Theoretical Study on the Catalytic Reduction Mechanism of NO by CO on Tetrahedral Rh<sub>4</sub> Subnanocluster

Yang, Haoxiong; Fu, Hongquan; Su, Ben-Fang; Xiang, Bo; Xu, Qianqian; Hu, Changwei

doi:10.1021/acs.jpca.5b07713

Cited by 17 publications

(11 citation statements)

References 64 publications

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“…Another important example is the theoretical study presented by Rempel et al, which showed that NO dissociation is accelerated on a stepped Rh(111) surface . Recently, many DFT calculations have been reported on NO reduction by small Rh clusters, which have shown that these clusters are advantageous in the NO dissociation step. − …”

Section: Introductionmentioning

confidence: 99%

First-Principles Microkinetic Analysis of NO + CO Reactions on Rh(111) Surface toward Understanding NO_x Reduction Pathways

Ishikawa

Tateyama

2018

J. Phys. Chem. C

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In the NO + CO catalytic reaction on Rh(111), it is known from experiments that N 2 O and N 2 are formed at low and high reaction temperatures, respectively, although the mechanism has not been fully understood. Here, we clarified its detailed mechanism using ab initio density functional theory (DFT) and microkinetic analysis. We considered that the catalytic cycle consists of following steps: NO dissociation, N 2 O formation, N 2 formation (via N−N recombination or N 2 O decomposition), and CO 2 formation. Their reaction energies and activation barriers were evaluated by DFT calculations and were then employed for the microkinetics and reactor simulation. We then demonstrated that N 2 O and N 2 are mainly formed at low and high temperatures, respectively, in agreement with experiments. This is because (i) N 2 O formation has a lower activation barrier than that of N 2 formation and thus has a faster rate at low temperature, whereas N 2 formation is dominant at high temperature because of the large exothermicity, and (ii) at a higher temperature, NO dissociation occurs more and thus sufficient amount of surface N atom is provided, accelerating N + N → N 2 . This study demonstrated that to analyze the catalytic reactions in a wide temperature range the combination of the DFT calculation, surface microkinetics, and reactor simulation plays a crucial role.

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Section: Introductionmentioning

confidence: 99%

First-Principles Microkinetic Analysis of NO + CO Reactions on Rh(111) Surface toward Understanding NO_x Reduction Pathways

Ishikawa

Tateyama

2018

J. Phys. Chem. C

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“…All density functional theory (DFT) calculations were conducted using Gaussian 09 program with the Lee–Yang–Parr correlation functional (B3LYP). , The basis set of Stuttgart/Dresden (SDD) and corresponding effective core potential (ECP) were employed for the Rh atoms, and 6-311+G(2d) was used for N atoms, , namely B3LYP/6-311+G(2d), SDD. The generalized gradient approximation (GGA) methods with the B3LYP functional have been proven to provide accurate energetic and geometric results for transition metals and nitrides. , Vibrational frequency calculations were performed to ensure that the reaction intermediates and transition states (TSs) have zero and one imaginary frequency, respectively. The corrections of zero-point energy were included for the energy analysis, and each imaginary frequency of the TSs was examined to ensure the vibration corresponds to the reaction pathway.…”

mentioning

confidence: 99%

“…The generalized gradient approximation (GGA) methods with the B3LYP functional have been proven to provide accurate energetic and geometric results for transition metals and nitrides. 72,73 Vibrational frequency calculations were performed to ensure that the reaction intermediates and transition states (TSs) have zero and one imaginary frequency, respectively. The corrections of zeropoint energy were included for the energy analysis, and each imaginary frequency of the TSs was examined to ensure the vibration corresponds to the reaction pathway.…”

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confidence: 99%

Plasma-Assisted Chain Reactions of Rh₃⁺ Clusters with Dinitrogen: N≡N Bond Dissociation

Cui

Jia

Zhang

et al. 2020

J. Phys. Chem. Lett.

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Dinitrogen activation is known as one of the most challenging subjects in chemistry. A number of well-defined metal complexes, nitrides, and clusters have been studied that show catalysis for dinitrogen activation. However, direct evidence of a complete cleavage of the N≡N triple bond at mild conditions is rather limited to date. Herein, we report a study on the dissociation of N2 on small rhodium clusters assisted by surface plasma radiation. From mass spectrometry observation, a few rhodium nitride clusters with an odd number of nitrogen atoms are produced, such as the Rh3N2m–1 + (m = 1–5) series, indicative of N≡N bond dissociation in the mild plasma atmosphere. Interestingly, Rh3N7 + is identified with outstanding mass abundance among the Rh n N2m–1 + products, and its ground-state structure is in the form of Rh3N(N2)3 + by capping a nitrogen atom on the top of Rh3 + plane and hanging three N2 molecules beneath the three Rh atoms respectively, giving rise to a C 3v symmetry and excellent stability. We demonstrate the catalysis of such a three-atom rhodium cluster and reveal a dinitrogen activation strategy by thermodynamics- and dynamics- favorable chain reactions of multiple N2 molecules with two rhodium clusters under plasma atmosphere.

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“…In these three technologies, the key step is the decomposition of adsorbed NO to produce adsorbed N 2 O. The N 2 O+CO reaction in CO-SCR is faster than the isolated N 2 O+CO reaction over Rh/Al 2 O 3 by an order of magnitude [16]. In CH 4 -SCR, the activation of the C-H bond in CH 4 serves as a rate determining step of the reaction of NO removal by CH 4 [17].…”

Section: Introductionmentioning

confidence: 99%

State-of-Art Review of NO Reduction Technologies by CO, CH4 and H2

et al. 2021

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Removal of nitrogen oxides during coal combustion is a subject of great concerns. The present study reviews the state-of-art catalysts for NO reduction by CO, CH4, and H2. In terms of NO reduction by CO and CH4, it focuses on the preparation methodologies and catalytic properties of noble metal catalysts and non-noble metal catalysts. In the technology of NO removal by H2, the NO removal performance of the noble metal catalyst is mainly discussed from the traditional carrier and the new carrier, such as Al2O3, ZSM-5, OMS-2, MOFs, perovskite oxide, etc. By adopting new preparation methodologies and introducing the secondary metal component, the catalysts supported by a traditional carrier could achieve a much higher activity. New carrier for catalyst design seems a promising aspect for improving the catalyst performance, i.e., catalytic activity and stability, in future. Moreover, mechanisms of catalytic NO reduction by these three agents are discussed in-depth. Through the critical review, it is found that the adsorption of NOx and the decomposition of NO are key steps in NO removal by CO, and the activation of the C-H bond in CH4 and H-H bonds in H2 serves as a rate determining step of the reaction of NO removal by CH4 and H2, respectively.

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Theoretical Study on the Catalytic Reduction Mechanism of NO by CO on Tetrahedral Rh₄ Subnanocluster

Cited by 17 publications

References 64 publications

First-Principles Microkinetic Analysis of NO + CO Reactions on Rh(111) Surface toward Understanding NO_x Reduction Pathways

First-Principles Microkinetic Analysis of NO + CO Reactions on Rh(111) Surface toward Understanding NO_x Reduction Pathways

Plasma-Assisted Chain Reactions of Rh₃⁺ Clusters with Dinitrogen: N≡N Bond Dissociation

State-of-Art Review of NO Reduction Technologies by CO, CH4 and H2

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Theoretical Study on the Catalytic Reduction Mechanism of NO by CO on Tetrahedral Rh4 Subnanocluster

Cited by 17 publications

References 64 publications

First-Principles Microkinetic Analysis of NO + CO Reactions on Rh(111) Surface toward Understanding NOx Reduction Pathways

First-Principles Microkinetic Analysis of NO + CO Reactions on Rh(111) Surface toward Understanding NOx Reduction Pathways

Plasma-Assisted Chain Reactions of Rh3+ Clusters with Dinitrogen: N≡N Bond Dissociation

State-of-Art Review of NO Reduction Technologies by CO, CH4 and H2

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Theoretical Study on the Catalytic Reduction Mechanism of NO by CO on Tetrahedral Rh₄ Subnanocluster

First-Principles Microkinetic Analysis of NO + CO Reactions on Rh(111) Surface toward Understanding NO_x Reduction Pathways

First-Principles Microkinetic Analysis of NO + CO Reactions on Rh(111) Surface toward Understanding NO_x Reduction Pathways

Plasma-Assisted Chain Reactions of Rh₃⁺ Clusters with Dinitrogen: N≡N Bond Dissociation