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Tang, Yuanhao; Zhang, Hua; Cui, Lixia; Ouyang, Chuying; Shi, Siqi; Tang, Weihua; Li, Hong; Lee, Jong‐Sook; Chen, Liquan

doi:10.1103/physrevb.82.125104

Cited by 117 publications

(58 citation statements)

References 67 publications

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“…For the Mn dopant in ceria, a U-correction for the Mn d-states must be added to correctly represent the electronic structure of Mn-doped CeO 2 [2,3,13,[17][18][19]34]. A U-value of 4 eV on the d-states of Mn has been confirmed to properly represent the Mn oxidation state under reducing conditions, in agreement with both x-ray adsorption near edge spectroscopy (XANES) and DFT results using the hybrid functional HSE06 [2,3].…”

Section: Electronic Structure Methodsmentioning

confidence: 69%

“…Compared with other oxides and metals that can be mixed with CeO 2 , MnO x can increase the stability of the catalyst [6], and is less expensive than other metals (Ag, Au, Pt, Pd) that can increase the activity of ceria [13][14][15][16]. Cen et al [17], Gupta et al [18], and Tang et al [19] all showed that the addition of Mn to the ceria surface increases the reducibility of the surface. Mn will dope into the lattice of ceria with oxygen vacancies present and also increases the reducibility and catalytic activity of the surface [3,13].…”

Section: Introductionmentioning

confidence: 95%

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Catalytic propane reforming mechanism over Mn-Doped CeO2 (111)

Krcha

Janik²

2015

Surface Science

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a b s t r a c t a r t i c l e i n f o Available online xxxx Keywords: Ceria DFT + U Manganese Doped oxide ReformingMnO x /CeO x mixed oxide systems exhibit encouraging hydrocarbon oxidation activity, without the inclusion of a noble metal. Using density functional theory (DFT) methods, we examined the oxidative reforming path of propane over the Mn-doped CeO 2 (1 1 1) surface. A plausible set of elementary reaction steps are identified for conversion of propane to CO/CO 2 and H 2 /H 2 O over the oxide surface. The rate-limiting reaction process may vary with redox conditions, with C-H dissociation limiting under more oxidizing conditions and more complex reaction sequences, including surface re-oxidation, limiting under highly reducing conditions. The possibility of intermediate desorption from the surface during the reforming process is low, with desorption energies of the intermediates being much less favorable than further surface reactions until CO/CO 2 products are formed. The reforming paths over Mn-doped ceria are similar to those previously identified over Zr-doped ceria. The extent of surface reduction and the electronic structure of the surface intermediates are examined.

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Section: Electronic Structure Methodsmentioning

confidence: 69%

Section: Introductionmentioning

confidence: 95%

Catalytic propane reforming mechanism over Mn-Doped CeO2 (111)

Krcha

Janik²

2015

Surface Science

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“…Whereas, in the case of aliovalent dopants the decrease in the defect formation energy is due to the structural distortion, and also due to the electronic modifications, which result in the generation of extra oxygen vacancies [24,25]. On the other hand, in aliovalent metal ions, bivalent dopants like Ca 2+ are not preferable.…”

Section: Introductionmentioning

confidence: 94%

Influence of isovalent and aliovalent dopants on the reactivity of cerium oxide for catalytic applications

2015

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“…Doping of an aliovalent cation in place of Ce leads to the reduction and formation of oxygen vacancies 19,20,21 . On the introduction of a dopant, oxygen vacancies are formed by both structural and electronic modifications in ceria 22,23 . An increase in the dopant concentration results into a greater likelihood of vacancy clustering 24 .…”

Section: Introductionmentioning

confidence: 99%

Role of Reduced CeO₂(110) Surface for CO₂ Reduction to CO and Methanol

et al. 2016

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Density functional theory (DFT) calculations were performed to study the mechanism of carbon dioxide (CO 2 ) reduction to carbon monoxide (CO) and methanol (CH 3 OH) on CeO 2 (110) surface. CO 2 dissociates to CO on interacting with the oxygen vacancy on reduced ceria surface.The oxygen atom heals the vacancy site and regenerates the stoichiometric surface via a redox mechanism with intrinsic activation and reaction energies of 259.2 kJ/mole and 238.6 kJ/mole respectively. Lateral interaction of oxygen vacancies were studied by the generation of two oxygen vacancies per unit of CeO 2 surface. Compared to a single isolated vacancy, the activation and reaction energies of CO 2 dissociation on a di-vacancy were approximately reduced to half of its value. Hydrogen atom co-adsorbed on the surface was observed to assist CO 2 dissociation by forming a carboxyl intermediate, CO 2 +H→COOH (∆E act = 39.0 kJ/mole, ∆H = -69.2 kJ/mole) which on subsequent dissociation produces CO via the redox mechanism. On hydrogenation, CO is likely to produce methanol. The energetics of CO hydrogenation to produce methanol showed exothermic steps with activation barriers comparable to the DFT calculations reported for Cu (111) and CeO 2-x /Cu(111) interface. While on the stoichiometric surface, COOH dissociation COOH→CO+OH (∆E act = 55.6 kJ/mole, ∆H =5.7 kJ/mole) is likely to be difficult as compared to rest of the elementary steps, whereas on the reduced surface the energetics of the same step were significantly lowered (∆E act = 47.4 kJ/mole, ∆H = -80.4 kJ/mole). In comparison, hydrogenation of methoxy, H 3 CO+H→H 3 COH, appears to be relatively difficult (∆E act = 58.7 kJ/mole) on the reduced surface.

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First-principles investigation on redox properties ofM-dopedCeO2(M=

Cited by 117 publications

References 67 publications

Catalytic propane reforming mechanism over Mn-Doped CeO2 (111)

Catalytic propane reforming mechanism over Mn-Doped CeO2 (111)

Influence of isovalent and aliovalent dopants on the reactivity of cerium oxide for catalytic applications

Role of Reduced CeO₂(110) Surface for CO₂ Reduction to CO and Methanol

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First-principles investigation on redox properties ofM-dopedCeO2(M=

Cited by 117 publications

References 67 publications

Catalytic propane reforming mechanism over Mn-Doped CeO2 (111)

Catalytic propane reforming mechanism over Mn-Doped CeO2 (111)

Influence of isovalent and aliovalent dopants on the reactivity of cerium oxide for catalytic applications

Role of Reduced CeO2(110) Surface for CO2 Reduction to CO and Methanol

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Product

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Role of Reduced CeO₂(110) Surface for CO₂ Reduction to CO and Methanol