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Unraveling Catalytic Mechanisms for CO Oxidation on Boron-Doped Fullerene: A Computational Study.

ABSTRACT: By means of spin-polarized density functional theory (DFT) computations, we unravel the reaction mechanisms of catalytic CO oxidation on B-doped fullerene. It is shown that O2 species favors to be chemically adsorbed via side-on configuration at the hex-C-B site with an adsorption energy of -1.07 eV. Two traditional pathways, Eley-Rideal (ER) and Langmuir-Hinshelwood (LH) mechanisms, are considered for the CO oxidation starting from O2 adsorption. CO species is able to bind at the B-top site of the B-doped fullerene with an adsorption energy of -0.78 eV. Therefore, CO oxidation that occurs starting from CO adsorption is also taken into account. Second reaction of CO oxidation occurs by the reaction of CO + O ? CO2 with a very high energy barrier of 1.56 eV. A trimolecular Eley-Rideal (TER) pathway is proposed to avoid leaving the O atom on the B-doped fullerene after the first CO oxidation. These predictions manifest that boron-doped fullerene is a potential metal-free catalyst for CO oxidation.

SUBMITTER: Chen KY

PROVIDER: S-EPMC7659142 | biostudies-literature | 2020 Nov

REPOSITORIES: biostudies-literature

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Unraveling Catalytic Mechanisms for CO Oxidation on Boron-Doped Fullerene: A Computational Study.

Chen Kai-Yang KY Wu Shiuan-Yau SY Chen Hsin-Tsung HT

ACS omega 20201102 44

By means of spin-polarized density functional theory (DFT) computations, we unravel the reaction mechanisms of catalytic CO oxidation on B-doped fullerene. It is shown that O<sub>2</sub> species favors to be chemically adsorbed via side-on configuration at the hex-C-B site with an adsorption energy of -1.07 eV. Two traditional pathways, Eley-Rideal (ER) and Langmuir-Hinshelwood (LH) mechanisms, are considered for the CO oxidation starting from O<sub>2</sub> adsorption. CO species is able to bind ...[more]

PMID: 33195940

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Project description: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 CeO2 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-1) follows the order Cu-Ce-O > Ce-Co-O > Ni-Ce-O > Mn-Ce-O > Fe-Ce-O > Ce-Zn-O > CeO2. Participation of mobile lattice oxygen species in the CO/O2 reaction does occur, the extent of which is heteroatom-dependent. For that, state-of-the-art transient isotopic 18O-labeled experiments involving 16O/18O exchange followed by step-gas CO/Ar or CO/O2/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 Olattice mobility was also found as well as its participation (as expressed with the α descriptor) in the reaction, following the order αCu > αCo> αMn > αZn. 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 CeO2 surface is more favorable (-16.63 eV), followed by Co, Mn, Zn (-14.46, -4.90, and -4.24 eV, respectively), and pure CeO2 (-0.63 eV). Also, copper compensates almost three times more charge (0.37e-) compared to Co and Mn, ca. 0.13e- and 0.10e-, 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 (Oa species) of different extents and of different populations of Oa species.

Dataset Information

Unraveling Catalytic Mechanisms for CO Oxidation on Boron-Doped Fullerene: A Computational Study.

Publications

Unraveling Catalytic Mechanisms for CO Oxidation on Boron-Doped Fullerene: A Computational Study.

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