Skip to main content
Log in

Effects of NH3 and tertiary ammoniums on Au/C catalyst in glycerol electrooxidation in alkaline media

  • Research Article
  • Published:
Journal of Applied Electrochemistry Aims and scope Submit manuscript

Abstract

The poisoning effect of ammonia, trimethyl ammonium (TMA), and triethyl ammonium (TEA) on an Au/C catalyst in glycerol electrooxidation was investigated by using cyclic voltammetry, chronoamperometry (CA), and chronopotentiometry (CP) techniques. These ternary ammoniums are the possible degradation products of quaternary ammonium functional groups that are mainly contained in anion exchange membranes (AEMs) used in fuel cells. The most poisonous species was NH3, followed by TEA and TMA, which is consistent with their pK a trends. Via a cyclic voltammogram, poisoning effects were observed from the shift of the potentials at maximum current density, the recovery of oxidation currents in negative scans, and the drops in current density as compared to the ammonium-free electrolyte. The maximum current density decreased about 44 % in the presence of 1 mM NH3, but it showed only small effects for TMA and TEA at this concentration. The poisoning effects of TMA and TEA were more pronounced at a concentration of 10 mM. TEA displayed harsh effects in the CA and CP results. The cause of the current drop was the strong adsorption of these species in the same potential region of glycerol electrooxidation. Finally, the results suggested the use of methyl-substituted amines as a functional group in an AEM when Au was used as the electrocatalyst.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6
Fig. 7
Fig. 8

Similar content being viewed by others

References

  1. Kwon Y, Lai SCS, Rodriguez P, Koper MTM (2011) Electrocatalytic oxidation of alcohols on gold in alkaline media: base or gold catalysis? J Am Chem Soc 133:6914–6917

    Article  CAS  Google Scholar 

  2. Zhang JH, Liang YJ, Li N, Li ZY, Xu CW, Jiang SP (2012) A remarkable activity of glycerol electrooxidation on gold in alkaline medium. Electrochim Acta 59:156–159

    Article  CAS  Google Scholar 

  3. Yongprapat S, Therdthianwong A, Therdthianwong S (2012) Au/C catalyst prepared by polyvinyl alcohol protection method for direct alcohol alkaline exchange membrane fuel cell application. J Appl Electrochem 42:483–490

    Article  CAS  Google Scholar 

  4. Bott-Neto JL, Garcia AC, Oliveira VL, de Souza NE, Tremiliosi-Filho G (2014) Au/C catalysts prepared by a green method towards C3 alcohol electrooxidation: a cyclic voltammetry and in situ FTIR spectroscopy study. J Electroanal Chem 735:57–62

    Article  CAS  Google Scholar 

  5. Simões M, Baranton S, Coutanceau C (2012) Electrochemical valorization of glycerol. ChemSusChem 5:2106–2124

    Article  Google Scholar 

  6. Padayachee D, Golovko V, Marshall AT (2013) The effect of MnO2 loading on the glycerol electrooxidation activity of Au/MnO2/C catalysts. Electrochim Acta 98:208–217

    Article  CAS  Google Scholar 

  7. Padayachee D, Golovko V, Ingham B, Marshall AT (2014) Influence of particle size on the electrocatalytic oxidation of glycerol over carbon-supported gold nanoparticles. Electrochim Acta 120:398–407

    Article  CAS  Google Scholar 

  8. Xin L, Zhang Z, Wang Z, Li W (2012) Simultaneous generation of mesoxalic acid and electricity from glycerol on a gold anode catalyst in anion-exchange membrane fuel cells. ChemCatChem 4:1105–1114

    Article  CAS  Google Scholar 

  9. Qi J, Xin L, Chadderdon DJ, Qiu Y, Jiang Y, Benipal N, Liang C, Li W (2014) Electrocatalytic selective oxidation of glycerol to tartronate on Au/C anode catalysts in anion exchange membrane fuel cells with electricity cogeneration. Appl Catal B 154–155:360–368

    Article  Google Scholar 

  10. Masato T, Masato N, Katsuhiko N, Isao T (2007) Surface poisoning during electrocatalytic monosaccharide oxidation reactions at gold electrodes in alkaline medium. Electrochem Commun 9:1892–1898

    Article  Google Scholar 

  11. Sami SB, Zekerya D, Tesshu K, Gyeong SB, Tadashi S, Isao T (2004) Effect of metal ad-layer on Au(111) electrodes on electrocatalytic oxidation of glucose in an alkaline solution. Electroanal Chem 567:175–183

    Article  Google Scholar 

  12. Ciriminna R, Pina CD, Rossi M, Pagliaro M (2014) Understanding the glycerol market. Eur J Lipid Sci Technol 10:1432–1439

    Article  Google Scholar 

  13. 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 93:354–362

    Article  Google Scholar 

  14. Merle G, Wessling M, Nijmeijer K (2011) Anion exchange membranes for alkaline fuel cells: a review. J Membr Sci 377:1–35

    Article  CAS  Google Scholar 

  15. Hickner MA, Herring AM, Coughlin EB (2013) Anion exchange membranes: current status and moving forward. J Polym Sci B 51:1727–1735

    Article  CAS  Google Scholar 

  16. Maurya S, Shin SH, Kim MK, Yun SH, Moon SH (2013) Stability of composite anion exchange membranes with various functional groups and their performance for energy conversion. J Membr Sci 443:28–35

    Article  CAS  Google Scholar 

  17. Macomber CS, Boncella JM, Pivovar BS, Rau JA (2008) Decomposition pathways of an alkaline fuel cell membrane material component via evolved gas analysis. J Therm Anal Calorim 93:225–229

    Article  CAS  Google Scholar 

  18. Switzer EE, Olson TS, Datye AK, Atanassov P, Hibbs MR, Fujimoto C, Cornelius CJ (2010) Novel KOH-free anion-exchange membrane fuel cell: performance comparison of alternative anion-exchange ionomers in catalyst ink. Electrochim Acta 55:3404–3408

    Article  CAS  Google Scholar 

  19. Kim H, Zhou J, Ünlü M, Anestis-Richard I, Joseph K, Kohl PA (2011) The effect of hydrophobicity in alkaline electrodes for passive DMFC. Electrochim Acta 56:3085–3090

    Article  CAS  Google Scholar 

  20. Yang D, Yu H, Li G, Zhao Y, Liu Y, Zhang C, Song W, Shao Z (2014) Fine microstructure of high performance electrode in alkaline anion exchange membrane fuel cells. J Power Sources 267:39–47

    Article  CAS  Google Scholar 

  21. Tremilio-Filho G, Dall’Antonia LH, Jerkiewicz G (1997) Limit to extent of formation of the quasi-two-dimensional oxide state on Au electrode. J Electroanal Chem 422:149–159

    Article  Google Scholar 

  22. de Vooys ACA, Koper MTM, van Santen RA, van Veen JAR (2001) The role of adsorbates in the electrochemical oxidation of ammonia on noble metal and transition metal electrodes. J Electroanal Chem 506:127–137

    Article  Google Scholar 

  23. de Vooys ACA, Mrozek MF, Koper MTM, van Santen RA, van Veen JAR, Weaver MJ (2001) The nature of chemisorbates formed from ammonia on gold and palladium electrodes as discerned from surface-enhanced Raman spectroscopy. Electrochem Commun 3:293–298

    Article  Google Scholar 

  24. Concha MBM, Chatenet M, Lima FHB, Ticianelli EA (2013) In situ Fourier infrared spectroscopy and on-line differential electrochemical mass spectrometry study of the NH3BH3 oxidation reaction on gold electrodes. Electrochim Acta 89:607–615

    Article  Google Scholar 

  25. Surplice NA, Brearley W (1975) The adsorption of carbon monoxide, ammonia, and wet air on gold. Surf Sci 52:62–74

    Article  CAS  Google Scholar 

  26. Kay BD, Lykke KR, Creighton JR, Ward SJ (1989) The influence of adsorbate–absorbate hydrogen bonding in molecular chemisorption: NH3, HF, and H2O on Au(111). J Chem Phys 91:5120–5121

    Article  CAS  Google Scholar 

  27. Deng X, Baker TA, Friend CM (2006) A pathway for NH addition to styrene promoted by gold. Angew Chem Int Ed 45:7075–7078

    Article  CAS  Google Scholar 

  28. Masui M, Sayo H, Tsuda Y (1968) Anodic oxidation of amines. Part I. Cyclic voltammetry of aliphatic amines at a stationary glassy-carbon electrode. J Chem Soc B Phys Org 973–976

  29. Smith JRL, Masheder D (1977) Amine oxidation. Part 13. Electrochemical oxidation of some substituted tertiary alkylamines. J Chem Soc Perkin Trans 2:1732–1736

    Article  Google Scholar 

  30. Hall HK (1957) Correlation of the base strengths of amines. J Am Chem Soc 79:5441–5444

    Article  CAS  Google Scholar 

  31. Nagle LC, Rohan JH (2006) Ammonia borane oxidation at gold microelectrodes in alkaline solutions. J Electrochem Soc 11:C773–C776

    Article  Google Scholar 

Download references

Acknowledgments

This work was financially supported by the National Nanotechnology Center of Thailand (NANOTEC) and the National Research University (NRU) Project of Thailand’s Office of the Higher Education Commission.

Author information

Authors and Affiliations

Authors

Corresponding author

Correspondence to S. Yongprapat.

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Yongprapat, S., Therdthianwong, A. & Therdthianwong, S. Effects of NH3 and tertiary ammoniums on Au/C catalyst in glycerol electrooxidation in alkaline media. J Appl Electrochem 45, 487–494 (2015). https://doi.org/10.1007/s10800-015-0821-4

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s10800-015-0821-4

Keywords

Navigation