Abstract
“Looking” on the other side of the pressure gap in heterogeneous catalysis is an essential step in identifying and understanding differences and similarities between the behavior of catalysts under actual operation conditions (operando) and under the near-vacuum conditions of traditional laboratory experiments. In this article, we demonstrate that real-space, atomic-scale imaging of active catalyst surfaces is possible under realistic or semirealistic reaction conditions with the reactor-STM, a scanning tunneling microscope that is fully integrated with a miniature flow reactor and housed inside an ultrahigh-vacuum system. This special-purpose instrument combines the merits of standard surface-science methods with operando STM observations of model catalysts in action. We illustrate the strength of this microscope with examples of CO oxidation on platinum surfaces.
Similar content being viewed by others
References
J. Wintterlin, Adv. Catal. 45 131 (2000).
P. Stoltze, J.K. Nørskov, Phys. Rev. Lett. 55, 2502 (1985).
J.A. Rodriguez, D.W. Goodman, Surf. Sci. Rep. 14, 1 (1991).
H. Over, Y.D. Kim, A.P. Seitsonen, S. Wendt, E. Lundgren, M. Schmid, P. Varga, A. Morgante, G. Ertl, Science 287, 1474 (2001).
B.L.M. Hendriksen, J.W.M. Frenken, Phys. Rev. Lett. 89, 046101 (2002).
P.B. Rasmussen, B.L.M. Hendriksen, H. Zeijlemaker, H.G. Ficke, J.W.M. Frenken, Rev. Sci. Instrum. 69, 3879 (1998).
B.L.M. Hendriksen, Model Catalysts in Action—High-Pressure Scanning Tunneling Microscopy, PhD thesis, Leiden University, Leiden, the Netherlands, 2003.
H. Bluhm, M. Hävecker, A. Knop-Gericke, M. Kiskinova, R. Schlögl, M. Salmeron, MRS Bull. 32 (12) (December 2007).
F.G. Requejo, E.L.D. Hebenstreit, D.F. Ogletree, M. Salmeron, J. Catal. 226, 83 (2004).
W.P.A. Jansen, A.W. Denier van der Gon, G.M. Wijers, Y.G.M. Rikers, H.H. Brongersma, P.W. van der Hoogen, J.A.M. de Laat, T.M. Maas, E.C.A. Dekkers, P. Brinkgreve, Rev. Sci. Instrum. 73, 354 (2002).
P.L. Gai, E.D. Boyes, S. Helveg, P.L. Hansen, S. Giorgio, C. Henry, MRS Bull. 32 (12) (December 2007).
P.L. Hansen, J.B. Wagner, S. Helveg, J.R. Rostrup-Nielsen, B.S. Clausen, H. Topsøe, Science 295, 2053 (2002).
G. Rupprechter, MRS Bull. 32 (12) (December 2007).
G.A. Beitel, A. Laskov, H. Oosterbeek, E.W. Kuipers, J. Phys. Chem. 100, 12494 (1996).
E. Ozensoy, C. Hess, D. Loffreda, P. Sautet, D.W. Goodman, J. Phys. Chem. B 109, 5415 (2005).
X. Su, P.S. Cremer, Y.R. Shen, G.A. Somorjai, Phys. Rev. Lett. 77, 3858 (1996).
G. Rupprechter, T. Dellwig, H. Unterhalt, H.-J. Freund, J. Phys. Chem. B 105, 3797 (2001).
H.H. Rotermund, Surf. Sci. 386, 10 (1997).
J. Evans, A. Puig-Molina, M. Tromp, MRS Bull. 32 (12) (December 2007).
A. Knop-Gericke, M. Hävecker, T. Schedel-Niedrig, R. Schlögl, Catal. Lett. 66, 215 (2000).
S. Ferrer, M.D. Ackermann, E. Lundgren, MRS Bull. 32 (12) (December 2007).
H. Isern, K. Peters, P. Steadman, O. Robach, J. Alvarez, E. Lundgren, S. Ferrer, Surf. Sci. 482–485, 101 (2001).
B.J. McIntyre, M. Salmeron, G.A. Somorjai, Rev. Sci. Instrum. 64, 687 (1993).
J.A. Jensen, K.B. Rider, Y. Chen, M. Salmeron, J. Vac. Sci. Technol. B 17, 1080 (1999).
E. Laegsgaard, L. Österlund, P. Thostrup, P.B. Rasmussen, I. Stensgaard, F. Besenbacher, Rev. Sci. Instrum. 72, 3537 (2001).
A. Kolmakov, D.W. Goodman, Rev. Sci. Instrum. 74, 2444 (2003).
M. Rößler, P. Geng, J. Wintterlin, Rev. Sci. Instrum. 76, 023705 (2005).
J.A. Jensen, K.B. Rider, M. Salmeron, G.A. Somorjai, Phys. Rev. Lett. 80, 1228 (1998).
E. Kruse Vestergaard, P. Thostrup, T. An, E. Laegsgaard, I. Stensgaard, B. Hammer, F. Besenbacher, Phys. Rev. Lett 88, 259601 (2002).
P. Cernota, K. Rider, H.A. Yoon, M. Salmeron, G.A. Somorjai, Surf. Sci. 445, 249 (2000).
K.B. Rider, K.S. Hwang, M. Salmeron, G.A. Somorjai, Phys. Rev. Lett. 86, 4330 (2001).
K.B. Rider, K.S. Hwang, M. Salmeron, G.A. Somorjai, J. Am. Chem. Soc. 124, 5588 (2002).
P. Thostrup, E. Kruse Vestergaard, T. An, E. Laegasgaard, F. Besenbacher, J. Chem. Phys. 118, 3724 (2003).
B.J. McIntyre, M. Salmeron, G.A. Somorjai, J. Vac. Sci. Technol. A 11, 1964 (1993).
L. Österlund, P.B. Rasmussen, P. Thostrup, E. Laegsgaard, I. Stensgaard, F. Besenbacher, Phys. Rev. Lett. 86, 460 (2001).
A. Kolmakov, D.W. Goodman, Surf. Sci. 490, L597 (2001).
M. Rössler, S. Günther, J. Wintterlin, J. Phys. Chem. C 111, 2242 (2006).
R.T. Vang, J.-G. Wang, J. Knudsen, J. Schnadt, E. Laegsgaard, I. Stensgaard, F. Besenbacher, J. Phys. Chem. B 109, 14262 (2005).
E.K. Vestergaard, R.T. Vang, J. Knudsen, T.M. Pedersen, T. An, E. Laegsgaard, I. Stensgaard, B. Hammer, F. Besenbacher, Phys. Rev. Lett. 95, 126101 (2005).
M. Montano, M. Salmeron, G.A. Somorjai, Surf. Sci. 600, 1809 (2006).
A. Menzel, K.-C. Chang, V. Komanicky, Y.V. Tolmachev, A.V. Tkachuk, Y.S. Chu, H. You, Phys. Rev. B 95, 035426 (2007).
Y. Jugnet, F.J. Cadete Santos Aires, C. Deranlot, L. Piccolo, J.C. Bertolini, Surf. Sci. 521, L639 (2002).
M.S. Hoogeman, D. Glastra van Loon, R.W.M. Loos, H.G. Ficke, E. de Haas, J.J. van der Linden, H. Zeijlemaker, L. Kuipers, M.F. Chang, M.A.J. Klik, J.W.M. Frenken, Rev. Sci. Instrum. 69, 2072 (1998).
M.J. Rost, D.A. Quist, J.W.M. Frenken, Phys. Rev. Lett. 91, 026101 (2003).
E. Vlieg, I.K. Robinson, K. Kern, Surf. Sci. 233, 248 (1990).
T. Gritsch, D. Coulman, R.J. Behm, G. Ertl, Phys. Rev. Lett. 63, 1086 (1989).
C. Quiros, O. Robach, H. Isern, P. Ordejón, S. Ferrer, Surf. Sci. 522, 161 (2003).
S.C. Bobaru, High-Pressure STM Studies of Oxidation Catalysis, PhD thesis, Leiden University, Leiden, the Netherlands, 2006.
M.D. Ackermann, B.L.M. Hendriksen, O. Robach, S.C. Bobaru, I. Popa, C. Quiros, H. Kim, S. Ferrer, J.W.M. Frenken, unpublished.
K. Reuter, M. Scheffler, Phys. Rev. B 65, 035406 (2001).
K. Reuter, M. Scheffler, Phys. Rev. Lett. 90, 046103 (2003).
K. Reuter, M. Scheffler, Phys. Rev. B 68, 045407 (2003).
P. Mars, D.W. van Krevelen, Chem. Eng. Sci. 3, 41 (1954).
G.A. Somorjai, Introduction to Surface Chemistry and Catalysis (Wiley-Interscience, New York, 1994).
B.L.M. Hendriksen, S.C. Bobaru, J.W.M. Frenken, Top. Catal. 36, 43 (2005).
M.D. Ackermann, T.M. Pedersen, B.L.M. Hendriksen, O. Robach, S.C. Bobaru, I. Popa, C. Quiros, H. Kim, B. Hammer, S. Ferrer, J.W.M. Frenken, Phys. Rev. Lett. 95, 255505 (2005).
STM movies can be viewed at Interface Physics Group Web site, Leiden University, www.physics.leidenuniv.nl/sections/cm/ip (accessed November 2007).
B.L.M. Hendriksen, S.C. Bobaru, J.W.M. Frenken, Surf. Sci. 552, 229 (2004).
M.J. Rost, L. Crama, P. Schakel, E. van Tol, G.B.E.M. van Velzen-Williams, C.F. Overgauw, H. ter Horst, H. Dekker, B. Okhuijsen, M. Seynen, A. Vijftigschild, P. Han, A.J. Katan, K. Schoots, R. Schumm, W.A. van Loo, T.H. Oosterkamp, J.W.M. Frenken, Rev. Sci. Instrum. 76, 053710 (2005).
J.W.M. Frenken, T.H. Oosterkamp, B.L.M. Hendriksen, M.J. Rost, Mater. Today 8, 20 (2005).
K. Reuter, D. Frenkel, M. Scheffler, Phys. Rev. Lett. 93, 116105 (2004).
J. Rogal, K. Reuter, M. Scheffler, Phys. Rev. B 75, 205433 (2007).
J. Rogal, K. Reuter, M. Scheffler, Phys. Rev. Lett. 98, 046101 (2007).
Rights and permissions
About this article
Cite this article
Frenken, J., Hendriksen, B. The Reactor-STM: A Real-Space Probe for Operando Nanocatalysis. MRS Bulletin 32, 1015–1021 (2007). https://doi.org/10.1557/mrs2007.210
Published:
Issue Date:
DOI: https://doi.org/10.1557/mrs2007.210