High NOx Reduction Activity of an Ultrathin Zirconia Film Covering a Cu Surface: A DFT Study

Koga, Hiroaki; Tada, Kohei; Hayashi, Akihito; Ato, Yoshinori; Okumura, Mitsutaka

doi:10.1007/s10562-017-2086-5

Cited by 20 publications

(12 citation statements)

References 46 publications

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“…Our calculation results for CO oxidation over two‐layer rutile(110) supported on two‐layer Au(112) with the rutile TiO 2 [001] ǁ Au[110] orientation also showed that CO oxidation can proceed on the surface of rutile(110) in this model catalyst 50. This was due to electron transfer from Au metal to the substrate through TiO 2 , while a similar effect was proposed by Freund and co‐workers 109.…”

Section: Discussionsupporting

confidence: 82%

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Advances in Gold Catalysis and Understanding the Catalytic Mechanism

Ishida

Koga

Okumura

et al. 2016

The Chemical Record

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When gold is deposited as nanoparticles (NPs) with mean diameters of 2-5 nm or clusters with mean diameters below 2 nm onto a variety of supports such as metal oxides, carbons, polymers, etc., the supported Au NPs exhibit unique catalytic properties, while bulk Au is almost inert as a catalyst. A lot of research works indicate that the key factors of the catalysis by supported Au NPs are the selection of the supports, the control of the Au NP size, the shape of the Au NPs, and the strong junction between Au NPs and the supports, because the perimeter zone around Au NPs acts as the active site for many reactions. In order to elucidate the origin of catalysis by supported Au NPs, the interplay between physicochemical analysis, computational studies, and rational experiments for catalysis by supported Au NPs is becoming more and more important. This article summarizes our experiences and progress in such interplay.

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Section: Discussionsupporting

confidence: 82%

“…Concurrently, the occupation of the antibonding orbitals weakens the O–O bond, activating O 2 for CO oxidation. A similar mechanism has been found by the majority of DFT studies,44–46 including ours 47–50. The supported Au clusters thus serve as electron donors to O 2 , as oxygen vacancies do.…”

Section: Co Oxidationsupporting

confidence: 84%

Advances in Gold Catalysis and Understanding the Catalytic Mechanism

Ishida

Koga

Okumura

et al. 2016

The Chemical Record

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“…Dimerization and its reverse process, homolytic cleavage, are basic chemical reactions, which are important for investigating heterogeneous reactions on surfaces [1,2,3,4,5,6,7,8,9,10,11,12]. For instance, dissociation of hydrogen on metal surfaces is an elementary reaction for hydrogenation by heterogeneous metal catalysts, and dimerization of nitrogen atoms and nitric monoxide (NO) molecules are regarded as elemental reactions for NO x elimination from exhaust gases.…”

Section: Introductionmentioning

confidence: 99%

Extent of Spin Contamination Errors in DFT/Plane-wave Calculation of Surfaces: A Case of Au Atom Aggregation on a MgO Surface

et al. 2019

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The aggregation of Au atoms onto a Au dimer (Au2) on a MgO (001) surface was calculated by restricted (spin-un-polarized) and unrestricted (spin-polarized) density functional theory calculations with a plane-wave basis and the approximate spin projection (AP) method. The unrestricted calculations included spin contamination errors of 0.0–0.1 eV, and the errors were removed using the AP method. The potential energy curves for the aggregation reaction estimated by the restricted and unrestricted calculations were different owing to the estimation of the open-shell structure by the unrestricted calculations. These results show the importance of the open-shell structure and correction of the spin contamination error for the calculation of small-cluster-aggregations and molecule dimerization on surfaces.

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“…Besides, ZrO 2 also provides abundant NO x adsorption sites [13][14][15], which is beneficial for NO reduction. Koga et al discovered that c-ZrO 2 (110) ultrathin film covering a Cu surface exhibited high NO x reduction activity [16].…”

Section: Introductionmentioning

confidence: 99%

Catalytic Reaction Mechanism of NO–CO on the ZrO2 (110) and (111) Surfaces

Cao

Zhang

Wang

et al. 2019

IJMS

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Due to the large population of vehicles, significant amounts of carbon monoxide (CO), nitrogen oxides (NOx), and unburned hydrocarbons (HC) are emitted into the atmosphere, causing serious pollution to the environment. The use of catalysis prevents the exhaust from entering the atmosphere. To better understand the catalytic mechanism, it is necessary to establish a detailed chemical reaction mechanism. In this study, the adsorption behaviors of CO and NO, the reaction of NO reduction with CO on the ZrO2 (110) and (111) surfaces was performed through periodic density functional theory (DFT) calculations. The detailed mechanism for CO2 and N2 formation mainly involved two intermediates N2O complexes and NCO species. Moreover, the existence of oxygen vacancies was crucial for NO reduction reactions. From the calculated energy, it was found that the pathway involving NCO intermediate interaction occurring on the ZrO2 (110) surface was most favorable. Gas phase N2O formation and dissociation were also considered in this study. The results indicated the role of reaction intermediates NCO and N2O in catalytic reactions, which could solve the key scientific problems and disputes existing in the current experiments.

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High NOx Reduction Activity of an Ultrathin Zirconia Film Covering a Cu Surface: A DFT Study

Cited by 20 publications

References 46 publications

Advances in Gold Catalysis and Understanding the Catalytic Mechanism

Advances in Gold Catalysis and Understanding the Catalytic Mechanism

Extent of Spin Contamination Errors in DFT/Plane-wave Calculation of Surfaces: A Case of Au Atom Aggregation on a MgO Surface

Catalytic Reaction Mechanism of NO–CO on the ZrO2 (110) and (111) Surfaces

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