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Design Aspects of Doped CeO 2 for Low-Temperature Catalytic CO Oxidation: Transient Kinetics and DFT Approach.
- Source :
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ACS applied materials & interfaces [ACS Appl Mater Interfaces] 2021 May 19; Vol. 13 (19), pp. 22391-22415. Date of Electronic Publication: 2021 Apr 09. - Publication Year :
- 2021
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Abstract
- CO elimination through oxidation over highly active and cost-effective catalysts is a way forward for many processes of industrial and environmental importance. In this study, doped CeO <subscript>2</subscript> with transition metals (TM = Cu, Co, Mn, Fe, Ni, Zr, and Zn) at a level of 20 at. % was tested for CO oxidation. The oxides were prepared using microwave-assisted sol-gel synthesis to improve catalyst's performance for the reaction of interest. The effect of heteroatoms on the physicochemical properties (structure, morphology, porosity, and reducibility) of the binary oxides M-Ce-O was meticulously investigated and correlated to their CO oxidation activity. It was found that the catalytic activity (per gram basis or TOF, s <superscript>-1</superscript> ) follows the order Cu-Ce-O > Ce-Co-O > Ni-Ce-O > Mn-Ce-O > Fe-Ce-O > Ce-Zn-O > CeO <subscript>2</subscript> . Participation of mobile lattice oxygen species in the CO/O <subscript>2</subscript> reaction does occur, the extent of which is heteroatom-dependent. For that, state-of-the-art transient isotopic <superscript>18</superscript> O-labeled experiments involving <superscript>16</superscript> O/ <superscript>18</superscript> O exchange followed by step-gas CO/Ar or CO/O <subscript>2</subscript> /Ar switches were used to quantify the contribution of lattice oxygen to the reaction. SSITKA-DRIFTS studies probed the formation of carbonates while validating the Mars-van Krevelen (MvK) mechanism. Scanning transmission electron microscopy-high-angle annular dark field imaging coupled with energy-dispersive spectroscopy proved that the elemental composition of dopants in the individual nanoparticle of ceria is less than their composition at a larger scale, allowing the assessment of the doping efficacy. Despite the similar structural features of the catalysts, a clear difference in the O <subscript>lattice</subscript> mobility was also found as well as its participation (as expressed with the α descriptor) in the reaction, following the order α <subscript>Cu</subscript> > α <subscript>Co</subscript> > α <subscript>Mn</subscript> > α <subscript>Zn</subscript> . Kinetic studies showed that it is rather the pre-exponential (entropic) factor and not the lowering of activation energy that justifies the order of activity of the solids. DFT calculations showed that the adsorption of CO on the Cu-doped CeO <subscript>2</subscript> surface is more favorable (-16.63 eV), followed by Co, Mn, Zn (-14.46, -4.90, and -4.24 eV, respectively), and pure CeO <subscript>2</subscript> (-0.63 eV). Also, copper compensates almost three times more charge (0.37 e <superscript>-</superscript> ) compared to Co and Mn, ca. 0.13 e <superscript>-</superscript> and 0.10 e <superscript>-</superscript> , respectively, corroborating for its tendency to be reduced. Surface analysis (X-ray photoelectron spectroscopy), apart from the oxidation state of the elements, revealed a heteroatom-ceria surface interaction (O <subscript>a</subscript> species) of different extents and of different populations of O <subscript>a</subscript> species.
Details
- Language :
- English
- ISSN :
- 1944-8252
- Volume :
- 13
- Issue :
- 19
- Database :
- MEDLINE
- Journal :
- ACS applied materials & interfaces
- Publication Type :
- Academic Journal
- Accession number :
- 33834768
- Full Text :
- https://doi.org/10.1021/acsami.1c02934