Mechanism of Nitric Oxide Oxidation Reaction (2NO + O<sub>2</sub> → 2NO<sub>2</sub>) Revisited

Gadzhiev, Oleg B.; Ignatov, Stanislav K.; Gangopadhyay, Shruba; Masunov, Artëm E.; Петров, А. И.

doi:10.1021/ct100754m

Cited by 49 publications

(53 citation statements)

References 16 publications

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“…Even qualitative estimation of energies was found to be correct . As a drawback, several examples had been reported where B3LYP and other density functionals resulted to qualitatively incorrect mechanistic prediction of even textbook reactions . In the present study, we verified that B3LYP/6‐31G(d) remains a reliable theory level by BSSE evaluation and inclusion of correlation effects not covered by the hybrid GGA approach.…”

Section: Resultssupporting

confidence: 74%

A proline mimetic for enantioselective aldol reaction: a quantum chemical study of a catalytic reaction with a sterically hindered l‐prolinamide derivative

Gadzhiev

Rosa

Meléndez-Bustamante

et al. 2012

J of Physical Organic Chem

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The direct aldol reaction between acetone and 4‐nitrobenzaldehyde catalyzed by sterically hindered l‐prolinamide derivative (64 atoms) of the (11S,12S)‐9,10‐dihydro‐9,10‐ethanoanthracene‐11,12‐diamine molecule has been investigated using density functional theory at the B3LYP/6‐31G(d) level of theory. The reliability of the B3LYP/6‐31G(d) calculations to elucidate the reaction mechanism and estimate activation and reaction energies was confirmed by energy calculation of the net reaction with full geometry optimizations of the reactants and product at the B3LYP/6‐311++G(2d,2p) as well as B2PLYP/def2‐TZVPP levels with correction to Van der Waals interaction. The calculations reveal that the l‐prolinamide derivative catalyzes the reaction according to a multistep enamine mechanism with highly activated C–C bond and/or enamine formation in the proposed mechanism. The final elementary reaction – the C–N bond cleavage in the chiral diol adduct – is accompanied by a very large barrier, which may inhibit further progression of the reaction. The origin of the enantioselectivity and the corresponding reaction paths to a chiral product were unambiguously identified. Copyright © 2012 John Wiley & Sons, Ltd.

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Section: Resultssupporting

confidence: 74%

A proline mimetic for enantioselective aldol reaction: a quantum chemical study of a catalytic reaction with a sterically hindered l‐prolinamide derivative

Gadzhiev

Rosa

Meléndez-Bustamante

et al. 2012

J of Physical Organic Chem

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“…1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 Similar to NO 3and NO 2 -, NO is also hydrogenated in the presence of Ni 2 P. However, this reaction is more complicated and less selective compared to the former two, in part because even in the absence of catalyst, NO can disproportionate-into NO xand NH 4 + products-and/or become oxidized-to NO x --by leftover O 2 in aqueous solution (Figure 4c, d). 75,76 Based on our results, we conclude that both NO 2and NO are competent intermediates in NO 3hydrogenation over Ni 2 P (Scheme 1b).…”

Section: Resultsmentioning

confidence: 58%

Mild and Selective Hydrogenation of Nitrate to Ammonia in the Absence of Noble Metals

et al. 2020

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Motivated by increased awareness about nitrate contamination of surface waters and its deleterious effects in human and animal health, we sought an alternative, non-noble metal catalyst for the chemical degradation of nitrate. First row transition metal phosphides recently emerged as excellent alternatives for hydrogen evolution and hydrotreating reactions. We demonstrate that a key member of this family, Ni2P, readily hydrogenates nitrate (NO3-) to ammonia (NH3) near ambient conditions with very high selectivity (96%). One of the few non-precious metal-based catalysts for this transformation, and among ca. 1% of catalysts with NH3 selectivity, Ni2P can be recycled multiple times with limited loss of activity. Both nitrite (NO2-) and nitric oxide (NO) intermediates are also hydrogenated. Density functional theory (DFT) indicates that-in the absence of a catalyst-nitrite hydrogenation is the reaction bottleneck. A variety of adsorbates (H, O, N, NO) induce surface reconstruction with top-layer Ni-rich surface stoichiometry. Critically, H saturation coverage on Ni2P(001) is only ca. 3 nm-2, significantly less than that on Pd(111) and Ni(111) of ca. 15-18 nm-2, which may play a key role in allowing coadsorption of NOx-. The ability of Earth-abundant, binary metal phosphides such as Ni2P to catalyze nitrate hydrogenation could transform and help us to better understand the basic science behind catalytic hydrogenation and, in turn, advance the next generation of oxyanion removal technologies. ABSTRACT:Motivated by increased awareness about nitrate contamination of surface waters and its deleterious effects in human and animal health, we sought an alternative, non-noble metal catalyst for the chemical degradation of nitrate. First-row transition metal phosphides recently emerged as excellent alternatives for hydrogen evolution and hydrotreating reactions. We demonstrate that a key member of this family, Ni 2 P readily hydrogenates nitrate (NO 3 -) to ammonia (NH 3 ) near ambient conditions with very high selectivity (96%). One of the few non-precious metal-based catalysts for this transformation, and among ca. 1% of catalysts with NH 3 selectivity, Ni 2 P can be recycled multiple times with limited loss of activity. Both nitrite (NO 2 -) and nitric oxide (NO) intermediates are also hydrogenated. Density functional theory (DFT) indicates that-in the absence of a catalyst-nitrite hydrogenation is the reaction bottleneck. A variety of adsorbates (H, O, N, NO) induce surface reconstruction with top-layer Ni-rich surface stoichiometry. Critically, H saturation coverage on Ni 2 P(001) is only ca. 3 nm -2 , significantly less than that on Pd(111) and Ni(111) of ca. 15-18 nm -2 , which may play a key role in allowing coadsorption of NO x -. The ability of Earth-abundant, binary metal phosphides such as Ni 2 P to catalyze nitrate hydrogenation could transform and help us better understand the basic science behind catalytic hydrogenation and, in turn, advance the next generation of oxyanion removal technologies. Triphenylphosph...

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“…In order to simulate the experimental data, the kinetic parameters of R11 were revised in the present work. Some uncertainty exists towards R11 [42], for which most reliable value of activation energy determined up to date is -4.41 [±3.33] kJ/mol [43]. We have taken the pre-exponential factor recommended by Atkinson et al [43] and varied the activation energy in the uncertainty limits, taking the inferior limit, what makes an apparent activation energy of -7.74 kJ/mol (-1850 cal/mol), and which seems to be adequate in all the experimental conditions of this work to reproduce properly the N O/N O 2 concentrations.…”

Section: Kinetic Modelmentioning

confidence: 99%

High pressure study of H oxidation and its interaction with NO

Colom-Díaz

Millera

Bilbao

et al. 2019

International Journal of Hydrogen Energy

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The present study deals with the oxidation of H 2 at high pressure and its interaction with N O. The high pressure behavior of the H 2 /N O x /O 2 system has been tested over a wide range of temperatures (500-1100 K) and different air excess ratios (λ= 0.5 -6.4). The experiments have been carried out in a tubular flow reactor at 10, 20 and 40 bar. N O has been found to promote H 2 oxidation under oxidizing conditions, reacting with HO 2 radicals to form the more active OH radical, which enhances the conversion of hydrogen. The onset temperature for hydrogen oxidation, when doped with N O, was approximately the same at all stoichiometries at high pressures (40 bar), and shifted to higher temperatures as the pressure decreases. The experimental results have been analyzed with an updated kinetic model. The reaction N O+N O+O 2 N O 2 +N O 2 has been found to be important at all conditions studied and its kinetic parameters have been modified, according to its activation energy uncertainty. Furthermore, the kinetic parameters of reaction HN O+H 2 N H+H 2 O have been estimated, in order to obtain a good prediction of the oxidation behavior of H 2 and N O conversion under reducing conditions. The kinetic model shows a good agreement between experimental results and model predictions over a wide range of conditions.

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Mechanism of Nitric Oxide Oxidation Reaction (2NO + O₂ → 2NO₂) Revisited

Cited by 49 publications

References 16 publications

A proline mimetic for enantioselective aldol reaction: a quantum chemical study of a catalytic reaction with a sterically hindered l‐prolinamide derivative

A proline mimetic for enantioselective aldol reaction: a quantum chemical study of a catalytic reaction with a sterically hindered l‐prolinamide derivative

Mild and Selective Hydrogenation of Nitrate to Ammonia in the Absence of Noble Metals

High pressure study of H oxidation and its interaction with NO

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Mechanism of Nitric Oxide Oxidation Reaction (2NO + O2 → 2NO2) Revisited

Cited by 49 publications

References 16 publications

A proline mimetic for enantioselective aldol reaction: a quantum chemical study of a catalytic reaction with a sterically hindered l‐prolinamide derivative

A proline mimetic for enantioselective aldol reaction: a quantum chemical study of a catalytic reaction with a sterically hindered l‐prolinamide derivative

Mild and Selective Hydrogenation of Nitrate to Ammonia in the Absence of Noble Metals

High pressure study of H oxidation and its interaction with NO

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Mechanism of Nitric Oxide Oxidation Reaction (2NO + O₂ → 2NO₂) Revisited