Mechanistic Understanding of NO<sub>2</sub> Dissociation on a Rutile TiO<sub>2</sub> (110) Surface: An Electronic Structure Study

Marutheeswaran, S.; Mishra, Shashi B.; Roy, Somnath C.; Nanda, B. R. K.

doi:10.1021/acs.jpcc.0c00525

Cited by 10 publications

(12 citation statements)

References 58 publications

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“…Both of their surfaces yield significantly more exothermic binding energies than our 3–4–2B structure with the binding of an O vacancy site in the defect-rich model resulting in binding energies substantially more exothermic than the binding of Ti without O vacancies. All other reports of this structure , are generally consistent with our 3–4–2B value. Rodriguez et al predicted a structure with two sites bridged by an N and O of NO 2 , with a much higher binding energy than our rotated HONO-like 3–4–1Tc .…”

Section: Resultssupporting

confidence: 93%

“…We now compare previously calculated binding energies in the literature for TiO 2 bulk solid with our cluster calculations (Table ). Calculated LBEs from our CCSD(T)/aD//B3LYP/aD (TiO 2 ) 3 cluster calculations are generally consistent with LBEs calculated using embedded cluster models, small cluster models, and plane-wave models , of rutile and anatase TiO 2 . Our physisorption LBEs for TiO 2 clusters are more exothermic than those reported in the literature for bulk solids.…”

Section: Resultssupporting

confidence: 75%

“…The most commonly reported structure ,, for NO 2 binding TiO 2 is a bridged NO 2 containing species where two Ti centers are bridged by the oxygens of NO 2 on TiO 2 . Using bulk TiO 2 models both with (defect-rich) and without (defect-free) O vacancy sites, Rodriguez et al predicted NO 2 binding energies at the plane-wave PW91 level.…”

Section: Resultsmentioning

confidence: 99%

“…Marutheeswaran et al . used electronic structure calculations at the plane-wave PBE-GGA level of theory to predict the disproportionation of NO 2 on TiO 2 .…”

Section: Introductionmentioning

confidence: 99%

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Reaction of NO₂ with Groups IV and VI Transition Metal Oxide Clusters

et al. 2020

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The addition of NO 2 to Group IV (MO 2 ) n and Group VI (MO 3 ) n (n = 1−3) nanoclusters was studied using both density functional theory (DFT) and coupled cluster theory (CCSD(T)). The structures and overall binding energetics were predicted for Lewis acid−base addition without transfer of spin (a physisorption-type process) and the formation of either cluster-ONO (HONO-like or bidentate bonding) or NO 3− formation where for both the spin is transferred to the metal oxide clusters (a chemisorption-type process). Only chemisorption of NO 2 is predicted to be thermodynamically allowed at temperatures ≥298 K for Group IV (MO 2 ) n clusters with the formation of surface chemisorbed NO 2 being by far the most energetically favorable. The ligand binding energies (LBEs) for physisorption and chemisorption on the TiO 2 nanoclusters are consistent with computational studies of the bulk solids. Chemisorption is only predicted to occur for (CrO 3 ) n clusters in the form of a terminal nitrate containing species whereas the larger chemisorbed nitrate structures for (MoO 3 ) n and (WO 3 ) n were found to be metastable and unlikely to form in any appreciable amount at temperatures of 298 K and higher. NO 2 is predicted to only be capable of physisorbing to (MoO 3 ) n and (WO 3 ) n at lower temperatures and therefore unlikely to bind NO 2 at temperatures ≥298 K. Correlations between the (MO 3 ) n NO 2 ligand bond energies and the chemical properties of the parent (MO 3 ) n clusters (Lewis acidity, ionization potentials, excitation energies, and M = O/M−O bond strengths) are described.

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Section: Resultssupporting

confidence: 93%

Section: Resultssupporting

confidence: 75%

Section: Resultsmentioning

confidence: 99%

“…Marutheeswaran et al . used electronic structure calculations at the plane-wave PBE-GGA level of theory to predict the disproportionation of NO 2 on TiO 2 .…”

Section: Introductionmentioning

confidence: 99%

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Reaction of NO₂ with Groups IV and VI Transition Metal Oxide Clusters

et al. 2020

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“…They concluded that NO 2 adsorption is in physisorptive without water. Another key finding is that the antibonding orbital population between Ti and On atoms has been found insignificant from the COHP figures [33] …”

Section: Introductionmentioning

confidence: 99%

Activation of NO₂ by Modifying the Porphyrin Unit with Oxygen in a MnN₄ Graphene Layer

2023

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In this article, the activation of NÀ O bonds in NO 2 molecules has been investigated by Density Functional Theory (DFT) calculations. Considering the graphene-based MnN 4 layer, nitrogen atoms in the porphyrin unit were sequentially replaced with oxygen atoms to create different MnN m O n /G (m + n = 4 and 1 < m � 4) layers. As more oxygen atoms are incorporated in porphyrin units for bare layers, the covalent character of the MnÀ O bonds is switched to the transit nature with respect to MnÀ N bonds. Moreover, the trend in bond strength decreasing in all oxygen-containing bonds is in line with the formation energy trends of bare layers. The same situation is also valid for the bonds between MnÀ N/O. For NO 2 adsorption configurations on all MnN m O n /G layers, NÀ O bonds in NO 2 are weakened by populating/depopulating antibonding/bonding orbitals, respectively. Even if the MnN 2 O 2 (hex)/G layer has a moderate NO 2 adsorption energy among the other layers, this layer provided the most significant activation over NÀ O bonds based on crystal orbital Hamilton population (COHP), crystal orbital bond index (COBI), and Atoms in Molecules (AIM) Bader Topological Analysis. Our results show that integrated COHP and integrated COBI values show a remarkable correlation with AIM-Bader parameters for the specific bonds which have descriptive capability over NO 2 molecule activation.

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Photocatalytic Oxidation of NO₂ on TiO₂: Evidence of a New Source of N₂O₅

Chu

Liu

et al. 2023

Angewandte Chemie

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N 2 O 5 is an important intermediate in the atmospheric nitrogen cycle. Using a flow tube reactor, N 2 O 5 was found to be released from the TiO 2 surface during the photocatalytic oxidation of NO 2 , revealing a previously unreported source of N 2 O 5 . The rate of N 2 O 5 release from TiO 2 was dependent on the initial NO 2 concentration, relative humidity, O 2 /N 2 ratio, and irradiation intensity. Experimental evidence and quantum chemical calculations showed that NO 2 can react with the surface hydroxyl groups and the generated electron holes on the TiO 2 , followed by combining with another NO 2 molecule to form N 2 O 5 . The latter was physisorbed on TiO 2 and had a low adsorption energy of À 0.13 eV. Box model simulations indicated that the new source of N 2 O 5 released from TiO 2 can increase the daytime N 2 O 5 concentration by up to 20 % in urban areas if abundant TiO 2 -containing materials and high NOx concentrations were present. This joint experimental/theoretical study not only demonstrates a new chemical mechanism for N 2 O 5 formation but also has important implications for air quality in urban areas.

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Mechanistic Understanding of NO₂ Dissociation on a Rutile TiO₂ (110) Surface: An Electronic Structure Study

Cited by 10 publications

References 58 publications

Reaction of NO₂ with Groups IV and VI Transition Metal Oxide Clusters

Reaction of NO₂ with Groups IV and VI Transition Metal Oxide Clusters

Activation of NO₂ by Modifying the Porphyrin Unit with Oxygen in a MnN₄ Graphene Layer

Photocatalytic Oxidation of NO₂ on TiO₂: Evidence of a New Source of N₂O₅

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Mechanistic Understanding of NO2 Dissociation on a Rutile TiO2 (110) Surface: An Electronic Structure Study

Cited by 10 publications

References 58 publications

Reaction of NO2 with Groups IV and VI Transition Metal Oxide Clusters

Reaction of NO2 with Groups IV and VI Transition Metal Oxide Clusters

Activation of NO2 by Modifying the Porphyrin Unit with Oxygen in a MnN4 Graphene Layer

Photocatalytic Oxidation of NO2 on TiO2: Evidence of a New Source of N2O5

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Mechanistic Understanding of NO₂ Dissociation on a Rutile TiO₂ (110) Surface: An Electronic Structure Study

Reaction of NO₂ with Groups IV and VI Transition Metal Oxide Clusters

Reaction of NO₂ with Groups IV and VI Transition Metal Oxide Clusters

Activation of NO₂ by Modifying the Porphyrin Unit with Oxygen in a MnN₄ Graphene Layer

Photocatalytic Oxidation of NO₂ on TiO₂: Evidence of a New Source of N₂O₅