Dissociation of dinitrogen on iron clusters: a detailed study of the Fe<sub>16</sub> + N<sub>2</sub> case

Chen, Bole; Gutsev, G. L.; Sun, Weiguo; Kuang, Xiao‐Yu; Lu, Cheng; Gutsev, Lavrenty G.; Алдошин, С. М.; Ramachandran, B.

doi:10.1039/d0cp05427e

Cited by 7 publications

(14 citation statements)

References 84 publications

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“…The largest difference of eight in the spin multiplicity belongs to the Fe 4 and Fe 4 N 2 pair, while the largest difference between the Fe n and Fe n N pairs is seven at n = 5. Similar differences of six and five were found previously for the Fe 16 –Fe 16 N 2 and Fe 16 –Fe 16 N pairs, respectively …”

Section: Resultssupporting

confidence: 89%

“…The electron affinities in three Fe n , Fe n N, and Fe n N 2 series rise from 0.61, 1.28, and 1.06 eV at n = 1 to 1.69, 1.93, and 2.00 eV at n = 10, respectively, that is, the largest EA ad value of 2.00 eV between the three series belongs to Fe 10 N 2 . The EA ad values of the triad Fe 16 , Fe 16 N, and Fe 16 N 2 computed at the same BPW91/6-311+G* level are 2.09 eV (the experimental values are 2.01 ± 0.08 and 2.09 ± 0.06), 1.98, and 2.09 eV, respectively.…”

Section: Resultsmentioning

confidence: 85%

“…Similar differences of six and five were found previously for the Fe 16 −Fe 16 N 2 and Fe 16 −Fe 16 N pairs, respectively. 21 3.3. Static Dipole Electric Polarizabilities.…”

Section: Resultsmentioning

confidence: 99%

“…19 Dissociative and associative attachment of N 2 to neutral and singly positively and singly negatively charged Fe n was theoretically studied for n = 4 and 16. 20,21 The results of such studies can be applied in assessing the capability of a particular cluster to promote nitrogen fixation. In particular, the sum of the binding energies of two nitrogen atoms in an iron nitride cluster should exceed the dissociation energy of a freestanding N 2 dimer to make dissociative attachment of N 2 energetically favorable.…”

Section: Introductionmentioning

confidence: 99%

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Evolution of Ferromagnetic and Antiferromagnetic States in Iron Nitride Clusters Fe_nN and Fe_nN₂ (n = 1–10)

et al. 2021

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First-principles density functional theory calculations on neutral and singly negatively and positively charged iron clusters Fe n and iron nitride clusters Fe n N and Fe n N 2 (n = 1−10) in the range of 1 ≤ n ≤ 10 revealed that there is a strong competition between ferromagnetic and antiferromagnetic states especially in the Fe n N 2 0,±1 cluster series. This phenomenon was related to superexchange via a bridging N atom between two iron atoms in the Fe n N 2 0,±1 cluster series and to a double superexchange effect via a Fe atom shared by two N atoms in the Fe n N 2 0,±1 series. A thorough examination of the structure−energy−spin state relationships in these clusters is conducted, leading to new insights and confirmation of available experimental results on structural parameters and dissociation energetics. The bond energies of both nitrogen atoms in the Fe n N 2 series are approximately the same. They weakly depend on the charge of the host cluster and fluctuate around 5.5 eV when moving along the series. The energy of N 2 desorption is relatively small; it varies by about 1.0 eV and depends on the charge of the cluster. The experimental finding that N 2 dissociates on the Fe n + clusters beginning with n = 4 was supported by the results of our computations. Our computed values of the Fe n + −N bonding energies agree with the experimental data within the experimental uncertainty bars. It was found that the attachment of one or two N atoms does not seriously affect the polarizability, electron affinity, or ionization energy of the host iron clusters independent of the charge.

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Section: Resultssupporting

confidence: 89%

Section: Resultsmentioning

confidence: 85%

“…Similar differences of six and five were found previously for the Fe 16 −Fe 16 N 2 and Fe 16 −Fe 16 N pairs, respectively. 21 3.3. Static Dipole Electric Polarizabilities.…”

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Evolution of Ferromagnetic and Antiferromagnetic States in Iron Nitride Clusters Fe_nN and Fe_nN₂ (n = 1–10)

et al. 2021

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“…As representatives, we selected three iron clusters; namely, the smallest iron cluster Fe 2 , a Fe 4 cluster which was found [23] to be capable of splitting the N 2 dimer, and a Fe 16 cluster which was recently studied with respect to its interactions with nitrogen atoms and an N 2 dimer. [45] Using gradient based methods, we found pathways for the complete CO 2 dissociation to C + O + O on each Fe n cluster for n = 2, 4, and 16.…”

Section: Introductionmentioning

confidence: 99%

Mechanisms of Complete Dissociation of CO₂ on Iron Clusters

et al. 2022

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Dissociation of CO 2 on iron clusters was studied by using semilocal density functional theory and basis sets of triple-zeta quality. Fe 2 , Fe 4 , and Fe 16 clusters were selected as the representative host clusters. When searching for isomers of Fe n CO 2 , n = 2, 4 and 16 corresponding to carbon dioxide attachment to the host clusters, its reduction to O and CO, and to the complete dissociation, it was found that the total spin magnetic moments of the lowest energy states of the isomers are often quenched with respect to those of initial reagents Fe n + CO 2 . Dissociation pathways of the Fe 2 + CO 2 , Fe 4 + CO 2 , and Fe 16 + CO 2 reactions contain several transition states separated by the local minima states; therefore, a natural question is where do the spin flips occur? Since lifetimes of magnetically excited states were shown to be of the order of 100 fs, the search for the CO 2 dissociation pathways was performed under the assumption that magnetic deexcitation may occur at the intermediate local minima. Two dissociation pathways were obtained for each Fe n + CO 2 reaction using the gradient-based methods. It was found that the Fe 2 + CO 2 reaction is endothermic with respect to both reduction and complete dissociation of CO 2 , whereas the Fe 4 + CO 2 and Fe 16 + CO 2 reactions are exothermic to both reduction and complete dissociation of carbon dioxide. The CO 2 reduction was found to be more favorable than its complete dissociation in the Fe 4 case.

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Photo‐ and Photoelectrocatalysis in Nitrogen Reduction Reactions to Ammonia: Interfaces, Mechanisms, and Modeling Simulations

Ješić,

Pomeroy,

Kamal

et al. 2024

Adv Energy and Sustain Res

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The Haber–Bosch process is a cornerstone in the field of ammonia production and represents a decisive advance in industrial chemistry. This method, developed in the early 20th century, revolutionizes agriculture and enables the mass production of fertilizers. As the world strives for sustainable energy and environmental protection, alternative methods such as the photo/photoelectrocatalytic nitrogen reduction reaction (NRR) are gaining momentum. By using sunlight, electricity, or a combination of both, these approaches promise sustainable ammonia production with renewable energy sources and innovative materials. Researchers are trying to understand the underlying principles, mechanisms, and advances of these methods to overcome the challenges and optimize their effectiveness. This research is a step toward sustainable energy and agriculture, and offers a greener and more efficient way forward. This review looks at advances in sustainable ammonia production, particularly through photo‐ and photoelectrocatalytic NRRs. It examines the hurdles in implementing these methods and provides an overview of the fundamentals of nitrogen fixation and a comparison of current mechanisms. In addition, thermodynamic, theoretical, and computational studies of these processes are summarized. Various photocatalysts and photoelectrocatalysts used for ammonia production are also presented.

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Dissociation of dinitrogen on iron clusters: a detailed study of the Fe₁₆ + N₂ case

Abstract: The coalescence of two Fe8N as well as the structure of the Fe16N2 cluster was studied using density functional theory with the generalized gradient approximation and a basis set of triple-zeta quality.

Cited by 7 publications

References 84 publications

Evolution of Ferromagnetic and Antiferromagnetic States in Iron Nitride Clusters Fe_nN and Fe_nN₂ (n = 1–10)

Evolution of Ferromagnetic and Antiferromagnetic States in Iron Nitride Clusters Fe_nN and Fe_nN₂ (n = 1–10)

Mechanisms of Complete Dissociation of CO₂ on Iron Clusters

Photo‐ and Photoelectrocatalysis in Nitrogen Reduction Reactions to Ammonia: Interfaces, Mechanisms, and Modeling Simulations

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Dissociation of dinitrogen on iron clusters: a detailed study of the Fe16 + N2 case

Abstract: The coalescence of two Fe8N as well as the structure of the Fe16N2 cluster was studied using density functional theory with the generalized gradient approximation and a basis set of triple-zeta quality.

Cited by 7 publications

References 84 publications

Evolution of Ferromagnetic and Antiferromagnetic States in Iron Nitride Clusters FenN and FenN2 (n = 1–10)

Evolution of Ferromagnetic and Antiferromagnetic States in Iron Nitride Clusters FenN and FenN2 (n = 1–10)

Mechanisms of Complete Dissociation of CO2 on Iron Clusters

Photo‐ and Photoelectrocatalysis in Nitrogen Reduction Reactions to Ammonia: Interfaces, Mechanisms, and Modeling Simulations

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Dissociation of dinitrogen on iron clusters: a detailed study of the Fe₁₆ + N₂ case

Evolution of Ferromagnetic and Antiferromagnetic States in Iron Nitride Clusters Fe_nN and Fe_nN₂ (n = 1–10)

Evolution of Ferromagnetic and Antiferromagnetic States in Iron Nitride Clusters Fe_nN and Fe_nN₂ (n = 1–10)

Mechanisms of Complete Dissociation of CO₂ on Iron Clusters