Using the NN dipole as a theoretical indicator for estimating the electrocatalytic performance of active sites in the nitrogen reduction reaction: single transition metal atoms embedded in two dimensional phthalocyanine

Liu, Fangfang; Song, Luying; Liu, Yunxia; Zheng, Fangfang; Wang, Lu; Palotás, Krisztián; Lin, Haiping; Li, Youyong

doi:10.1039/c9ta12345h

Cited by 56 publications

(35 citation statements)

References 53 publications

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“…[ 41 ] According to previous investigations, the performance of the catalyst for HER can be judged according to Sbatatier principle, [ 47 ] which indicates that when H atoms are adsorbed on the surface of the catalyst, the free energy of hydrogenation is lower and the HER process is better. [ 33,48 ] Based on the above consideration, we investigate the limiting potential of the HER reaction on the Mo 2 B 2 surface which is displayed in Figure a. The limiting barrier of Heyrovsky step (

{normalH}^{+} + {normalH}^{+} + 2 {normale}^{-} \to {normalH}_{2}

) is about 0.57 eV, which is lower than the energy barrier for nitrogen reduction on Mo III @N 2 and Mo I @N 2 but is higher than limiting potential of Mo II @N 2 .…”

Section: Resultsmentioning

confidence: 99%

“…All the structure relaxation and electronic energy calculation were carried out by the spin-polarized DFT [33,34] in the Vienna ab initio Simulation Package (VASP). [3,9,35] The core electrons were described through the projector augmented wave and the electron interaction was described by the generalized gradient approximation with the revised Perdew-Burke-Ernzerhof.…”

Section: Computational Detailsmentioning

confidence: 99%

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A Theoretical Evaluation of Possible N₂ Reduction Mechanism on Mo₂B₂

Wang

Huo

et al. 2021

Advcd Theory and Sims

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2D MBene has similar properties to MXene, and it has received widespread attention as an efficient ammonia synthesis catalyst. Herein, the catalytic effect of 2D Mo2B2 applied to the electrochemical nitrogen reduction reaction (NRR) by the first principles calculation is studied. It is found that 2D Mo2B2 can form different adsorption structures which have different electronic properties, and active N2 molecules effectively. These different structures have different catalytic mechanism on the NRR process. In addition, the possibility of NRR reactions on these structures is explored and it is found that when N2 adsorbed obliquely on 2D Mo2B2, it has the lowest overpotential (0.34 V). This work provides important reference for exploring more excellent NRR catalysis in experiments and expands the application of transition metal borides in catalysis.

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{normalH}^{+} + {normalH}^{+} + 2 {normale}^{-} \to {normalH}_{2}

) is about 0.57 eV, which is lower than the energy barrier for nitrogen reduction on Mo III @N 2 and Mo I @N 2 but is higher than limiting potential of Mo II @N 2 .…”

Section: Resultsmentioning

confidence: 99%

Section: Computational Detailsmentioning

confidence: 99%

A Theoretical Evaluation of Possible N₂ Reduction Mechanism on Mo₂B₂

Wang

Huo

et al. 2021

Advcd Theory and Sims

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“…Nitrogen fixation in nature occurs through nitrogenase, and the active site in nitrogenase is the iron‐molybdenum (FeMo) cofactor [33,76] . Therefore, Mo‐based catalysts are of great versatility in the field of electrocatalytic nitrogen reduction [35,77–81] …”

Section: Resultsmentioning

confidence: 99%

Theoretical Insights on Au‐based Bimetallic Alloy Electrocatalysts for Nitrogen Reduction Reaction with High Selectivity and Activity

Shi

Xiang

et al. 2021

ChemSusChem

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Electrochemical reduction of nitrogen to produce ammonia at moderate conditions in aqueous solutions holds great prospect but also faces huge challenges. Considering the high selectivity of Au‐based materials to inhibit competitive hydrogen evolution reaction (HER) and high activity of transition metals such as Fe and Mo toward the nitrogen reduction reaction (NRR), it was proposed that Au‐based alloy materials could act as efficient catalysts for N2 fixation based on density functional theory simulations. Only on Mo3Au(111) surface the adsorption of N2 is stronger than H atom. Thermodynamics combined with kinetics studies were performed to investigate the influence of composition and ratio of Au‐based alloys on NRR and HER. The binding energy and reorganization energy affected performance for the initial N2 activation and hydrogenation process. By considering the free‐energy diagram, the computed potential‐determining step was either the first or the fifth hydrogenation step on metal catalysts. The optimum catalytic activity could be achieved by adjusting atomic proportion in alloys to make all intermediate species exhibit moderate adsorption. Free‐energy diagrams of N2 hydrogenation via Langmuir‐Hinshelwood mechanism and hydrogen evolution via Tafel mechanism were compared to reveal that the Mo3Au surface showed satisfactory catalytic performance by simultaneously promoting NRR and suppressing HER. Theoretical simulations demonstrated that Au‐Mo alloy materials could be applied as high‐performance electrocatalysts for NRR.

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“…Recently, the dipole of adsorbed N≡N was proposed as the descriptor for eNRR activity. 100 In this way, several new electrocatalysts with superior performance were successfully screened out. One possible limitation is that the descriptors are only suitable for describing specific electrocatalytic reactions.…”

Section: Design Criteriamentioning

confidence: 99%

Understanding Single-Atom Catalysis in View of Theory

Zhang

Luo

et al. 2021

JACS Au

110

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In the past decade, isolated single atoms have been successfully dispersed on various substrates, with their potential applications being intensively investigated in different reactions. While the essential target of research in single-atom catalysis is the precise synthesis of stable single-atom catalysts (SACs) with clear configurations and impressive catalytic performance, theoretical investigations have also played important roles in identifying active sites, revealing catalytic mechanisms, and establishing structure–activity relationships. Nevertheless, special attention should still be paid in theoretical works to the particularity of SACs. In this Perspective, we will summarize the theoretical progress made on the understanding of the rich phenomena in single-atom catalysis. We focus on the determination of local structures of SACs via comparison between experiments and simulations, the discovery of distinctive catalytic mechanisms induced by multiadsorption, synergetic effects, and dynamic evolutions, to name a few, the proposal of criteria for theoretically designing SACs, and the extension of original concepts of single-atom catalysis. We hope that this Perspective will inspire more in-depth thinking on future theoretical studies of SACs.

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Using the NN dipole as a theoretical indicator for estimating the electrocatalytic performance of active sites in the nitrogen reduction reaction: single transition metal atoms embedded in two dimensional phthalocyanine

Abstract: The dipole of the NN triple bond in an adsorbed N2 molecule as an efficient theoretical indicator for estimating NRR activities.

Cited by 56 publications

References 53 publications

A Theoretical Evaluation of Possible N₂ Reduction Mechanism on Mo₂B₂

A Theoretical Evaluation of Possible N₂ Reduction Mechanism on Mo₂B₂

Theoretical Insights on Au‐based Bimetallic Alloy Electrocatalysts for Nitrogen Reduction Reaction with High Selectivity and Activity

Understanding Single-Atom Catalysis in View of Theory

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Using the NN dipole as a theoretical indicator for estimating the electrocatalytic performance of active sites in the nitrogen reduction reaction: single transition metal atoms embedded in two dimensional phthalocyanine

Abstract: The dipole of the NN triple bond in an adsorbed N2 molecule as an efficient theoretical indicator for estimating NRR activities.

Cited by 56 publications

References 53 publications

A Theoretical Evaluation of Possible N2 Reduction Mechanism on Mo2B2

A Theoretical Evaluation of Possible N2 Reduction Mechanism on Mo2B2

Theoretical Insights on Au‐based Bimetallic Alloy Electrocatalysts for Nitrogen Reduction Reaction with High Selectivity and Activity

Understanding Single-Atom Catalysis in View of Theory

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A Theoretical Evaluation of Possible N₂ Reduction Mechanism on Mo₂B₂

A Theoretical Evaluation of Possible N₂ Reduction Mechanism on Mo₂B₂