Direct Hydrogenation of Dinitrogen and Dioxygen via Eley–Rideal Reactions

Yao, Yunxi; Giapis, Konstantinos P.

doi:10.1002/anie.201604899

Cited by 6 publications

(3 citation statements)

References 40 publications

(35 reference statements)

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“…2a) as may be expected given the quasi-linear nature of the triatomic CO 2 + ion 21,22 . We consider next a kinematic model in which—as for diatomic molecules scattering on metal surfaces 23 —the leading O atom first collides with a surface Au atom, followed by a second collision of the CO moiety without prompt dissociation of the CO 2 molecule. Applying BCT to this sequential-collision model yields a kinematic factor of 0.7870, which agrees very well with the CO 2 + exit energy data (Fig.…”

Section: Resultsmentioning

confidence: 99%

Direct dioxygen evolution in collisions of carbon dioxide with surfaces

et al. 2019

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The intramolecular conversion of CO 2 to molecular oxygen is an exotic reaction, rarely observed even with extreme optical or electronic excitation means. Here we show that this reaction occurs readily when CO 2 ions scatter from solid surfaces in a two-step sequential collision process at hyperthermal incidence energies. The produced O 2 is preferentially ionized by charge transfer from the surface over the predominant atomic oxygen product, leading to direct detection of both O 2 + and O 2 − . First-principles simulations of the collisional dynamics reveal that O 2 production proceeds via strongly-bent CO 2 configurations, without visiting other intermediates. Bent CO 2 provides dynamic access to the symmetric dissociation of CO 2 to C+O 2 with a calculated yield of 1 to 2% depending on molecular orientation. This unexpected collision-induced transformation of individual CO 2 molecules provides an accessible pathway for generating O 2 in astrophysical environments and may inspire plasma-driven electro- and photo-catalytic strategies for terrestrial CO 2 reduction.

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Section: Resultsmentioning

confidence: 99%

Direct dioxygen evolution in collisions of carbon dioxide with surfaces

et al. 2019

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“…Here, taking d(111) as an example, the reaction activation energies were calculated via the climbing image nudged elastic band (CI-NEB) method. , The barriers at varying potentials were estimated by the method proposed by Janik et al, where all electrochemical hydrogenation reactions are based on Eley-Rideal-like (E-R) mechanism. , A hydrogen adsorbed on the catalyst surface (*H) is transferred to a H 2 O molecule, which assists a Heyrovsky-like H + to attack the adsorbed intermediates to achieve the protonation reactions. The chemical potential of *H is assumed to be equal with that of a proton–electron pair at the equilibrium potential (U 0 ), which can be calculated by the computational hydrogen electrode (CHE) model at varying potentials.…”

Section: Resultsmentioning

confidence: 99%

Potential Dependence of Ammonia Selectivity of Electrochemical Nitrate Reduction on Copper Oxide

Yang

Long

et al. 2022

ACS Sustainable Chem. Eng.

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Nitrate electrochemical reduction (eNO 3 RR) has been considered as an alternative strategy for decentralized ammonia production, while there are two critical issues regarding high overpotential and poor selectivity because of nitrite production at low overpotentials. Therefore, it is significant to understand the reaction mechanism of ammonia and nitrite selectivity. In addition, it was found that hydrogen evolution reaction (HER) can become notable and drastically affects the Faradaic efficiency. In this work, taking copper oxide as an example, we have combined density functional theory (DFT) calculations and microkinetic modeling (MKM) to understand the products selectivity and Faradaic efficiency of eNO 3 RR to NH 3 at varying potentials. Our models are consistent qualitatively with the experimental results, describing well the competition of ammonia, nitrite, and hydrogen. As the charge transfer coefficient (β) for *NO 2 protonation (*NO 2 to HNO 2 (g)) is smaller than that of *NO hydrogenation (*NO to *NHO), ammonia production becomes more favorable gradually. As the larger charge transfer coefficient (β) for HER compared to *NO hydrogenation (*NO to *NHO), ammonia production becomes less preferable at high overpotentials. The present mechanistic insights can provide design principles of eNO 3 RR activity and selectivity over ammonia, nitrite, and hydrogen.

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“…The scattering apparatus and associated ion beam-line have been described in detail elsewhere. [25][26][27] Isotopically-pure reactive beams of O + and O 2 + , extracted from an inductively-coupled plasma and mass-filtered, are directed onto a polycrystalline Pt surface (4N purity, ESPI) which is pre-cleaned by sputtering in situ with an Ar + gun. Beam energy is controlled by varying externally the plasma bias with respect to ground.…”

Section: Methodsmentioning

confidence: 99%

Dynamic nitroxyl formation in the ammonia oxidation on platinum via Eley–Rideal reactions

Yao

Giapis

2016

Phys. Chem. Chem. Phys.

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For over 90 years, nitroxyl (HNO) has been postulated to be an important reaction intermediate in the catalytic oxidation of ammonia to NO and its by-products (N, NO), but never proven to form or exist on catalytic surfaces. Here we show evidence from reactive ion beam experiments that HNO can form directly on the surface of polycrystalline Pt exposed to NHvia Eley-Rideal abstraction reactions of adsorbed NH by energetic O and O projectiles. The dynamic formation of HNO in a single collision followed up by prompt rebound from the surface prevents subsequent reactive interactions with other surface adsorbates and enables its detection. In addition to HNO, NO and OH are also detected as direct products in what constitutes the concurrent abstraction of three surface adsorbates, namely NH, N, and H, by O projectiles with entirely predictable kinematics. While its relation to thermal catalysis may be tenuous, dynamic HNO formation could be important on grain surfaces of interstellar or cometary matter under astrophysical conditions.

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Direct Hydrogenation of Dinitrogen and Dioxygen via Eley–Rideal Reactions

Abstract: This is the author manuscript accepted for publication and has undergone full peer review but has not been through the copyediting, typesetting, pagination and proofreading process, which may lead to differences between this version and the Version of Record.

Cited by 6 publications

References 40 publications

Direct dioxygen evolution in collisions of carbon dioxide with surfaces

Direct dioxygen evolution in collisions of carbon dioxide with surfaces

Potential Dependence of Ammonia Selectivity of Electrochemical Nitrate Reduction on Copper Oxide

Dynamic nitroxyl formation in the ammonia oxidation on platinum via Eley–Rideal reactions

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