Advertisement

Springer Nature is making SARS-CoV-2 and COVID-19 research free. View research | View latest news | Sign up for updates

In situ imaging of electrode processes on solid electrolytes by photoelectron microscopy and microspectroscopy – the role of the three-phase boundary

The electrochemical polarisation of metal catalyst films on solid electrolyte substrates can basically lead to three different effects: (a) the generation of mobile surface species (spillover) which spread over the catalyst surface and modify the catalytic activity, (b) potential-controlled segregation of impurities in the catalyst and (c) potential-dependent surface energy (electrocapillarity). The generation of spillover species occurs at the three-phase boundary between metal, solid electrolyte and gas phase and is highly localized. The spreading occurs via diffusion and leads to time-dependent and inhomogeneous surface concentrations. The kinetics of the spillover process can only be observed with in situ surface-analytical techniques in combination with electrochemical methods which offer sufficient resolution in space and time. Model experiments with UV and X-ray photoelectron emission microscopy (PEEM and SPEM) are summarized and discussed with respect to their relevance for the better understanding of electrochemical promotion in catalysis.

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

References

  1. 1

    C.G. Vayenas, S. Bebelis, C. Pliangos, S. Brosda and D. Tsiplakides, Electrochemical Activation of Catalysis (Springer, 2002)

  2. 2

    W. Zipprich H.-D. Wiemhoefer U. Vohrer W. Goepel (1995) Ber. Bunsen-Ges. 99 IssueID11 1406 Occurrence Handle1:CAS:528:DyaK2MXptlSksLc%3D

  3. 3

    J. Nicole Ch. Comninellis (1998) J. Appl. Electrochem. 28 IssueID3 223 Occurrence Handle10.1023/A:1003295112211 Occurrence Handle1:CAS:528:DyaK1cXitVOrsbY%3D

  4. 4

    S. Völkening E. Schütz J. Janek R. Imbihl (1999) Phys. Chem. Chem. Phys. 1 5241

  5. 5

    L. Ploense M. Salazar B. Gurau E.S. Smotkin (2000) Solid State Ionics 136–137 713–720 Occurrence Handle10.1016/S0167-2738(00)00567-1

  6. 6

    V.D. Belyaev T.I Politova V.A. Sobyanin (2000) Solid State Ionics 136–137 721 Occurrence Handle10.1016/S0167-2738(00)00501-4

  7. 7

    M.R. Lambert A. Palermo F.J. Williams M.S. Tikhov (2000) Solid State Ionics 136–137 677 Occurrence Handle10.1016/S0167-2738(00)00509-9

  8. 8

    S. Kim G.L. Haller (2000) Solid State Ionics 136–137 693 Occurrence Handle10.1016/S0167-2738(00)00514-2

  9. 9

    D. Poulidi M.A. Castillo-del-Rio R. Salar I.S. Metcalfe (2003) Solid State Ionics 162–163 305 Occurrence Handle10.1016/S0167-2738(03)00224-8 Occurrence Handle1:CAS:528:DC%2BD3sXns1els78%3D

  10. 10

    P.M. Leiva C.G. Sanchez (2003) J. Solid State Electrochem. 7 IssueID9 588 Occurrence Handle10.1007/s10008-003-0417-5 Occurrence Handle1:CAS:528:DC%2BD3sXnsFGrtr4%3D

  11. 11

    J. Fleig J. Jamnik (2005) Electrochem. Soc. 152 IssueID4 E138 Occurrence Handle10.1149/1.1862479 Occurrence Handle1:CAS:528:DC%2BD2MXjslSjtb0%3D

  12. 12

    C.G. Vayenas S. Bebelis S. Neophytides I.V. Yentekakis Yi. Jiang (1993) Stud. Surf. Sci. Catal. 77 111 Occurrence Handle1:CAS:528:DyaK2cXhslCms70%3D

  13. 13

    C.G. Vayenas R.M. Lambert S. Ladas S. Bebelis S. Neophytides M.S. Tikov N.C. Filkin M. Tsiplakides D. Cavalc K. Besocke (1997) Stud. Surf. Sci. Catal. 112 39 Occurrence Handle1:CAS:528:DyaK1cXovF2jsg%3D%3D Occurrence Handle10.1016/S0167-2991(97)80822-1

  14. 14

    G. Foti I. Bolzonella Ch. Comninellis (2004) J. Appl. Electrochem. 34 9 Occurrence Handle10.1023/B:JACH.0000005575.92134.60 Occurrence Handle1:CAS:528:DC%2BD3sXptlCks7w%3D

  15. 15

    B. Luerssen S. Guenther S. Marbach M. Kiskinova J. Janek R. Imbihl (2000) Chem. Phys. Lett. 316 331 Occurrence Handle10.1016/S0009-2614(99)01302-0 Occurrence Handle1:CAS:528:DC%2BD3cXltVagsg%3D%3D

  16. 16

    J.-Y. Go S.-I. Pyun (2004) J. Korean Electrochem. Soc. 7 IssueID4 211 Occurrence Handle1:CAS:528:DC%2BD2MXmtFyjtQ%3D%3D

  17. 17

    M. Makri C.G. Vayenas S. Bebelis K.H. Besocke C. Cavalca (1996) Ionics 2 IssueID3&4 248 Occurrence Handle10.1007/BF02376030 Occurrence Handle1:CAS:528:DyaK1cXnt1ajuw%3D%3D

  18. 18

    S.P. Jiang W. Wang (2005) Electrochem. Solid-State Lett. 8 IssueID2 A115 Occurrence Handle10.1149/1.1847689 Occurrence Handle1:CAS:528:DC%2BD2MXkslejsA%3D%3D

  19. 19

    J. Fleig (2003) Adv. Electrochem. Sci. Eng. 8 1 Occurrence Handle1:CAS:528:DC%2BD3sXlslegtLY%3D

  20. 20

    B. Luerssen J. Janek S. Guenther M. Kiskinova R. Imbihl (2002) Phys. Chem. Chem. Phys. 4 IssueID12 2673 Occurrence Handle10.1039/b109893d Occurrence Handle1:CAS:528:DC%2BD38XktVegtbw%3D

  21. 21

    J.F. Williams A. Palermo M.S. Tikhov R.M. Lambert (2000) J. Phys. Chem. B 104 IssueID3 615 Occurrence Handle10.1021/jp993037i Occurrence Handle1:CAS:528:DyaK1MXotFKgsbk%3D

  22. 22

    F. Svegl, B. Orel, V. Kaucic and K. Kalcher, in: Scientific Papers of the University of Pardubice, Series A: Faculty of Chemical Technology 3 (1998) 257

  23. 23

    D.I. Kondarides G.N. Papatheodorou C.G. Vayenas X.E. Verykios X.E. Ber (1993) Buns. Ges. 97 IssueID5 709 Occurrence Handle1:CAS:528:DyaK3sXksFWksbo%3D

  24. 24

    A.R. Rojas H.E. Esparza-Ponce L. Fuentes A. Lopez-Ortiz A. Keer J. Reyes-Gasga (2005) J. Phys. D. Appl. Phys. 38 IssueID13 2276 Occurrence Handle10.1088/0022-3727/38/13/029 Occurrence Handle1:CAS:528:DC%2BD2MXmsVKjtLs%3D

  25. 25

    Y.L. Liu C. Jiao (2005) Solid State Ionics 176 IssueID5&6 435 Occurrence Handle10.1016/j.ssi.2004.08.018 Occurrence Handle1:CAS:528:DC%2BD2MXitVSntQ%3D%3D

  26. 26

    K.-N. Kim J. Moon J.-W. Son J. Kim H.-W. Lee J.-H. Lee B.-K. Kim (2005) J. Korean Ceram. Soc. 42 IssueID7 509 Occurrence Handle1:CAS:528:DC%2BD2MXns1SrsLw%3D Occurrence Handle10.4191/KCERS.2005.42.7.509

  27. 27

    S.G. Neophytides D. Tsiplakides C.G. Vayenas (1998) J. Catal. 178 IssueID2 414 Occurrence Handle10.1006/jcat.1998.2155 Occurrence Handle1:CAS:528:DyaK1cXmtlChs70%3D

  28. 28

    H. Yokokawa T. Horita N. Sakai K. Yamaji M.E. Brito Y.-P. Xiong H. Kishimoto (2004) Solid State Ionics 174 IssueID1–4 205 Occurrence Handle10.1016/j.ssi.2004.05.030 Occurrence Handle1:CAS:528:DC%2BD2cXhtVaru7%2FO

  29. 29

    W.-F. Zhang P. Schmidt-Zhang U. Guth (2004) Solid State Ionics 169 IssueID1–4 121 Occurrence Handle10.1016/j.ssi.2003.10.004 Occurrence Handle1:CAS:528:DC%2BD2cXksF2rsbc%3D

  30. 30

    X.J. Chen S.H. Chan K.A. Khor (2003) Solid State Ionics 164 IssueID1&2 17 Occurrence Handle10.1016/j.ssi.2003.08.006 Occurrence Handle1:CAS:528:DC%2BD3sXos1ahtr4%3D

  31. 31

    T. Murai K. Yashiro A. Kaimai H. Matsumoto Y. Nigara T. Kawada J. Mizusaki (2004) Trans. Mater. Res. Soc. Jpn. 29 IssueID8 3439 Occurrence Handle1:CAS:528:DC%2BD2MXhtVensLc%3D

  32. 32

    T. Murai K. Yashiro A. Kaimai T. Otake H. Matsumoto T. Kawada J. Mizusaki (2005) Solid State Ionics 176 IssueID31–34 2399 Occurrence Handle10.1016/j.ssi.2005.06.029 Occurrence Handle1:CAS:528:DC%2BD2MXhtVGjsr3I

  33. 33

    R. Imbihl J. Janek (2000) Solid State Ionics 136–137 699 Occurrence Handle10.1016/S0167-2738(00)00565-8

  34. 34

    B. Luerssen E. Mutoro H. Fischer S. Günther R. Imbihl J. Janek (2006) Angew. Chem. Int. Ed. 45 1473 Occurrence Handle10.1002/anie.200503708 Occurrence Handle1:CAS:528:DC%2BD28XitF2qtbg%3D

  35. 35

    V. Brichzin J. Fleig (2002) Solid State Ionics 152–153 499 Occurrence Handle10.1016/S0167-2738(02)00379-X

  36. 36

    J. Fleig (2002) J. Power Sources 105 IssueID2 228 Occurrence Handle10.1016/S0378-7753(01)00944-2 Occurrence Handle1:CAS:528:DC%2BD38XitVyjuro%3D

  37. 37

    T. Kenjo Y. Yamakoshi K. Wada (1993) J. Electrochem. Soc. 140 2151 Occurrence Handle10.1149/1.2220788 Occurrence Handle1:CAS:528:DyaK3sXmtlKgurg%3D

  38. 38

    M.E. Kordesch, in: The Handbook of Surface Imaging and Visualization (ed.) Hubbard A.T. (CRC Press, 1995), Ch. 43

  39. 39

    G.F. Rempfer O.H. Griffith (1992) Ultramicroscopy 47 35 Occurrence Handle10.1016/0304-3991(92)90184-L Occurrence Handle1:STN:280:DyaK3s7islejtw%3D%3D

  40. 40

    S. Günther B. Kaulich L. Gregoratti M. Kiskinova (2002) Prog. Surf. Sci. 70 187 Occurrence Handle10.1016/S0079-6816(02)00007-2

  41. 41

    M. Mundschau (1991) Ultramicroscopy 36 29 Occurrence Handle10.1016/0304-3991(91)90136-T Occurrence Handle1:CAS:528:DyaK3MXmtFGntb8%3D

  42. 42

    O.H. Griffith (1986) Appl. Surf. Sci. 26 IssueID3 265 Occurrence Handle10.1016/0169-4332(86)90068-1 Occurrence Handle1:CAS:528:DyaL28XmtVGmtL4%3D

  43. 43

    L. Casalis W. Jark M. Kishinova D. Lonza P. Melpignano D. Morris R. Rosei A. Savoia A. Abrami C. Fava P. Furlan R. Pugliese D. Vivoda G. Sandrin F.-Q. Wei (1995) Rev. Sci. Instrum. 66 IssueID10 4870 Occurrence Handle10.1063/1.1146167 Occurrence Handle1:CAS:528:DyaK2MXovVGgs74%3D

  44. 44

    M. Mari L. Casalis L. Gregoratti S. Günther A. Kolmakov J. Kovac D. Lonza M. Kiskinova (1997) Electron. Spectrosc. Relat. Phenom. 84 73 Occurrence Handle10.1016/S0368-2048(97)00010-8

  45. 45

    T. Kinoshita (2002) J. Electron. Spectrosc. Relat. Phenom. 124 175 Occurrence Handle10.1016/S0368-2048(02)00053-1 Occurrence Handle1:CAS:528:DC%2BD38XksValtLg%3D

  46. 46

    G.N. Derry P.N. Ross (1985) J. Chem. Phys. 82 2772 Occurrence Handle10.1063/1.448274 Occurrence Handle1:CAS:528:DyaL2MXhsleitLk%3D

  47. 47

    S. Günther, Habilitationsschrift, Universität Hannover (2003)

  48. 48

    P.R. Norton J.A. Davies T.E. Jackmann (1982) Surf. Sci. 122 L593 Occurrence Handle10.1016/0039-6028(82)90054-1 Occurrence Handle1:CAS:528:DyaL3sXktFWktA%3D%3D

  49. 49

    C. Puglia A. Nilsson B. Hernnas O. Karies P. Bennich N. Martensson (1995) Surf. Sci. 342 119 Occurrence Handle10.1016/0039-6028(95)00798-9 Occurrence Handle1:CAS:528:DyaK2MXpslKrsrw%3D

  50. 50

    R.B. Banks, in: Growth and Diffusion Phenomena (Springer-Verlag, Berlin, Heidelberg, 1994) p. 341

  51. 51

    J.V. Barth (2000) Surf. Sci. Rep. 40 75 Occurrence Handle10.1016/S0167-5729(00)00002-9 Occurrence Handle1:CAS:528:DC%2BD3cXntFCrtLc%3D

  52. 52

    M.U. Kislyuk I.I. Tretykov R.K. Nartikoev (1981) Kinetika i Kataliz 22 1287 Occurrence Handle1:CAS:528:DyaL3MXmt1Kgt78%3D

  53. 53

    J. Janek C. Korte (1998) Solid State Ionics 116 181 Occurrence Handle10.1016/S0167-2738(98)00415-9

  54. 54

    B. Luerßen, H. Fischer, S. Günther and J. Janek, in: Proc. of Asian Conf. Solid State Ionics, Vol. 9, eds. B.V.R. Chowdari, H.-I. Yoo, G.M. Choi and I.-H. Lee (2004) p. 139

  55. 55

    S. Ladas S. Kennou S. Bebelis C.G. Vayenas (1993) J. Phys. Chem. 97 8845 Occurrence Handle10.1021/j100137a004 Occurrence Handle1:CAS:528:DyaK3sXls12it7k%3D

  56. 56

    H. Fischer, B. Luerßen, E. Mutoro, S. Guenther and J. Janek, to be published

  57. 57

    R. Danoix-Souchet A. D’Huysser (1997) Surf. Interf. Anal. 25 747 Occurrence Handle10.1002/(SICI)1096-9918(199709)25:10<747::AID-SIA296>3.0.CO;2-F Occurrence Handle1:CAS:528:DyaK2sXmsVWqsb8%3D

  58. 58

    H.P. Bonzel A.M. Franken G. Pirug (1981) Surf. Sci. 104 625 Occurrence Handle10.1016/0039-6028(81)90083-2 Occurrence Handle1:CAS:528:DyaL3MXhvVWhsbY%3D

Download references

Author information

Correspondence to J. Janek.

Rights and permissions

Reprints and Permissions

About this article

Cite this article

Janek, J., Luerßen, B., Mutoro, E. et al. In situ imaging of electrode processes on solid electrolytes by photoelectron microscopy and microspectroscopy – the role of the three-phase boundary. Top Catal 44, 399–407 (2007). https://doi.org/10.1007/s11244-006-0132-4

Download citation

Keywords

  • spillover
  • zirconia solid electrolyte
  • platinum
  • surface diffusion
  • electrochemical promotion
  • NEMCA