Reaction of SO2 with Group IV and VI transition metal oxide clusters

Flores, Luis A.; Murphy, Julia G.; Copeland, William B.; Dixon, David A.

doi:10.1016/j.comptc.2017.10.002

Cited by 7 publications

(21 citation statements)

References 45 publications

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“…The bridging nitrates ( 2–4–3B ) are all either near thermoneutral (Ti) or endothermic (Zr and Hf) on the free energy scale at 298 K. These results suggest that the terminal M(O) oxygens are more reactive toward chemisorption than their bridging M(−O–M) counterparts for Group IV dimers. This result is consistent with previous predictions of chemisorption of SO 2 and CO 2 to Group IV dimers. The overall trend of Ti > Hf > Zr agrees with the Lewis acidity trend. , No clear correlation is noted between the formation of “ONO-cluster” species from binding to the excited triplets and the Lewis acidities of the bare dimers.…”

Section: Resultssupporting

confidence: 93%

“…The adsorption strength of NO 2 to Group IV trimers, regardless of physisorption or chemisorption, is stronger than that for the dimers. This result suggests that the trimers have more structural flexibility than the dimers, and is consistent with trends previous predicted for SO 2 and CO 2 adsorption to these clusters.…”

Section: Resultssupporting

confidence: 92%

“…The results show that the spin is transferred to the metal from the NO 2 when the NO 3 – is formed. 1–4–3T formation can be described as a lattice oxygen (formally O 2– ) from the metal oxide transferring one electron and bonding to the N to form the NO 3 – in the same way that addition of CO 2 and SO 2 , to the metal oxide involves a two electron donation to form CO 3 2– and SO 3 –2 . The spin moves from the lattice oxygen which is donating the electron to the metal to which the NO 3 – is bonded and there may be some redox at the metal.…”

Section: Resultsmentioning

confidence: 99%

“…The CCSD(T)/a(D,T,Q) energies were then extrapolated to the complete basis set limit (CBS) according to the extrapolation formula Because of convergence issues starting from Hartree–Fock orbitals, the CCSD(T) energies for the (CrO 3 ) n NO 2 complexes were calculated using DFT orbitals calculated with the PW91 − exchange-correlation functional following our previous work. ,, A natural population analysis (NPA) based on natural bond orbitals (NBOs) − was performed for the B3LYP/aD minima to provide a charge transfer analysis and determine the possibility of redox for each adsorption reaction.…”

Section: Methodsmentioning

confidence: 99%

“…Our group has previously studied the interactions of H 2 O, − alcohols, − SO 2 , and CO 2 with Group IV (MO 2 ) n and Group VI (MO 3 ) n nanoclusters using electronic structure methods at the density functional theory (DFT) and coupled cluster theory (CCSD(T)) levels; for the reactions of alcohols, it was shown that the higher level CCSD(T) calculations were needed for good agreement with experiment. In the current work, we build on this prior work by performing an extensive computational investigation into the physisorption and chemisorption of NO 2 onto Group IV (MO 2 ) n and Group VI (MO 3 ) n nanoclusters ( n = 1–3).…”

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: 92%

Section: Resultsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

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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Nano Pt/TiO2 photocatalyst for ultrafast production of sulfamic acid derivatives using 4-nitroacetanilides as nitrogen precursor in continuous flow reactors

Mohamed¹,

Attia²

2023

Environ Sci Pollut Res

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The design of reactors based on high performance photocatalysts is an important research in catalytic hydrogenation. In this work, modification of titanium dioxide nanoparticles (TiO2 NPs) was achieved by preparation of Pt/TiO2 nanocomposites (NCs) through photo-deposition method. Both nanocatalysts were used for the photocatalytic removal of SOx from the flue gas at room temperature in the presence of hydrogen peroxide, water, and nitroacetanilide derivatives under visible light irradiation. In this approach, chemical deSOx was achieved along with protection of the nanocatalyst from sulfur poising through the interaction of the released SOx from SOx-Pt/TiO2 surface with p-nitroacetanilide derivatives to produce simultaneous aromatic sulfonic acids. Pt/TiO2 NCs have a bandgap of 2.64 eV in visible light range, which is lower than the bandgap of TiO2 NPs, whereas TiO2 NPs have a mean size of 4 nm and a high specific surface area of 226 m2/g. Pt/TiO2 NCs showed high photocatalytic sulfonation of some phenolic compounds using SO2 as a sulfonating agent along with the existence of p-nitroactanilide derivatives. The conversion of p-nitroacetanilide followed the combination processes of adsorption and catalytic oxidation–reduction reactions. Construction of an online continuous flow reactor–high-resolution time-of-flight mass spectrometry system had been investigated, realizing real-time and automatic monitoring of completion the reaction. 4-nitroacetanilide derivatives (1a-1e) was converted to its corresponding sulfamic acid derivatives (2a–2e) in 93–99% isolated yields of within 60 s. It is expected to offer a great opportunity for ultrafast detection of pharmacophores.

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Sub-nm titanium dioxide clusters: efficient photocatalysts for clean SOx conversion under visible light irradiation

Ahmed,

Mohamed,

Habib

et al. 2024

Chem. Pap.

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Reaction of SO2 with Group IV and VI transition metal oxide clusters

Cited by 7 publications

References 45 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

Nano Pt/TiO2 photocatalyst for ultrafast production of sulfamic acid derivatives using 4-nitroacetanilides as nitrogen precursor in continuous flow reactors

Sub-nm titanium dioxide clusters: efficient photocatalysts for clean SOx conversion under visible light irradiation

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Reaction of SO2 with Group IV and VI transition metal oxide clusters

Cited by 7 publications

References 45 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

Nano Pt/TiO2 photocatalyst for ultrafast production of sulfamic acid derivatives using 4-nitroacetanilides as nitrogen precursor in continuous flow reactors

Sub-nm titanium dioxide clusters: efficient photocatalysts for clean SOx conversion under visible light irradiation

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

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