Dissociation of N2O promoted by Rh6 clusters. A ZORA/DFT/PBE study

Francisco-Rodriguez, H.I.; Bertin, V.; Agacino, Esther; Poulain, E.; Castro, Miguel

doi:10.1016/j.molcata.2015.06.005

Cited by 8 publications

(19 citation statements)

References 39 publications

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“…We have validated this method in previous works, obtaining good results for the interaction of Rh 5 and Rh 6 with N 2 O , and for other transition metals. The ground state and low-lying excited state geometries and spin multiplicities of the Rh 6 – and Rh 6 + ions were determined using the geometries previously identified for the neutral Rh 6 particle as inputs . We have obtained that structures around octahedral and triangular prism forms define the ground states of Rh 6 – and Rh 6 + , at the PBE/ZORA level of theory.…”

Section: Introductionmentioning

confidence: 61%

“…The exchange-correlation was taken into account with the PBE functional, which is free of empirical parameters . We have validated this method in previous works, obtaining good results for the interaction of Rh 5 and Rh 6 with N 2 O , and for other transition metals. The ground state and low-lying excited state geometries and spin multiplicities of the Rh 6 – and Rh 6 + ions were determined using the geometries previously identified for the neutral Rh 6 particle as inputs .…”

Section: Introductionmentioning

confidence: 86%

“…By means of the ZORA/PBE method, we have studied the reduction of N 2 O on neutral Rh 5 and Rh 6 clusters. , It was found that a square pyramid, in a sextet, defines the ground state (GS) of Rh 5 . This state, jointly with the degenerate quartet and octet, is active for the N 2 O reaction.…”

Section: Introductionmentioning

confidence: 99%

“…In the case of Rh 5 , the 4d orbital energies fall in between those of HOMO and LUMO of N 2 O. For neutral Rh 6 , there are many degenerate states, of different geometries (octahedral and triangular prism) and multiplicities (1 and 7), which are active to reduce N 2 O …”

Section: Introductionmentioning

confidence: 99%

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Charge and Geometrical Effects on the Catalytic N₂O Reduction by Rh₆^– and Rh₆⁺ Clusters

et al. 2016

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The catalytic conversion of nitrous oxide (N 2 O) is of crucial environmental relevance because this chemical compound is a greenhouse gas with an important contribution to climate change, even larger than CO 2, depleting the ozone layer. Recently, reduction of N 2 O catalyzed by rhodium subnanoclusters has been the subject of intensive research, both experimental and theoretical, finding dependencies of reaction rate on the size and geometry and electronic structure of the cluster. In this work, the catalytic reduction mechanism of N 2 O by Rh 6 − and Rh 6 + ionic clusters has been studied by means of density functional theory calculations within the zeroorder-regular approximation (ZORA), which explicitly includes relativistic effects. The N 2 O + Rh 6 − and N 2 O + Rh 6 + reaction pathways were approached starting from a comprehensive search of different stable adsorption modes; transition states were determined as well. We have obtained that the Rh 6 − anions present the lowest activation barriers without spin selectivity. The N 2 O reduction pathway on the Rh 6 − anion was more favorable that the simple desorption channel, whereas on Rh 6 + both channels are in competition, as was experimentally observed. The N 2 O reduction on Rh 6 − and Rh 6 + is sensitive to the charge; it seems to be independent of geometry.

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Section: Introductionmentioning

confidence: 61%

Section: Introductionmentioning

confidence: 86%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Charge and Geometrical Effects on the Catalytic N₂O Reduction by Rh₆^– and Rh₆⁺ Clusters

et al. 2016

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“…The decomposition of N 2 O onto the surfaces of the rare earth element (Nd, Pr, Tb and Y)-doped NiO catalysts [12] and Ag-doped Co 3 O 4 catalysts [13] was studied, the results showing that the doping of rare earth elements or Ag can improve the catalytic activity of the catalyst. Based on the density functional theory, many researchers had investigated the adsorption and decomposition mechanisms of N 2 O on the surfaces of CaO [14], anatase TiO 2 [15], Rh 6 cluster [16], Ag 7 Au 6 alloy nanocluster [17] and fullerene-like boron nitride nanocage [18]. It is found that these materials can be served as promising catalysts for N 2 O decomposing to N 2 and a dissociated oxygen atom.…”

Section: Introductionmentioning

confidence: 99%

DFT Study of N2O Adsorption onto the Surface of M-Decorated Graphene Oxide (M = Mg, Cu or Ag)

et al. 2019

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In order to reduce the harm of nitrous oxide (N2O) on the environment, it is very important to find an effective way to capture and decompose this nitrous oxide. Based on the density functional theory (DFT), the adsorption mechanism of N2O on the surfaces of M-decorated (M = Mg, Cu or Ag) graphene oxide (GO) was studied in this paper. The results show that the effects of N2O adsorbed onto the surfaces of Mg–GO by O-end and Cu–GO by N-end are favorable among all of the adsorption types studied, whose adsorption energies are −1.40 eV and −1.47 eV, respectively. Both adsorption manners belong to chemisorption. For Ag–GO, however, both the adsorption strength and electron transfer with the N2O molecule are relatively weak, indicating it may not be promising for N2O removal. Moreover, when Gibbs free energy analyses were applied for the two adsorption types on Mg–GO by O-end and Cu–GO by N-end, it was found that the lowest temperatures required to undergo a chemisorption process are 209 °C and 338 °C, respectively. After being adsorbed onto the surface of Mg–GO by O-end, the N2O molecule will decompose into an N2 molecule and an active oxygen atom. Because of containing active oxygen atom, the structure O–Mg–GO has strong oxidizability, and can be reduced to Mg–GO. Therefore, Mg–GO can be used as a catalyst for N2O adsorption and decomposition. Cu–GO can be used as a candidate material for its strong adsorption to N2O.

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Dissociation of N2O on anatase TiO2 (001) surface – The effect of oxygen vacancy and presence of Ag cluster

Sowmiya

Senthilkumar

2016

Applied Surface Science

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Dissociation of N2O promoted by Rh6 clusters. A ZORA/DFT/PBE study

Cited by 8 publications

References 39 publications

Charge and Geometrical Effects on the Catalytic N₂O Reduction by Rh₆^– and Rh₆⁺ Clusters

Charge and Geometrical Effects on the Catalytic N₂O Reduction by Rh₆^– and Rh₆⁺ Clusters

DFT Study of N2O Adsorption onto the Surface of M-Decorated Graphene Oxide (M = Mg, Cu or Ag)

Dissociation of N2O on anatase TiO2 (001) surface – The effect of oxygen vacancy and presence of Ag cluster

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Dissociation of N2O promoted by Rh6 clusters. A ZORA/DFT/PBE study

Cited by 8 publications

References 39 publications

Charge and Geometrical Effects on the Catalytic N2O Reduction by Rh6– and Rh6+ Clusters

Charge and Geometrical Effects on the Catalytic N2O Reduction by Rh6– and Rh6+ Clusters

DFT Study of N2O Adsorption onto the Surface of M-Decorated Graphene Oxide (M = Mg, Cu or Ag)

Dissociation of N2O on anatase TiO2 (001) surface – The effect of oxygen vacancy and presence of Ag cluster

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Charge and Geometrical Effects on the Catalytic N₂O Reduction by Rh₆^– and Rh₆⁺ Clusters

Charge and Geometrical Effects on the Catalytic N₂O Reduction by Rh₆^– and Rh₆⁺ Clusters