Abstract
Sulfated zirconia (S–ZrO2) is a versatile solid acid catalyst that has wide application in hydrocarbon conversion reactions. In our previous work, we have developed well-dispersed ZrO2 nanoparticles supported on multi-walled carbon nanotubes (MWCNT) to form a ZrO2/MWCNT composite, which, upon sulfation, becomes a S–ZrO2/MWCNT solid acid catalyst. While X-ray absorption spectroscopy (XAS) of this composite at the C, O, Zr K-edges has been well studied in our previous reports, XAS at the S K-edge is complicated by the Zr L-edges that bracket the S K-edge. In this study, we have used conventional S XANES, together with first-derivative and third-derivative analysis, to probe the sulfur species formed during the catalyst preparation and their interaction with Zr. We have also designed combined Zr and S XANES, which spans 400 eV and covers all three Zr L-edges and the S K-edge, to study the Zr and S interaction. Such use of multiple-edge XANES to study the S–ZrO2 system at low X-ray energy (2,200–2,600 eV) was first reported in the previous publication of our research group, and in this paper we elaborate on the comprehensive study of our catalyst system using this method.
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Acknowledgments
The authors (C. L., L. P. and G. L. H. of Yale University) are grateful to the DOE, Office of Basic Energy Sciences, grant DE-FG02-01ER15183, and AFOSR MURI grant FA9550-08-0309 for financial support. The use of the Advanced Photon Source, an Office of Science User Facility operated for the U.S. Department of Energy (DOE) Office of Science by Argonne National Laboratory, was supported by the U.S. DOE under Contract No. DE-AC02-06CH11357. Electron Microscopy work was carried out by Dong Su at the Center for Functional Nanomaterials, Brookhaven National Laboratory, which is supported by the U. S. Department of Energy, Office of Basic Energy Sciences, under Contract No. DE-AC02-98CH10886. Use of the National Synchrotron Light Source, Brookhaven National Laboratory, was supported by the U. S. Department of Energy, Office of Science, Office of Basic Energy Sciences, under Contract No. DE-AC02-98CH10886, and we wish to thank the beam line scientists Dario Arena, George Sterbinsky, and Jing Liu of U4B for their onsite help. We would also like to thank Fang Fang, Gayatri Keskar, Magdalena Majewska, Fang Ren, and Nan Yi of our research group, and Hong Wang of Nanyang Technological University (Singapore) for their assistance and help in collecting data on the beamlines.
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Liu, C., Bolin, T., Northrup, P. et al. Combined Zr and S XANES Analysis on S–ZrO2/MWCNT Solid Acid Catalyst. Top Catal 57, 693–705 (2014). https://doi.org/10.1007/s11244-013-0226-8
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DOI: https://doi.org/10.1007/s11244-013-0226-8