sánchez CM, Vidal-Iglesias FJ, Solla-Gullón J, Montiel V et al (2010) Scanning electrochemical microscopy for studying electrocatalysis on shape-controlled gold nanoparticles and nanorods. Electrochim Acta 55(27):8252–8257Google Scholar
  13. 13.
    Urchaga P, Baranton S, Coutanceau C (2013) Changes in COchem oxidative stripping activity induced by reconstruction of Pt (111) and (100) surface nanodomains. Electrochim Acta 92(438–445Google Scholar
  14. 14.
    Hebié S, Napporn TW, Morais C, Kokoh KB (2016) Size-dependent Electrocatalytic activity of free gold nanoparticles for the glucose oxidation reaction. ChemPhysChem 17(10):1454–1462Google Scholar
  15. 15.
    Hamelin A (1996) Cyclic voltammetry at gold single-crystal surfaces. Part 1. Behaviour at low-index faces. J Electroanal Chem 407(1–2):1–11Google Scholar
  16. 16.
    Hebié S, Kokoh KB, Servat K, Napporn T (2013) Shape-dependent electrocatalytic activity of free gold nanoparticles toward glucose oxidation. Gold Bull 46(4):311–318Google Scholar
  17. 17.
    Maillard F, Savinova ER, Stimming U (2007) CO monolayer oxidation on Pt nanoparticles: further insights into the particle size effects. J Electroanal Chem 599(2):221–232Google Scholar
  18. 18.
    Mayrhofer KJJ, Arenz M, Blizanac BB, Stamenkovic V et al (2005) CO surface electrochemistry on Pt-nanoparticles: a selective review. Electrochim Acta 50(25):5144–5154Google Scholar
  19. 19.
    Urchaga P, Baranton S, Coutanceau C, Jerkiewicz G (2012) Electro-oxidation of COchem on Pt Nanosurfaces: solution of the peak multiplicity puzzle. Langmuir 28(7):3658–3663Google Scholar
  20. 20.
    Wang ZL, Mohamed MB, Link S, El-Sayed MA (1999) Crystallographic facets and shapes of gold nanorods of different aspect ratios. Surf Sci 440(1–2):L809–L814Google Scholar
  21. 21.
    Tollan C, Echeberria J, Marcilla R, Pomposo J et al (2009) One-step growth of gold nanorods using a β-diketone reducing agent. J Nanopart Res 11(5):1241–1245Google Scholar
  22. 22.
    Coutanceau C, Urchaga P, Baranton S (2012) Diffusion of adsorbed CO on platinum (100) and (111) oriented nanosurfaces. Electrochem Commun 22(109–112Google Scholar
  23. 23.
    Ferreira PJ, La O’ GJ, Shao-Horn Y, Morgan D et al (2005) Instability of Pt/C electrocatalysts in proton exchange membrane fuel cells. J Electrochem Soc 152(11):A2256–A2271Google Scholar
  24. 24.
    Gasteiger HA, Kocha SS, Sompalli B, Wagner FT (2005) Activity benchmarks and requirements for Pt, Pt-alloy, and non-Pt oxygen reduction catalysts for PEMFCs. Appl Catal B Environ 56(1–2):9–35Google Scholar
  25. 25.
    Sompalli B, Litteer BA, Gu W, Gasteiger HA (2007) Membrane degradation at catalyst layer edges in PEMFC MEAs. J Electrochem Soc 154(12):B1349–B1357Google Scholar
  26. 26.
    Chen S, Gasteiger HA, Hayakawa K, Tada T et al (2010) Platinum-alloy cathode catalyst degradation in proton exchange membrane fuel cells: nanometer-scale compositional and morphological changes. J Electrochem Soc 157(1):A82–A97Google Scholar
  27. 27.
    Xie J, Wood DL, More KL, Atanassov P et al (2005) Microstructural changes of membrane electrode assemblies during PEFC durability testing at high humidity conditions. J Electrochem Soc 152(5):A1011–A1020Google Scholar
  28. 28.
    Borup R, Meyers J, Pivovar B, Kim YS et al (2007) Scientific aspects of polymer electrolyte fuel cell durability and degradation. Chem Rev 107(10):3904–3951Google Scholar
  29. 29.
    Guilminot E, Corcella A, Charlot F, Maillard F et al (2007) Detection of Ptz+ ions and Pt nanoparticles inside the membrane of a used PEMFC. J Electrochem Soc 154(1):B96–B105Google Scholar
  30. 30.
    Guilminot E, Corcella A, Iojoiu C, Berthomé G et al (2007) Membrane and active layer degradation upon proton exchange membrane fuel cell steady-state operation – Part I: platinum dissolution and redistribution within the membrane electrode assembly. J Electrochem Soc 154(11):B1106–B1114Google Scholar
  31. 31.
    Iojoiu C, Guilminot E, Maillard F, Chatenet M et al (2007) Membrane and active layer degradation following PEMFC steady-state operation. J Electrochem Soc 154(11):B1115–B1120Google Scholar
  32. 32.
    Chatenet M, Guétaz L, Maillard F (2009) Electron microscopy to study MEA materials and structure degradation. In: Vielstich W, Gasteiger HA, Yokokawa H (eds) Handbook of fuel cells: fundamentals, technology, and applications, vol 5. Wiley, Oxford, pp 844–860Google Scholar
  33. 33.
    Dubau L, Maillard F, Chatenet M, André J et al (2010) Nanoscale compositional changes and modification of the surface reactivity of Pt3Co/C nanoparticles during proton-exchange membrane fuel cell operation. Electrochim Acta 56(2):776–783Google Scholar
  34. 34.
    Dubau L, Maillard F, Chatenet M, Guétaz L et al (2010) Durability of Pt3Co/C cathodes in a 16 cell PEMFC stack: macro/microstructural changes and degradation mechanisms. J Electrochem Soc 157(12):B1887–B1895Google Scholar
  35. 35.
    Dubau L, Durst J, Maillard F, Guétaz L et al (2011) Further insights into the durability of Pt3Co/C electrocatalysts: formation of “hollow” Pt nanoparticles induced by the Kirkendall effect. Electrochim Acta 56(28):10658–10667Google Scholar
  36. 36.
    Dubau L, Lopez-Haro M, Castanheira L, Durst J et al (2013) Probing the structure, the composition and the ORR activity of Pt3Co/C nanocrystallites during a 3422 h PEMFC ageing test. Appl Catal B Environ 142:801–808Google Scholar
  37. 37.
    Durst J, Lamibrac A, Charlot F, Dillet J et al (2013) Degradation heterogeneities induced by repetitive start/stop events in proton exchange membrane fuel cell: inlet vs. outlet and channel vs. land. Appl Catal B Environ 138–139:416–426Google Scholar
  38. 38.
    Lopez-Haro M, Dubau L, Guétaz L, Bayle-Guillemaud P et al (2014) Atomic-scale structure and composition of Pt3Co/C nanocrystallites during real PEMFC operation: a STEM–EELS study. Appl Catal B Environ 152–153:300–308Google Scholar
  39. 39.
    Shao-Horn Y, Sheng W, Chen S, Ferreira P et al (2007) Instability of supported platinum nanoparticles in low-temperature fuel cells. Top Catal 46(3):285–305Google Scholar
  40. 40.
    Dubau L, Durst J, Maillard F, Chatenet M et al (2012) Heterogeneities of aging within a PEMFC MEA. Fuel Cells 12(2):188–198Google Scholar
  41. 41.
    Lamibrac A, Maranzana G, Dillet J, Lottin O et al (2012) Local degradations resulting from repeated start-ups and shut-downs in proton exchange membrane fuel cell (PEMFC). Energy Procedia 29:318–324Google Scholar
  42. 42.
    Nikkuni FR, Vion-Dury B, Dubau L, Maillard F et al (2014) The role of water in the degradation of Pt3Co/C nanoparticles: an identical location transmission electron microscopy study in polymer electrolyte environment. Appl Catal B Environ 156–157:301–306Google Scholar
  43. 43.
    Nikkuni FR, Dubau L, Ticianelli EA, Chatenet M (2015) Accelerated degradation of Pt3Co/C and Pt/C electrocatalysts studied by identical-location transmission electron microscopy in polymer electrolyte environment. Appl Catal B Environ 176–177:486–499Google Scholar
  44. 44.
    Mayrhofer KJJ, Meier JC, Ashton SJ, Wiberg GKH et al (2008) Fuel cell catalyst degradation on the nanoscale. Electrochem Commun 10(8):1144–1147Google Scholar
  45. 45.
    Meier JC, Galeano C, Katsounaros I, Witte J et al (2014) Design criteria for stable Pt/C fuel cell catalysts. Beilstein J Nanotechnol 5(1):44–67Google Scholar
  46. 46.
    Dubau L, Castanheira L, Berthomé G, Maillard F (2013) An identical-location transmission electron microscopy study on the degradation of Pt/C nanoparticles under oxidizing, reducing and neutral atmosphere. Electrochim Acta 110:273–281Google Scholar
  47. 47.
    Hartl K, Hanzlik M, Arenz M (2011) IL-TEM investigations on the degradation mechanism of Pt/C electrocatalysts with different carbon supports. Energy Environ Sci 4(1):234–238Google Scholar
  48. 48.
    Zana A, Speder J, Roefzaad M, Altmann L et al (2013) Probing degradation by IL-TEM: the influence of stress test conditions on the degradation mechanism. J Electrochem Soc 160(6):F608–F615Google Scholar
  49. 49.
    Dubau L, Maillard F (2016) Unveiling the crucial role of temperature on the stability of oxygen reduction reaction electrocatalysts. Electrochem Commun 63:65–69Google Scholar
  50. 50.
    Castanheira L, Dubau L, Maillard F (2014) Accelerated stress tests of Pt/HSAC electrocatalysts: an identical-location transmission electron microscopy study on the influence of intermediate characterizations. Electrocatalysis 5(2):125–135Google Scholar
  51. 51.
    Yu YC, Xin HLL, Hovden R, Wang DL et al (2012) Three-dimensional tracking and visualization of hundreds of Pt-Co fuel cell nanocatalysts during electrochemical aging. Nano Lett 12(9):4417–4423Google Scholar
  52. 52.
    Baldizzone C, Gan L, Hodnik N, Keeley GP et al (2015) Stability of dealloyed porous Pt/Ni nanoparticles. ACS Catal 5(9):5000–5007Google Scholar
  53. 53.
    Meier JC, Galeano C, Katsounaros I, Topalov AA et al (2012) Degradation mechanisms of Pt/C fuel cell catalysts under simulated start-stop conditions. ACS Catal 2(5):832–843Google Scholar
  54. 54.
    Mucal. http://csrri.iit.edu/periodic-table.html. Accessed 14 Feb 2017
  55. 55.
    Russell AE, Rose A (2004) X-ray absorption spectroscopy of low temperature fuel cell catalysts. Chem Rev Columbus 104(10):4613–4636Google Scholar
  56. 56.
    Siebel A, Gorlin Y, Durst J, Proux O et al (2016) Identification of catalyst structure during the hydrogen oxidation reaction in an operating PEM fuel cell. ACS Catal 6(11):7326–7334Google Scholar
  57. 57.
    Croze V, Ettingshausen F, Melke J, Soehn M et al (2010) The use of in situ X-ray absorption spectroscopy in applied fuel cell research. J Appl Electrochem 40(5):877–883Google Scholar
  58. 58.
    Wandt J, Freiberg A, Thomas R, Gorlin Y et al (2016) Transition metal dissolution and deposition in Li-ion batteries investigated by operando X-ray absorption spectroscopy. J Mater Chem A 4(47):18300–18305Google Scholar
  59. 59.
    Adora S, Soldo-Olivier Y, Faure R, Durand R et al (2001) Electrochemical preparation of platinum nanocrystallites on activated carbon studied by X-ray absorption spectroscopy. J Phys Chem B 105(43):10489–10495Google Scholar
  60. 60.
    Mukerjee S, McBreen J (1998) Effect of particle size on the electrocatalysis by carbon-supported Pt electrocatalysts: an in situ XAS investigation. J Electroanal Chem 448(2):163–171Google Scholar
  61. 61.
    Murthi VS, Urian RC, Mukerjee S (2004) Oxygen reduction kinetics in low and medium temperature acid environment: correlation of water activation and surface properties in supported Pt and Pt alloy electrocatalysts. J Phys Chem B 108(30):11011–11023Google Scholar
  62. 62.
    Teliska M, Murthi VS, Mukerjee S, Ramaker DE (2007) Site-specific vs specific adsorption of anions on Pt and Pt-based alloys. J Phys Chem C 111(26):9267–9274Google Scholar
  63. 63.
    Dixon D, Habereder A, Farmand M, Kaserer S et al (2012) Space resolved, in operando X-ray absorption spectroscopy: investigations on both the anode and cathode in a direct methanol fuel cell. J Phys Chem C 116(13):7587–7595Google Scholar
  64. 64.
    Melke J, Schoekel A, Dixon D, Cremers C et al (2010) Ethanol oxidation on carbon-supported Pt, PtRu, and PtSn catalysts studied by operando X-ray absorption spectroscopy. J Phys Chem C 114(13):5914–5925Google Scholar
  65. 65.
    Markovic NM, Schmidt TJ, Stamenkovic V, Ross PN (2001) Oxygen reduction reaction on Pt and Pt bimetallic surfaces: a selective review. Fuel Cells 1(2):105–116Google Scholar
  66. 66.
    Wang JX, Markovic NM, Adzic RR (2004) Kinetic analysis of oxygen reduction on Pt(111) in acid solutions: intrinsic kinetic parameters and anion adsorption effects. J Phys Chem B 108:4127–4133Google Scholar
  67. 67.
    Stamenkovic VR, Mun BS, Arenz M, Mayrhofer KJJ et al (2007) Trends in electrocatalysis on extended and nanoscale Pt-bimetallic alloy surfaces. Nat Mater 6(3):241–247Google Scholar
  68. 68.
    Jia Q, Caldwell K, Strickland K, Ziegelbauer JM et al (2015) Improved oxygen reduction activity and durability of dealloyed PtCox catalysts for proton exchange membrane fuel cells: strain, ligand, and particle size effects. ACS Catal 5(1):176–186Google Scholar
  69. 69.
    Pourbaix M (1979) Atlas of electrochemical equilibria in aqueous solutions. National Association of Corrosion Engineers, Houston, p 453Google Scholar
  70. 70.
    Jia Q, Li J, Caldwell K, Ramaker DE et al (2016) Circumventing metal dissolution induced degradation of Pt-alloy catalysts in proton exchange membrane fuel cells: revealing the asymmetric volcano nature of redox catalysis. ACS Catal 6(2):928–938Google Scholar
  71. 71.
    Durst J, Lopez-Haro M, Dubau L, Chatenet M et al (2014) Reversibility of Pt-skin and Pt-skeleton nanostructures in acidic media. J Phys Chem Lett 5(3):434–439Google Scholar
  72. 72.
    Maillard F, Dubau L, Durst J, Chatenet M et al (2010) Durability of Pt3Co/C nanoparticles in a proton-exchange membrane fuel cell: direct evidence of bulk co segregation to the surface. Electrochem Commun 12(9):1161–1164Google Scholar
  73. 73.
    Mukerjee S, Srinivasan S, Soriaga MP, McBreen J (1995) Role of structural and electronic-properties of Pt and Pt alloys on electrocatalysis of oxygen reduction – an in-situ XANES and EXAFS investigation. J Electrochem Soc 142(5):1409–1422Google Scholar
  74. 74.
    Teliska M, O’Grady WE, Ramaker DE (2004) Determination of H adsorption sites on Pt/C electrodes in HClO4 from Pt L23 X-ray absorption spectroscopy. J Phys Chem B 108(7):2333–2344Google Scholar
  75. 75.
    Teliska M, O’Grady WE, Ramaker DE (2005) Determination of O and OH adsorption sites and coverage in situ on Pt electrodes from Pt L23 X-ray absorption spectroscopy. J Phys Chem B 109(16):8076–8084Google Scholar
  76. 76.
    Bard AJ, Faulkner LR (1993) Electrochemical methods. Wiley, WeinheimGoogle Scholar
  77. 77.
    Bewick A, Kunimatsu K (1980) Infra red spectroscopy of the electrode-electrolyte interphase. Surf Sci 101(1–3):131–138Google Scholar
  78. 78.
    Bewick A, Kunimatsu K, Pons BS (1980) Infrared-spectroscopy of the electrode-electrolyte interphase. Electrochim Acta 25(4):465–468Google Scholar
  79. 79.
    Beden B, Bewick A, Lamy C (1983) A comparative-study of formic-acid adsorption on a platinum-electrode by both electrochemical and emirs techniques. J Electroanal Chem 150(1–2):505–511Google Scholar
  80. 80.
    Bewick A, Kunimatsu K, Pons BS, Russell JW (1984) Electrochemically modulated infrared-spectroscopy (emirs)-experimental details. J Electroanal Chem 160(1–2):47–61Google Scholar
  81. 81.
    Beden B, Bewick A, Lamy C (1983) A study by electrochemically modulated infrared reflectance spectroscopy of the electrosorption of formic-acid at a platinum-electrode. J Electroanal Chem 148(1):147–160Google Scholar
  82. 82.
    Leung LWH, Weaver MJ (1988) Real-time ftir spectroscopy as a quantitative kinetic probe of competing electrooxidation pathways for small organic-molecules. J Phys Chem 92(14):4019–4022Google Scholar
  83. 83.
    Corrigan DS, Weaver MJ (1988) Mechanisms of formic-acid, methanol, and carbon-monoxide electrooxidation at platinum as examined by single potential alteration infrared-spectroscopy. J Electroanal Chem 241(1–2):143–162Google Scholar
  84. 84.
    Davidson T, Pons BS, Bewick A, Schmidt PP (1981) Vibrational spectroscopy of the electrode-electrolyte interface – use of fourier-transform infrared-spectroscopy. J Electroanal Chem 125(1):237–241Google Scholar
  85. 85.
    Pons S, Davidson T, Bewick A (1984) Vibrational spectroscopy of the electrode electrolyte interface .4. Fourier-transform infrared-spectroscopy – experimental considerations. J Electroanal Chem 160(1–2):63–71Google Scholar
  86. 86.
    Pons S, Davidson T, Bewick A (1983) Vibrational spectroscopy of the electrode solution interphase .2. Use of fourier-transform spectroscopy for recording infrared-spectra of radical ion intermediates. J Am Chem Soc 105(7):1802–1805Google Scholar
  87. 87.
    Pons S (1983) The use of fourier-transform infrared-spectroscopy for insitu recording of species in the electrode electrolyte solution interphase. J Electroanal Chem 150(1–2):495–504Google Scholar
  88. 88.
    Lin WF, Sun SG (1996) In situ FTIRS investigations of surface processes of Rh electrode – novel observation of geminal adsorbates of carbon monoxide on Rh electrode in acid solution. Electrochim Acta 41(6):803–809Google Scholar
  89. 89.
    Pons S, Davidson T, Bewick A (1982) Vibrational spectroscopy of the electrode solution interface .3. Use of fourier-transform spectroscopy for observing double-layer reorganization. J Electroanal Chem 140(1):211–216Google Scholar
  90. 90.
    Li JT, Zhou ZY, Broadwell I, Sun SG (2012) In-situ infrared spectroscopic studies of electrochemical energy conversion and storage. Acc Chem Res 45(4):485–494Google Scholar
  91. 91.
    Iwasita T, Nart FC (1990) Bulk effects in external reflection ir spectroscopy- the interpretation of adsorption data for ionic species. J Electroanal Chem 295(1–2):215–224Google Scholar
  92. 92.
    Iwasita T, Nart FC (1997) In situ infrared spectroscopy at electrochemical interfaces. Prog Surf Sci 55(4):271–340Google Scholar
  93. 93.
    Bae IT, Scherson DA, Yeager EB (1990) Infrared spectroscopic determination of ph changes in diffusionally decoupled thin-layer electrochemical-cells. Anal Chem 62(1):45–49Google Scholar
  94. 94.
    Bae IT, Xing XK, Yeager EB, Scherson D (1989) Ionic transport effects in insitu fourier-transform infrared reflection absorption-spectroscopy. Anal Chem 61(10):1164–1167Google Scholar
  95. 95.
    Osawa M (1997) Dynamic processes in electrochemical reactions studied by surface-enhanced infrared absorption spectroscopy (SEIRAS). Bull Chem Soc Jpn 70(12):2861–2880Google Scholar
  96. 96.
    Miki A, Ye S, Osawa M (2002) Surface-enhanced IR absorption on platinum nanoparticles: an application to real-time monitoring of electrocatalytic reactions. Chem Commun 0(14):1500–1501Google Scholar
  97. 97.
    Golden WG, Kunimatsu K, Seki H (1984) Application of polarization-modulated fourier-transform infrared reflection absorption-spectroscopy to the study of carbon-monoxide adsorption and oxidation on a smooth platinum-electrode. J Phys Chem 88(7):1275–1277Google Scholar
  98. 98.
    Golden WG, Saperstein DD, Severson MW, Overend J (1984) Infrared reflection absorption-spectroscopy of surface species – a comparison of fourier-transform and dispersion methods. J Phys Chem 88(3):574–580Google Scholar
  99. 99.
    Golden WG, Dunn DS, Overend J (1981) A method for measuring infrared reflection-absorption spectra of molecules adsorbed on low-area surfaces at monolayer and submonolayer concentrations. J Catal 71(2):395–404Google Scholar
  100. 100.
    Kunimatsu K, Kita H (1987) Infrared spectroscopic study of methanol and formic-acid adsorbates on a platinum-electrode .2. Role of the linear co(a) derived from methanol and formic-acid in the electrocatalytic oxidation of ch3oh and hcooh. J Electroanal Chem 218(1–2):155–172Google Scholar
  101. 101.
    Christensen P, Hamnett A (2000) In-situ techniques in electrochemistry – ellipsometry and FTIR. Electrochim Acta 45(15–16):2443–2459Google Scholar
  102. 102.
    Osawa M, Yoshii K (1997) In situ and real-time surface-enhanced infrared study of electrochemical reactions. Appl Spectrosc 51(4):512–518Google Scholar
  103. 103.
    Osawa M, Yoshii K, Ataka K, Yotsuyanagi T (1994) Real-time monitoring of electrochemical dynamics by submillisecond time-resolved surface-enhanced infrared attenuated-total-reflection spectroscopy. Langmuir 10(3):640–642Google Scholar
  104. 104.
    Noda H, Wan LJ, Osawa M (2001) Dynamics of adsorption and phase formation of p-nitrobenzoic acid at Au(111) surface in solution: a combined surface-enhanced infrared and STM study. Phys Chem Chem Phys 3(16):3336–3342Google Scholar
  105. 105.
    Wandlowski T, Ataka K, Pronkin S, Diesing D (2004) Surface enhanced infrared spectroscopy – Au(1 1 1-20 nm)/sulphuric acid – new aspects and challenges. Electrochim Acta 49(8):1233–1247Google Scholar
  106. 106.
    Nichols RJ, Bewick A (1988) Sniftirs with a flow cell – the identification of the reaction intermediates in methanol oxidation at pt anodes. Electrochim Acta 33(11):1691–1694Google Scholar
  107. 107.
    Roth JD, Weaver MJ (1991) The electrooxidation of carbon-monoxide on platinum as examined by surface infrared-spectroscopy under forced hydrodynamic conditions. J Electroanal Chem 307(1–2):119–137Google Scholar
  108. 108.
    Bellec V, De Backer MG, Levillain E, Sauvage FX et al (2001) In situ time-resolved FTIR spectroelectrochemistry: study of the reduction of TCNQ. Electrochem Commun 3(9):483–488Google Scholar
  109. 109.
    Sun SG, Lin Y (1994) Kinetic aspects of oxidation of isopropanol on pt electrodes investigated by in-situ time-resolved ftir spectroscopy. J Electroanal Chem 375(1–2):401–404Google Scholar
  110. 110.
    Zhou ZY, Lin SC, Chen SP, Sun SG (2005) In situ step-scan time-resolved microscope FTIR spectroscopy working with a thin-layer cell. Electrochem Commun 7(5):490–495Google Scholar
  111. 111.
    Kunimatsu K, Yoda T, Tryk DA, Uchida H et al (2010) In situ ATR-FTIR study of oxygen reduction at the Pt/Nafion interface. Phys Chem Chem Phys 12(3):621–629Google Scholar
  112. 112.
    Xia XH, Liess HD, Iwasita T (1997) Early stages in the oxidation of ethanol at low index single crystal platinum electrodes. J Electroanal Chem 437(1–2):233–240Google Scholar
  113. 113.
    Tian N, Zhou ZY, Yu NF, Wang LY et al (2010) Direct electrodeposition of Tetrahexahedral Pd nanocrystals with high-index facets and high catalytic activity for ethanol electrooxidation. J Am Chem Soc 132(22):7580Google Scholar
  114. 114.
    Tian N, Zhou ZY, Sun SG, Ding Y et al (2007) Synthesis of tetrahexahedral platinum nanocrystals with high-index facets and high electro-oxidation activity. Science 316(5825):732–735Google Scholar
  115. 115.
    Zhou ZY, Huang ZZ, Chen DJ, Wang Q et al (2010) High-index faceted platinum nanocrystals supported on carbon black as highly efficient catalysts for ethanol Electrooxidation. Angew Chem Int Ed 49(2):411–414Google Scholar
  116. 116.
    Silva LC, Maia G, Passos RR, de Souza EA et al (2013) Analysis of the selectivity of PtRh/C and PtRhSn/C to the formation of CO2 during ethanol electrooxidation. Electrochim Acta 112:612–619Google Scholar
  117. 117.
    Soares LA, Morais C, Napporn TW, Kokoh KB et al (2016) Beneficial effects of rhodium and tin oxide on carbon supported platinum catalysts for ethanol electrooxidation. J Power Sources 315:47–55Google Scholar
  118. 118.
    Almeida TS, Palma LM, Morais C, Kokoh KB et al (2013) Effect of adding a third metal to carbon-supported PtSn-based Nanocatalysts for direct ethanol fuel cell in acidic medium. J Electrochem Soc 160(9):F965–F971Google Scholar
  119. 119.
    Yang YY, Ren J, Li QX, Zhou ZY et al (2014) Electrocatalysis of ethanol on a Pd electrode in alkaline media: an in situ attenuated total reflection surface-enhanced infrared absorption spectroscopy study. ACS Catal 4(3):798–803Google Scholar
  120. 120.
    Beyhan S, Uosaki K, Feliu JM, Herrero E (2013) Electrochemical and in situ FTIR studies of ethanol adsorption and oxidation on gold single crystal electrodes in alkaline. J Electroanal Chem 707:89–94Google Scholar
  121. 121.
    Pech-Rodriguez WJ, Gonzalez-Quijano D, Vargas-Gutierrez G, Morais C et al (2017) Electrochemical and in situ FTIR study of the ethanol oxidation reaction on PtMo/C nanomaterials in alkaline media. Appl Catal B Environ 203:654–662Google Scholar
  122. 122.
    Buso-Rogero C, Brimaud S, Solla-Gullon J, Vidal-Iglesias FJ et al (2016) Ethanol oxidation on shape-controlled platinum nanoparticles at different pHs: a combined in situ IR spectroscopy and online mass spectrometry study. J Electroanal Chem 763:116–124Google Scholar
  123. 123.
    Delpeuch AB, Maillard F, Chatenet M, Soudant P et al (2016) Ethanol oxidation reaction (EOR) investigation on Pt/C, Rh/C, and Pt-based bi- and tri-metallic electrocatalysts: a DEMS and in situ FTIR study. Appl Catal B Environ 181:672–680Google Scholar
  124. 124.
    Zhou ZY, Wang QA, Lin JL, Tian N et al (2010) In situ FTIR spectroscopic studies of electrooxidation of ethanol on Pd electrode in alkaline media. Electrochim Acta 55(27):7995–7999Google Scholar
  125. 125.
    Ren J, Yang YY, Zhang BW, Tian N et al (2013) H-D kinetic isotope effects of alcohol electrooxidation on Au, Pd and Pt electrodes in alkaline solutions. Electrochem Commun 37:49–52Google Scholar
  126. 126.
    Allen JB, Faulkner LR (2001) Electrochemical methods: fundamuntals and applications, 2nd edn. Wiley, New York, p 850Google Scholar
  127. 127.
    Scholz F (2010) Electroanalytical methods: guide to experiments and applications. Springer, Berlin/Heidelberg, p 388Google Scholar
  128. 128.
    Kwon Y, Schouten KJP, Koper MTM (2011) Mechanism of the catalytic oxidation of glycerol on polycrystalline gold and platinum electrodes. ChemCatChem 3(7):1176–1185Google Scholar
  129. 129.
    Kwon Y, Koper MTM (2010) Combining voltammetry with HPLC: application to electro-oxidation of glycerol. Anal Chem 82(13):5420–5424Google Scholar
  130. 130.
    Gomes J, Tremiliosi-Filho G (2011) Spectroscopic studies of the glycerol electro-oxidation on polycrystalline au and Pt surfaces in acidic and alkaline media. Electrocatalysis 2(2):96–105Google Scholar
  131. 131.
    Jeffery DZ, Camara GA (2010) The formation of carbon dioxide during glycerol electrooxidation in alkaline media: first spectroscopic evidences. Electrochem Commun 12(8):1129–1132Google Scholar
  132. 132.
    Kwon Y, Birdja Y, Spanos I, Rodriguez P et al (2012) Highly selective electro-oxidation of glycerol to dihydroxyacetone on platinum in the presence of bismuth. ACS Catal 2(5):759–764Google Scholar
  133. 133.
    Simões M, Baranton S, Coutanceau C (2011) Enhancement of catalytic properties for glycerol electrooxidation on Pt and Pd nanoparticles induced by Bi surface modification. Appl Catal B Environ 110:40–49Google Scholar
  134. 134.
    Simões M, Baranton S, Coutanceau C (2012) Electrochemical valorisation of glycerol. ChemSusChem 5(11):2106–2124Google Scholar
  135. 135.
    Fernández PS, Martins ME, Camara GA (2012) New insights about the electro-oxidation of glycerol on platinum nanoparticles supported on multi-walled carbon nanotubes. Electrochim Acta 66:180–187Google Scholar
  136. 136.
    Holade Y, Morais C, Servat K, Napporn TW et al (2013) Toward the electrochemical valorization of glycerol: fourier transform infrared spectroscopic and chromatographic studies. ACS Catal 3(10):2403–2411Google Scholar
  137. 137.
    Simões M, Baranton S, Coutanceau C (2010) Electro-oxidation of glycerol at Pd based nano-catalysts for an application in alkaline fuel cells for chemicals and energy cogeneration. Appl Catal B Environ 93(3–4):354–362Google Scholar
  138. 138.
    Sun S-G (1998) Studying electrocatalytic oxidation of small organic molecules with in-situ infra spectroscopy. In: Lipkowski J, Ross PN (eds) Electrocatalysis. Wiley-VCH, Inc., New York, (USA), pp 243–290Google Scholar
  139. 139.
    Demarconnay L, Brimaud S, Coutanceau C, Léger JM (2007) Ethylene glycol electrooxidation in alkaline medium at multi-metallic Pt based catalysts. J Electroanal Chem 601(1–2):169–180Google Scholar
  140. 140.
    Palma LM, Almeida TS, Morais C, Napporn TW et al (2017) Effect of co-catalyst on the selective electrooxidation of glycerol over ruthenium-based nanomaterials. ChemElectroChem 4(1):39–45Google Scholar
  141. 141.
    Innocent B, Pasquier D, Ropital F, Hahn F et al (2010) FTIR spectroscopy study of the reduction of carbon dioxide on lead electrode in aqueous medium. Appl Catal B Environ 94(3–4):219–224Google Scholar
  142. 142.
    Eneau-Innocent B, Pasquier D, Ropital F, Leger JM et al (2010) Electroreduction of carbon dioxide at a lead electrode in propylene carbonate: a spectroscopic study. Appl Catal B Environ 98(1–2):65–71Google Scholar
  143. 143.
    Xiang DM, Magana D, Dyer RB (2014) CO2 reduction catalyzed by Mercaptopteridine on glassy carbon. J Am Chem Soc 136(40):14007–14010Google Scholar
  144. 144.
    Firet NJ, Smith WA (2017) Probing the reaction mechanism of CO2 electroreduction over Ag films via operando infrared spectroscopy. ACS Catal 7(1):606–612Google Scholar
  145. 145.
    Chang SC, Weaver MJ (1990) Coverage-dependent and potential-dependent binding geometries of carbon-monoxide at ordered low-index platinum aqueous and rhodium aqueous interfaces – comparisons with adsorption in corresponding metal vacuum environments. Surf Sci 238(1–3):142–162Google Scholar
  146. 146.
    Chang SC, Weaver MJ (1991) Insitu infrared-spectroscopy at single-crystal metal-electrodes – an emerging link between electrochemical and ultrahigh-vacuum surface science. J Phys Chem 95(14):5391–5400Google Scholar
  147. 147.
    Yajima T, Uchida H, Watanabe M (2004) In-situ ATR-FTIR spectroscopic study of electro-oxidation of methanol and adsorbed CO at Pt-Ru alloy. J Phys Chem B 108(8):2654–2659Google Scholar
  148. 148.
    Ma J, Habrioux A, Morais C, Alonso-Vante N (2014) Electronic modification of Pt via Ti and se as tolerant cathodes in air-breathing methanol microfluidic fuel cells. Phys Chem Chem Phys 16(27):13820–13826Google Scholar
  149. 149.
    Ma J, Habrioux A, Morais C, Lewera A et al (2013) Spectroelectrochemical probing of the strong interaction between platinum nanoparticles and graphitic domains of carbon. ACS Catal 3(9):1940–1950Google Scholar
  150. 150.
    Abidat I, Morais C, Pronier S, Guignard N et al (2017) Effect of gradual reduction of graphene oxide on the CO tolerance of supported platinum nanoparticles. Carbon 111:849–858Google Scholar
  151. 151.
    Bruckenstein S, Gadde RR (1971) Use of a porous electrode for in situ mass spectrometric determination of volatile electrode reaction products. J Am Chem Soc 93(3):793–794Google Scholar
  152. 152.
    Wolter O, Heitbaum J (1984) Differential electrochemical mass spectroscopy (DEMS) – a new method for the study of electrode processes. Ber Bunsenges Phys Chem 88(1):2–6Google Scholar
  153. 153.
    Baltruschat H (2004) Differential electrochemical mass spectrometry. J Am Soc Mass Spectrom 15(12):1693–1706Google Scholar
  154. 154.
    Sreekanth N, Phani KL (2014) Selective reduction of CO2 to formate through bicarbonate reduction on metal electrodes: new insights gained from SG/TC mode of SECM. Chem Commun 50(76):11143–11146Google Scholar
  155. 155.
    Li CW, Kanan MW (2012) CO2 reduction at low overpotential on Cu electrodes resulting from the reduction of thick Cu2O films. J Am Chem Soc 134(17):7231–7234Google Scholar
  156. 156.
    Koga O, Hori Y (1993) Reduction of adsorbed co on a Ni electrode in connection with the electrochemical reduction of CO2. Electrochim Acta 38(10):1391–1394Google Scholar
  157. 157.
    Li W (2010) Electrocatalytic reduction of CO2 to small organic molecule fuels on metal catalysts. In: Advances in CO2 conversion and utilization, vol 1056. American Chemical Society, Washington DC, pp 55–76Google Scholar
  158. 158.
    Chen Y, Li CW, Kanan MW (2012) Aqueous CO2 reduction at very low Overpotential on oxide-derived au nanoparticles. J Am Chem Soc 134(49):19969–19972Google Scholar
  159. 159.
    Hansen HA, Varley JB, Peterson AA, Nørskov JK (2013) Understanding trends in the Electrocatalytic activity of metals and enzymes for CO2 reduction to CO. J Phys Chem Lett 4(3):388–392Google Scholar
  160. 160.
    Baturina OA, Lu Q, Padilla MA, Xin L et al (2014) CO2 electroreduction to hydrocarbons on carbon-supported cu nanoparticles. ACS Catal 4(10):3682–3695Google Scholar
  161. 161.
    Ren D, Deng Y, Handoko AD, Chen CS et al (2015) Selective electrochemical reduction of carbon dioxide to ethylene and ethanol on copper(I) oxide catalysts. ACS Catal 5(5):2814–2821Google Scholar
  162. 162.
    Varela AS, Kroschel M, Reier T, Strasser P (2016) Controlling the selectivity of CO2 electroreduction on copper: the effect of the electrolyte concentration and the importance of the local pH. Catal Today 260:8–13Google Scholar
  163. 163.
    Zhang S, Kang P, Meyer TJ (2014) Nanostructured tin catalysts for selective electrochemical reduction of carbon dioxide to Formate. J Am Chem Soc 136(5):1734–1737Google Scholar
  164. 164.
    Liu Z, Masel RI, Chen Q, Kutz R et al (2016) Electrochemical generation of syngas from water and carbon dioxide at industrially important rates. J CO2 Util 15:50–56Google Scholar
  165. 165.
    Ma M, Trześniewski BJ, Xie J, Smith WA (2016) Selective and efficient reduction of carbon dioxide to carbon monoxide on oxide-derived nanostructured silver Electrocatalysts. Angew Chem Int Ed 55(33):9748–9752Google Scholar
  166. 166.
    Camilo MR, Silva WO, Lima FHB (2017) Investigation of electrocatalysts for selective reduction of CO2 to CO: monitoring the reaction products by on line mass spectrometry and gas chromatography. J Braz Chem Soc. 28(9):1803–1815Google Scholar
  167. 167.
    Sarkar A, Manthiram A (2010) Synthesis of Pt@Cu Core−Shell nanoparticles by galvanic displacement of Cu by Pt4+ ions and their application as electrocatalysts for oxygen reduction reaction in fuel cells. J Phys Chem C 114(10):4725–4732Google Scholar
  168. 168.
    Zhang J, Lima FHB, Shao MH, Sasaki K et al (2005) Platinum monolayer on nonnoble metal−Noble metal Core−Shell nanoparticle electrocatalysts for O2 reduction. J Phys Chem B 109(48):22701–22704Google Scholar
  169. 169.
    Kiros Y (1996) Electrocatalytic properties of Co, Pt, and Pt-Co on carbon for the reduction of oxygen in alkaline fuel cells. J Electrochem Soc 143(7):2152–2157Google Scholar
  170. 170.
    Kedzierzawski P, Augustynski J (1994) Poisoning and activation of the gold cathode during Electroreduction of CO2. J Electrochem Soc 141(5):L58–L60Google Scholar
  171. 171.
    Wang H, Jusys Z, Behm RJ (2006) Ethanol electro-oxidation on carbon-supported Pt, PtRu and Pt3Sn catalysts: a quantitative DEMS study. J Power Sources 154(2):351–359Google Scholar
  172. 172.
    Sato AG, Silva GCD, Paganin VA, Biancolli ALG et al (2015) New, efficient and viable system for ethanol fuel utilization on combined electric/internal combustion engine vehicles. J Power Sources 294:569–573Google Scholar
  173. 173.
    Lai SCS, Kleijn SEF, Öztürk FTZ, van Rees Vellinga VC et al (2010) Effects of electrolyte pH and composition on the ethanol electro-oxidation reaction. Catal Today 154(1–2):92–104Google Scholar
  174. 174.
    Queiroz AC, Silva WO, Rodrigues IA, Lima FHB (2014) Identification of bimetallic electrocatalysts for ethanol and acetaldehyde oxidation: probing C2-pathway and activity for hydrogen oxidation for indirect hydrogen fuel cells. Appl Catal B Environ 160–161:423–435Google Scholar
  175. 175.
    Sao-Joao S, Giorgio S, Penisson JM, Chapon C et al (2005) Structure and deformations of Pd−Ni Core−Shell nanoparticles. J Phys Chem B 109(1):342–347Google Scholar
  176. 176.
    Kowal A, Li M, Shao M, Sasaki K et al (2009) Ternary Pt/Rh/SnO2 electrocatalysts for oxidizing ethanol to CO2. Nat Mater 8(4):325–330Google Scholar

Copyright information

© Springer-Verlag GmbH Germany, part of Springer Nature 2018

Authors and Affiliations

  • Têko W. Napporn
    • 1
  • Laetitia Dubau
    • 2
    • 3
  • Claudia Morais
    • 1
  • Mariana R. Camilo
    • 4
  • Julien Durst
    • 2
    • 3
  • Fabio H. B. Lima
    • 4
  • Frédéric Maillard
    • 2
    • 3
  • K. Boniface Kokoh
    • 1
  1. 1.IC2MP UMR 7285 CNRS University of PoitiersPoitiersFrance
  2. 2.University of Grenoble AlpesGrenobleFrance
  3. 3.CNRSGrenobleFrance
  4. 4.IQSC, University of São PauloSão CarlosBrazil

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