Characteristics of Desulfation Behavior for Pre-Sulfated Pt-BaO/CeO2 Lean NOx Trap Catalysts: The Role of the CeO2 Support

Journal Article · Thu Dec 17 04:00:00 EST 2009 · Journal of Physical Chemistry C, 113(50):21123-21129

DOI:https://doi.org/10.1021/jp9062548· OSTI ID:972334

Kim, Do Heui; Kwak, Ja Hun; Szanyi, Janos; Wang, Xianqin; Li, Guosheng; Hanson, Jonathan C; Peden, Charles HF

The desulfation of pre-sulfated Pt-BaO/CeO2 lean NOx trap catalysts was investigated by H2 TPRX (temperature programmed reaction), in-situ TR-XRD (time-resolved X-ray diffraction) and in-situ S K-edge XANES (X-ray absorption near edge spectroscopy) techniques. Compared with Pt-BaO/Al2O3 materials, the reductive treatment in H2 for a CeO2 supported sample up to 1073 K hardly removes any sulfur species. However, the results of in-situ TR-XRD measurements demonstrate that the quantity of a BaS phase formed on Pt-BaO/CeO2 is much smaller than that on Pt-BaO/Al2O3, implying that the formation of BaS crystallites, which occurs during the reduction from sulfate (SO42-) to sulfide (S2-), is significantly suppressed in the CeO2-supported catalyst. As the desulfation temperature increases under reducing conditions (in H2), the in-situ S XANES spectra show that, compared with alumina-supported samples, the reduction temperature for sulfates (S6+) decreases by about 150 K. Concomitantly, the formation of sulfur species with lower oxidation states (S2- - S4+) is enhanced. The step jump of S XANES spectra before and after desulfation are very similar, implying that the amount of sulfur-containing species removed during the reductive treatment is negligible, in agreement with the results of H2 TPRX. These results suggest that H2S produced by the reduction of BaSO4 is readily re-adsorbed on the ceria support to form ceria-sulfur complexes (e.g. CeS2). The high affinity of ceria for H2S, combined with the ease of reducibility of the ceria support gives rise to various oxidation states of sulfur after high temperature H2 treatments. Thus, the results of this study clearly show that the ceria support strongly affects the overall desulfation mechanism. The intrinsic role of the ceria support during desulfation, and its effect on the overall NOx storage processes are discussed on the basis of the characterization results obtained here.

• Research Organization: Pacific Northwest National Laboratory (PNNL), Richland, WA (US), Environmental Molecular Sciences Laboratory (EMSL)
• Sponsoring Organization: USDOE
• DOE Contract Number: AC05-76RL01830
• OSTI ID: 972334
• Report Number(s): PNNL-SA-67217; 35404; 19800; 17507; VT0401000
• Journal Information: Journal of Physical Chemistry C, 113(50):21123-21129, Journal Name: Journal of Physical Chemistry C, 113(50):21123-21129 Journal Issue: 50 Vol. 113; ISSN 1932-7447
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
ABSORPTION
AFFINITY
CATALYSTS
Environmental Molecular Sciences Laboratory
SPECTRA
SPECTROSCOPY
STORAGE
SULFATES
SULFIDES
SULFUR
VALENCE
X-RAY DIFFRACTION