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Spectroscopic elucidation of reaction pathways of acetaldehyde on platinum and palladium in acidic media

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Abstract

The electrochemical behavior of acetaldehyde on palladium and platinum electrodes in acidic media was comparatively studied by means of differential electrochemical mass spectrometry (DEMS) and in situ Fourier transform infrared spectroscopy (FTIRS) combined with cyclic voltammetry. It was observed that acetaldehyde decomposition depends on the catalyst material, applied potential, and reactant concentration. Additionally, it was detected that acetaldehyde adsorbs and dissociates at potentials lower than 0.60 V vs RHE, producing methane and adsorbed CO on Pd; while C2-species, CHx and COad are formed on Pt. Besides carbon dioxide, acetic acid and adsorbed acetate were observed at E > 0.6 V, and their contribution increased with acetaldehyde concentration. Differences between Pt and Pd in potential dependence of the products and intermediates were established. Calibration of the mass spectrometer, together with the use of labeled acetaldehyde and IR spectra, allows establishment of the nature of adsorbed species and products for both Pt and Pd at different potentials, elucidating global reaction pathways for acetaldehyde on these two noble metals.

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References

  1. Antolini E (2007) Catalysts for direct ethanol fuel cells. J Power Sources 170(1):1–12

    Article  CAS  Google Scholar 

  2. Dillon R, Srinivasan S, Aricò AS, Antonucci V (2004) International activities in DMFC R&D: status of technologies and potential applications. J Power Sources 127(1–2):112–126

    Article  CAS  Google Scholar 

  3. Iwasita T, Pastor E (1994) A DEMS and FTIR spectroscopic investigation of adsorbed ethanol on polycrystalline platinum. Electrochim Acta 39(4):531–537

    Article  CAS  Google Scholar 

  4. Pastor E, Iwasita T (1994) D/H exchange of ethanol at platinum electrodes. Electrochim Acta 39(4):547–551

    Article  CAS  Google Scholar 

  5. Mostafa E, Abd-El-Latif AEAA, Ilsley R, Attard G, Baltruschat H (2012) Quantitative DEMS study of ethanol oxidation: effect of surface structure and Sn surface modification. Phys Chem Chem Phys 14(46):16115–16129

    Article  CAS  Google Scholar 

  6. Wu G, Swaidan R, Cui G (2007) Electrooxidations of ethanol, acetaldehyde and acetic acid using PtRuSn/C catalysts prepared by modified alcohol-reduction process. J Power Sources 172(1):180–188

    Article  CAS  Google Scholar 

  7. Gomes JF, Bergamaski K, Pinto MFS, Miranda PB (2013) Reaction intermediates of ethanol electro-oxidation on platinum investigated by SFG spectroscopy. J Catal 302:67–82

    Article  CAS  Google Scholar 

  8. Arvia AJ (1982) Electrocátalisis: aspectos básicos y aplicaciones. FECIC, La Plata

    Google Scholar 

  9. Bittins-Cattaneo B, Wilhelm S, Cattaneo E, Buschmann HW, Vielstich W (1988) Intermediates and products of ethanol oxidation on platinum in acid solution. Ber Bunsenges Phys Chem Chem Phys 92(11):1210–1218

    Article  CAS  Google Scholar 

  10. Cases F, Vázquez JL, Pérez JM, Aldaz A, Clavilier J (1990) Dissociative adsorption of acetaldehyde on Pt(h, k, l) basal surfaces. J Electroanal Chem 281(1–2):283–288

    Article  CAS  Google Scholar 

  11. Podlovchenko BI, Petry OA, Frumkin AN, Lal H (1966) The behaviour of a platinized-platinum electrode in solutions of alcohols containing more than one carbon atom, aldehydes and formic acid. J Electroanal Chem 11(1):12–25, 1959

    CAS  Google Scholar 

  12. Rasch B, Iwasita T (1990) The electrochemical adsorption and oxidation of acetaldehyde on polycrystalline platinum in acidic solution-A SNIFTIRS study. Electrochim Acta 35(6):989–993

    Article  CAS  Google Scholar 

  13. Rodríguez JL, Pastor E, Xia XH, Iwasita T (2000) Reaction intermediates of acetaldehyde oxidation on Pt(111) and Pt(100). An in situ FTIR study. Langmuir 16(12):5479–5486

    Article  Google Scholar 

  14. Farias MJS, Camara GA, Tanaka AA, Iwasita T (2007) Acetaldehyde electrooxidation: the influence of concentration on the yields of parallel pathways. J Electroanal Chem 600(2):236–242

    Article  CAS  Google Scholar 

  15. Silva-Chong J, Méndez E, Rodríguez JL, Arévalo MC, Pastor E (2002) Reactivity of acetaldehyde at platinum and rhodium in acidic media. A DEMS study. Electrochim Acta 47(9):1441–1449

    Article  CAS  Google Scholar 

  16. Sun S, Heinen M, Jusys Z, Behm RJ (2012) Electrooxidation of acetaldehyde on a carbon supported Pt catalyst at elevated temperature/pressure: an on-line differential electrochemical mass spectrometry study. J Power Sources 204:1–13

    Article  CAS  Google Scholar 

  17. Zhao H, Kim J, Koel BE (2003) Adsorption and reaction of acetaldehyde on Pt(1 1 1) and Sn/Pt(1 1 1) surface alloys. Surf Sci 538(3):147–159

    Article  CAS  Google Scholar 

  18. Delbecq F, Vigné F (2005) Acetaldehyde on Pt(111) and Pt/Sn(111): a DFT study of the adsorption structures and of the vibrational spectra. J Phys Chem B 109(21):10797–10806

    Article  CAS  Google Scholar 

  19. Jusys Z, Behm RJ (2008) DEMS analysis of small organic molecule electrooxidation: a high-temperature high-pressure DEMS study. ECS Trans 16(2 PART 2):1243–1251

    Article  CAS  Google Scholar 

  20. Kokoh KB, Hahn F, Belgsir EM, Lamy C, De Andrade AR, Olivi P, Motheo AJ, Tremiliosi-Filho G (2004) Electrocatalytic oxidation of acetaldehyde on Pt alloy electrodes. Electrochim Acta 49(13):2077–2083

    Article  CAS  Google Scholar 

  21. Lai SCS, Kleyn SEF, Rosca V, Koper MTM (2008) Mechanism of the dissociation and electrooxidation of ethanol and acetaldehyde on platinum as studied by SERS. J Phys Chem C 112(48):19080–19087

    Article  CAS  Google Scholar 

  22. Lai SCS, Koper MTM (2008) Electro-oxidation of ethanol and acetaldehyde on platinum single-crystal electrodes. Faraday Discuss 140:399–416

    Article  CAS  Google Scholar 

  23. Liakopoulos C, Poulopoulos S, Philippopoulos C (2001) Kinetic studies of acetaldehyde oxidation over Pt/Rh and Pd monolithic catalysts in a spinning-basket flow reactor. Ind Eng Chem Res 40(6):1476–1481

    Article  CAS  Google Scholar 

  24. Wang H, Jusys Z, Behm RJ (2004) Ethanol and acetaldehyde adsorption on a carbon-supported Pt catalyst: a comparative DEMS study. Fuel Cells 4(1–2):113–125

    Article  CAS  Google Scholar 

  25. Wang H, Jusys Z, Behm RJ (2006) Electrooxidation of acetaldehyde on carbon-supported Pt, PtRu and Pt3Sn and unsupported PtRu0.2 catalysts: a quantitative DEMS study. J Appl Electrochem 36(11):1187–1198

    Article  CAS  Google Scholar 

  26. Méndez E, Rodríguez JL, Arévalo MC, Pastor E (2002) Comparative study of ethanol and acetaldehyde reactivities on rhodium electrodes in acidic media. Langmuir 18(3):763–772

    Article  Google Scholar 

  27. Silva-Chong JA, Guillén-Villafuerte O, Rodríguez JL, Pastor E (2008) DEMS study on the nature of acetaldehyde adsorbates at Pt and Pd by isotopic labelling. J Solid State Electrochem 12(5):517–522

    Article  CAS  Google Scholar 

  28. Wolter O, Heitbaum J (1984) Differential electrochemical mass spectrometry (DEMS)—a new method for the study of electrode processes. Ber Bunsenges Phys Chem Chem Phys 88(1):2–6

    Article  CAS  Google Scholar 

  29. Baltruschat H (1999) In: Wieckowski A (ed) Interfacial electrochemistry: theory, experiment, and applications, vol 484. vol 1. Marcel Dekker, New York, p 577

    Google Scholar 

  30. Iwasita T, Nart VFC (1997) In situ infrared spectroscopy at electrochemical interfaces. Prog Surf Sci 55(4):271–340

    Article  CAS  Google Scholar 

  31. Vargas A, Santarossa G, Baiker A (2011) Ab initio molecular dynamics investigation of the coadsorption of acetaldehyde and hydrogen on a platinum nanocluster. J Phys Chem C 115(21):10661–10667

    Article  CAS  Google Scholar 

  32. Colmati F, Antolini E, Gonalez ER (2007) Ethanol oxidation on carbon supported Pt-Sn electrocatalysts prepared by reduction with formic acid. J Electrochem Soc 154(1):B39–B47

    Article  CAS  Google Scholar 

  33. De Souza JPI, Queiroz SL, Bergamaski K, Gonzalez ER, Nart FC (2002) Electro-oxidation of ethanol on Pt, Rh, and PtRh electrodes. A study using DEMS and in-situ FTIR techniques. J Phys Chem B 106(38):9825–9830

    Article  Google Scholar 

  34. Rousseau S, Coutanceau C, Lamy C, Léger JM (2006) Direct ethanol fuel cell (DEFC): electrical performances and reaction products distribution under operating conditions with different platinum-based anodes. J Power Sources 158(1):18–24

    Article  CAS  Google Scholar 

  35. Vigier F, Coutanceau C, Hahn F, Belgsir EM, Lamy C (2004) On the mechanism of ethanol electro-oxidation on Pt and PtSn catalysts: electrochemical and in situ IR reflectance spectroscopy studies. J Electroanal Chem 563(1):81–89

    Article  CAS  Google Scholar 

  36. Gootzen JFE, Visscher W, van Veen JAR (1996) Characterization of ethanol and 1,2-ethanediol adsorbates on platinized platinum with Fourier transform infrared spectroscopy and differential electrochemical mass spectrometry. Langmuir 12(21):5076–5082

    Article  CAS  Google Scholar 

  37. Chang SC, Leung LWH, Weaver MJ (1990) Metal crystallinity effects in electrocatalysis as probed by real-time FTIR spectroscopy: electrooxidation of formic acid, methanol, and ethanol on ordered low-index platinum surfaces. J Phys Chem 94(15):6013–6021

    Article  CAS  Google Scholar 

  38. Leung L-WH, Chang S-C, Weaver MJ (1989) Real-time FTIR spectroscopy as an electrochemical mechanistic probe: electrooxidation of ethanol and related species on well-defined Pt (111) surfaces. J Electroanal Chem Interfacial Electrochem 266(2):317–336

    Article  CAS  Google Scholar 

  39. Perez JM, Beden B, Hahn F, Aldaz A, Lamy C (1989) “In situ” infrared reflectance spectroscopic study of the early stages of ethanol adsorption at a platinum electrode in acid medium. J Electroanal Chem Interfacial Electrochem 262(1–2):251–261

    Article  CAS  Google Scholar 

Download references

Acknowledgments

This work has been supported by the Spanish Ministry of Innovation and Competitiveness under project CTQ2011-28913-C02-02.

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Authors and Affiliations

  1. Dpto. Química Física, Instituto de Materiales y Nanotecnología, Universidad de La Laguna, Avda. Astrofísico Francisco Sánchez s/n, 38071, La Laguna, Tenerife, Spain

    G. García, J. Silva-Chong, J. L. Rodríguez & E. Pastor

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  1. G. García
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  2. J. Silva-Chong
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  3. J. L. Rodríguez
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  4. E. Pastor
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Correspondence to E. Pastor.

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Supporting information Fig. S1

Cyclic voltammogram of Pd in 0.1 M HClO4 (black and blue lines) and electrochemical behavior of 0.02 M acetaldehyde in 0.1 M HClO4 on porous Pd (red line). v = 0.010 V s−1, A Pd = 18 cm2 (PDF 28 kb)

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García, G., Silva-Chong, J., Rodríguez, J.L. et al. Spectroscopic elucidation of reaction pathways of acetaldehyde on platinum and palladium in acidic media. J Solid State Electrochem 18, 1205–1213 (2014). https://doi.org/10.1007/s10008-013-2283-0

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  • DOI: https://doi.org/10.1007/s10008-013-2283-0

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