skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Destruction of SO2 on Au and Cu Nanoparticles Dispersed on MgO(100) and CeO2(111)

Abstract

When going from periodic surfaces to isolated clusters or nanoparticles, there is a big increase in the reactivity of Au and Cu toward SO{sub 2}. Density functional calculations indicate that the enhancement in the SO{sub 2} adsorption energy is due to the presence of corner sites (i.e., metal atoms with a low coordination number) and the fluxionality of the nanoparticles. Therefore, small Au particles bind SO{sub 2} stronger than a periodic Au(100) surface. However, the S ? Au and O ? Au interactions are not strong enough to induce the rupture of the S-O bonds. In contrast, the dissociation of SO{sub 2} on Cu particles is a very exothermic process, even more exothermic than on a periodic Cu(100) surface. Experiments of synchrotron-based high-resolution photoemission and X-ray absorption spectroscopy show big differences in the DeSOx activity of Au and Cu nanoparticles dispersed on MgO(100) and CeO{sub 2}(111). The heat of adsorption of the SO{sub 2} on Au nanoparticles supported on MgO(100) or CeO{sub 2}(111) was 0.2 to 0.4 eV larger than on Au(100) with negligible dissociation of the molecule. The full decomposition of SO{sub 2} was observed only after O vacancies were introduced in the ceria support. The O vacancies inmore » ceria either played a direct role in the dissociation of SO{sub 2} (cracking of the molecule at the oxide-metal interface) or enhanced the chemical activity of the supported Au nanoparticles. The addition of Cu particles to MgO(100) or CeO{sub 2}(111) generates systems that are extremely active for the destruction of SO{sub 2}. At 100-150 K, the SO{sub 2} adsorbs molecularly on the supported Cu particles. Heating to temperatures above 200 K leads to massive dissociation of the SO{sub 2}. A comparison of the behavior of SO{sub 2} on Cu/MgO(100) and Cu/CeO{sub 2-x}(111) shows how important the reducibility of the oxide support in DeSOx operations can be.« less

Authors:
; ; ; ;
Publication Date:
Research Org.:
Brookhaven National Laboratory (BNL) National Synchrotron Light Source
Sponsoring Org.:
DOE - Office Of Science
OSTI Identifier:
1004643
Report Number(s):
BNL-90238-2011-JA
Journal ID: ISSN 1089-5639; ISSN 1520-5215; JPCAFH; R&D Project: CO-009; KC0302010; TRN: US201104%%1008
DOE Contract Number:  
DE-AC02-98CH10886
Resource Type:
Journal Article
Journal Name:
Journal of Physical Chemistry A: Molecules, Spectroscopy, Kinetics, Environment, amp General Theory
Additional Journal Information:
Journal Volume: 114; Journal Issue: 111; Journal ID: ISSN 1089-5639
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ABSORPTION SPECTROSCOPY; ADSORPTION; ADSORPTION HEAT; ATOMS; COORDINATION NUMBER; DISSOCIATION; FUNCTIONALS; HEATING; OXIDES; PHOTOEMISSION; RUPTURES; THERMODYNAMIC ACTIVITY; VACANCIES; inorganic; organic; physical and analytical chemistry; national synchrotron light source

Citation Formats

Rodriguez, J A, Liu, P, Pérez, M, Liu, G, and Hrbek, J. Destruction of SO2 on Au and Cu Nanoparticles Dispersed on MgO(100) and CeO2(111). United States: N. p., 2010. Web. doi:10.1021/jp905761s.
Rodriguez, J A, Liu, P, Pérez, M, Liu, G, & Hrbek, J. Destruction of SO2 on Au and Cu Nanoparticles Dispersed on MgO(100) and CeO2(111). United States. https://doi.org/10.1021/jp905761s
Rodriguez, J A, Liu, P, Pérez, M, Liu, G, and Hrbek, J. Thu . "Destruction of SO2 on Au and Cu Nanoparticles Dispersed on MgO(100) and CeO2(111)". United States. https://doi.org/10.1021/jp905761s.
@article{osti_1004643,
title = {Destruction of SO2 on Au and Cu Nanoparticles Dispersed on MgO(100) and CeO2(111)},
author = {Rodriguez, J A and Liu, P and Pérez, M and Liu, G and Hrbek, J},
abstractNote = {When going from periodic surfaces to isolated clusters or nanoparticles, there is a big increase in the reactivity of Au and Cu toward SO{sub 2}. Density functional calculations indicate that the enhancement in the SO{sub 2} adsorption energy is due to the presence of corner sites (i.e., metal atoms with a low coordination number) and the fluxionality of the nanoparticles. Therefore, small Au particles bind SO{sub 2} stronger than a periodic Au(100) surface. However, the S ? Au and O ? Au interactions are not strong enough to induce the rupture of the S-O bonds. In contrast, the dissociation of SO{sub 2} on Cu particles is a very exothermic process, even more exothermic than on a periodic Cu(100) surface. Experiments of synchrotron-based high-resolution photoemission and X-ray absorption spectroscopy show big differences in the DeSOx activity of Au and Cu nanoparticles dispersed on MgO(100) and CeO{sub 2}(111). The heat of adsorption of the SO{sub 2} on Au nanoparticles supported on MgO(100) or CeO{sub 2}(111) was 0.2 to 0.4 eV larger than on Au(100) with negligible dissociation of the molecule. The full decomposition of SO{sub 2} was observed only after O vacancies were introduced in the ceria support. The O vacancies in ceria either played a direct role in the dissociation of SO{sub 2} (cracking of the molecule at the oxide-metal interface) or enhanced the chemical activity of the supported Au nanoparticles. The addition of Cu particles to MgO(100) or CeO{sub 2}(111) generates systems that are extremely active for the destruction of SO{sub 2}. At 100-150 K, the SO{sub 2} adsorbs molecularly on the supported Cu particles. Heating to temperatures above 200 K leads to massive dissociation of the SO{sub 2}. A comparison of the behavior of SO{sub 2} on Cu/MgO(100) and Cu/CeO{sub 2-x}(111) shows how important the reducibility of the oxide support in DeSOx operations can be.},
doi = {10.1021/jp905761s},
url = {https://www.osti.gov/biblio/1004643}, journal = {Journal of Physical Chemistry A: Molecules, Spectroscopy, Kinetics, Environment, amp General Theory},
issn = {1089-5639},
number = 111,
volume = 114,
place = {United States},
year = {2010},
month = {3}
}