Hostname: page-component-7bb8b95d7b-fmk2r Total loading time: 0 Render date: 2024-09-20T13:05:56.376Z Has data issue: false hasContentIssue false
  • English
  • Français

Analysis of Catalytic Gas Products Using Electron Energy-Loss Spectroscopy and Residual Gas Analysis for Operando Transmission Electron Microscopy

Published online by Cambridge University Press:  12 May 2014

Benjamin K. Miller  and
Peter A. Crozier
Benjamin K. Miller
Affiliation:
School for Engineering of Matter, Transport and Energy, Arizona State University, Tempe, AZ 85287-6106, USA
Peter A. Crozier*
Affiliation:
School for Engineering of Matter, Transport and Energy, Arizona State University, Tempe, AZ 85287-6106, USA
*
*Corresponding author. crozier@asu.edu
Get access

Abstract

Operando transmission electron microscopy (TEM) of catalytic reactions requires that the gas composition inside the TEM be known during the in situ reaction. Two techniques for measuring gas composition inside the environmental TEM are described and compared here. First, electron energy-loss spectroscopy, both in the low-loss and core-loss regions of the spectrum was utilized. The data were quantified using a linear combination of reference spectra from individual gasses to fit a mixture spectrum. Mass spectrometry using a residual gas analyzer was also used to quantify the gas inside the environmental cell. Both electron energy-loss spectroscopy and residual gas analysis were applied simultaneously to a known 50/50 mixture of CO and CO2, so the results from the two techniques could be compared and evaluated. An operando TEM experiment was performed using a Ru catalyst supported on silica spheres and loaded into the TEM on a specially developed porous pellet TEM sample. Both techniques were used to monitor the conversion of CO to CO2 over the catalyst, while simultaneous atomic resolution imaging of the catalyst was performed.

Keywords

operandoin situ TEMenvironmental TEM (ETEM)mass spectrometryEELScatalyst
Type
EDGE Special Issue
Information
Microscopy and Microanalysis , Volume 20 , Issue 3 , June 2014 , pp. 815 - 824
Copyright
© Microscopy Society of America 2014 

Access options

Get access to the full version of this content by using one of the access options below. (Log in options will check for institutional or personal access. Content may require purchase if you do not have access.)

References

Bañares, M.A. & Wachs, I.E. (2002). Molecular structures of supported metal oxide catalysts under different environments. J Raman Spectrosc 33, 359–380.CrossRefGoogle Scholar
Behrens, M., Studt, F., Kasatkin, I., Kuhl, S., Havecker, M., Abild-Pedersen, F., Zander, S., Girgsdies, F., Kurr, P., Kniep, B.-L., Tovar, M., Fischer, R.W., Norskov, J.K. & Schlogl, R. (2012). The active site of methanol synthesis over Cu/ZnO/Al2O3 industrial catalysts. Science 336, 893–897.Google Scholar
Bell, A.T., Gates, B.C., Ray, D. & Thompson, M.R. (2008). Basic research needs: Catalysis for energy, US Department of Energy Basic Energy Sciences Workshop. http://science.energy.gov/~/media/bes/pdf/reports/files/cat_rpt.pdf Google Scholar
Benson, E.E., Kubiak, C.P., Sathrum, A.J. & Smieja, J.M. (2009). Electrocatalytic and homogeneous approaches to conversion of CO2 to liquid fuels. Chem Soc Rev 38, 89–99.CrossRefGoogle ScholarPubMed
Cheng, X., Shi, Z., Glass, N., Zhang, L., Zhang, J., Song, D., Liu, Z.-S., Wang, H. & Shen, J. (2007). A review of PEM hydrogen fuel cell contamination: Impacts, mechanisms, and mitigation. J Power Sources 165, 739–756.CrossRefGoogle Scholar
Chenna, S., Banerjee, R. & Crozier, P.A. (2011). Atomic-scale observation of the Ni activation process for partial oxidation of methane using in situ environmental TEM. Chem Cat Chem 3, 1051–1059.Google Scholar
Chenna, S. & Crozier, P.A. (2012 a). In situ environmental transmission electron microscopy to determine transformation pathways in supported Ni nanoparticles. Micron 43, 1188–1194.Google Scholar
Chenna, S. & Crozier, P.A. (2012 b). Operando transmission electron microscopy: A technique for detection of catalysis using electron energy-loss spectroscopy in the transmission electron microscope. ACS Catal 2, 2395–2402.Google Scholar
Creemer, J.F., Helveg, S., Hoveling, G.H., Ullmann, S., Molenbroek, A.M., Sarro, P.M. & Zandbergen, H.W. (2008). Atomic-scale electron microscopy at ambient pressure. Ultramicroscopy 108, 993–998.CrossRefGoogle ScholarPubMed
Crozier, P.A. (2011). Nanocharacterization of heterogeneous catalysts by ex situ and in situ STEM. In Scanning Transmission Electron Microscopy, Pennycook, S.J. & Nellist, P.D. (Eds.), pp. 537–582. New York, NY: Springer New York.Google Scholar
Crozier, P.A. & Chenna, S. (2011). In situ analysis of gas composition by electron energy-loss spectroscopy for environmental transmission electron microscopy. Ultramicroscopy 111, 177–185.Google Scholar
Flege, J., Hrbek, J. & Sutter, P. (2008). Structural imaging of surface oxidation and oxidation catalysis on Ru(0001). Phys Rev B 78, 165407–1–165407–5.Google Scholar
Gao, F., Wang, Y., Cai, Y. & Goodman, D.W. (2009). CO oxidation over Ru(0001) at near-atmospheric pressures: From chemisorbed oxygen to RuO2 . Surf Sci 603, 1126–1134.Google Scholar
Goodman, D.W., Peden, C.H.F. & Chen, M.S. (2007 a). CO oxidation on ruthenium: The nature of the active catalytic surface. Surf Sci 601, L124–L126.Google Scholar
Goodman, D.W., Peden, C.H.F. & Chen, M.S. (2007 b). Reply to comment on “CO oxidation on ruthenium: The nature of the active catalytic surface” by H. Over, M. Muhler, A.P. Seitsonen. Surf Sci 601, 5663–5665.CrossRefGoogle Scholar
Gorte, R.J. & Vohs, J.M. (2011). Catalysis in solid oxide fuel cells. Annu Rev Chem Biomol Eng 2, 9–30.Google Scholar
Helveg, S., López-Cartes, C., Sehested, J., Hansen, P.L., Clausen, B.S., Rostrup-Nielsen, J.R., Abild-Pedersen, F. & Nørskov, J.K. (2004). Atomic-scale imaging of carbon nanofibre growth. Nature 427, 426–429.Google Scholar
Jinschek, J.R. & Helveg, S. (2012). Image resolution and sensitivity in an environmental transmission electron microscope. Micron 43, 1156–1168.Google Scholar
Kudo, A. & Miseki, Y. (2009). Heterogeneous photocatalyst materials for water splitting. Chem Soc Rev 38, 253–278.Google Scholar
Mitchell, D.R.G. & Schaffer, B. (2005). Scripting-customised microscopy tools for Digital MicrographTM . Ultramicroscopy 103, 319–332.Google Scholar
O’Hanlon, J. (2003). A user’s guide to vacuum technology. 3rd ed. Hoboken NJ: Wiley-Interscience.CrossRefGoogle Scholar
Over, H., Balmes, O. & Lundgren, E. (2009). Direct comparison of the reactivity of the non-oxidic phase of Ru(0001) and the RuO2 phase in the CO oxidation reaction. Surf Sci 603, 298–303.Google Scholar
Over, H. & Muhler, M. (2003). Catalytic CO oxidation over ruthenium—bridging the pressure gap. Prog Surf Sci 72, 3–17.Google Scholar
Over, H., Muhler, M. & Seitsonen, A.P. (2007). Comment on “CO oxidation on ruthenium: The nature of the active catalytic surface” by D.W. Goodman, C.H.F. Peden, M.S. Chen. Surf Sci 601, 5659–5662.Google Scholar
Rosenthal, D., Girgsdies, F., Timpe, O., Blume, R., Weinberg, G., Teschner, D. & Schlögl, R. (2009). On the CO-oxidation over oxygenated Ruthenium. Z Phys Chem 223, 183–208.Google Scholar
Sharma, R. (2012). Experimental set up for in situ transmission electron microscopy observations of chemical processes. Micron 43, 1147–1155.Google Scholar
Sharma, R. & Crozier, P.A. (2005). Environmental transmission electron microscopy in nanotechnology. In Handbook of Microscopy for Nanotechnology, Yao, N. & Wang, Z.L. (Eds.), pp. 531–565. Boston, MA: Kluwer Academic Publishers.Google Scholar
Wagner, J.B., Cavalca, F., Damsgaard, C.D., Duchstein, L.D.L. & Hansen, T.W. (2012). Exploring the environmental transmission electron microscope. Micron 43, 1169–1175.Google Scholar
Yokosawa, T., Alan, T., Pandraud, G., Dam, B. & Zandbergen, H. (2012). In-situ TEM on (de)hydrogenation of Pd at 0.5–4.5 bar hydrogen pressure and 20–400°C. Ultramicroscopy 112, 47–52.Google Scholar