Dual transition metal atoms embedded in N-doped graphene for electrochemical nitrogen fixation under ambient conditions

Liu, Yi; Song, Bingyi; Huang, Chuixiu; Yang, Li‐Ming

doi:10.1039/d1ta11024a

Cited by 42 publications

(22 citation statements)

References 47 publications

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“…Significantly, the redistributions of charge density can be revealed based on the charge density difference. 45 The Bader charge analysis can detect each atom's charge distribution and the transfer amount. Furthermore, the d-band center (ε d ) could be used as descriptors for the catalytic activity.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

“…The charge density ρ( r ) is used to describe the electron density distribution of the catalyst model, and it is highly correlated with the intermediate species during electrochemical reactions. Significantly, the redistributions of charge density can be revealed based on the charge density difference . The Bader charge analysis can detect each atom’s charge distribution and the transfer amount.…”

Section: Resultsmentioning

confidence: 99%

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Screening of the Transition Metal Single Atom Anchored on α-Borophene Catalysts as a Feasible Strategy for Electrosynthesis of Urea

2022

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Theoretical study of the electrochemical CO2 reduction reaction (CO2RR) and N2 reduction reaction synergistic synthesis of urea via C–N bond coupling, which has provided a high-efficiency approach to developing renewable energy conversion and storage, could also play a significant role in reducing carbon dioxide emissions. However, the practical design and development of electrocatalysts with high activity and selectivity for urea exhibits remain many challenges. Herein, building up a screening strategy based on density functional theory calculations on the transition metal single atom anchored on α-borophene nanosheets provided a route for systematically exploring catalytic activity and electronic properties of the catalyst during CO2 and N2 electroreduction. M@α-B (Ti, Cr, Nb, Mo, and Ta) exhibits promising catalytic activity and selectivity toward the production of urea with the working potentials of −0.31, −0.16, −0.32, and −0.31 V, respectively, during the electrochemical reaction process. Furthermore, the superior activity is closely related to the d-band center and the charge density transfer of active center atoms. To gain insights into the intrinsic correlation between the binding and structural properties, the d-band center position of these M@α-B materials and the limiting potential are used to estimate the catalytic activity of catalysts. Thus, a volcano plot has established a base on the limiting potential with the d-band center positions, and a new descriptor (φ) is suggested to gain insights into the intrinsic correlation from the viewpoint of atomic properties, which involves the electronegativity and the number of d orbital electrons (N d) of metal atoms. Therefore, a moderate limiting potential (−0.4 < U L < 0 V) and d-band center (−0.2 < ?d < 0.8 eV) lead to high catalytic activity and both thermodynamic and electronic properties of materials. The theoretical landscape for screening M@α-B toward CO2 and N2 conversion into urea will provide a practical approach to gaining insights into the electrochemical reaction mechanism for urea synthesis. It also motivates the experimental efforts to explore the electrocatalysts for other electrochemical reactions.

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Section: ■ Results and Discussionmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Screening of the Transition Metal Single Atom Anchored on α-Borophene Catalysts as a Feasible Strategy for Electrosynthesis of Urea

2022

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“…After spontaneous adsorption on the catalyst surface, the N 2 molecule will undergo six proton-electron pairs (H + /e – ) transfer process and finally be reduced to form a NH 3 molecule. Among them, the first protonation step (*N 2 + H + +e – → *N 2 H) and the last (sixth) protonation step (*NH 2 + H + + e – → *NH 3 ) have been proved to be the most likely PDS in the whole NRR process, mainly because these two steps exhibit large uphill in free energy and are generally the most difficult process in NRR. ,,,− In detail, if the NN bond wants to be weakened or even broken, it needs to input enough energy and overcome the kinetic obstacle; the N atom of the *NH 2 intermediate is sp 3 hybridized, with three fully filled and one-half filled orbital, which makes *NH 2 stably adsorbed on the catalyst surface, while *NH 3 has four fully filled orbitals, which makes its adsorption energy lower than that of *NH 2 , which leads to the fact that the hydrogenation of *NH 2 → *NH 3 is usually thermodynamically unfavorable and shows an obvious uphill reaction process. Based on literature reading and our experience, we used Δ G *N 2 →*N 2 H < 0.65 and Δ G *NH 2 →*NH 3 < 0.65 eV as criteria for follow-up screening procedures, and the results are shown in Figure .…”

Section: Resultsmentioning

confidence: 99%

Embedding Double Transition Metal Atoms in B-Modified Two-Dimensional Carbon-Rich Conjugated Frameworks for Efficient Ammonia Synthesis

Jiao

Guo

2022

Inorg. Chem.

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It is important to develop an efficient green catalyst for electrochemical nitrogen reduction under environmental conditions to replace the Haber−Bosch process with high energy consumption, limited economic scale of production, and high CO 2 emissions, but there are still some difficulties in its development and design. In this work, based on 2D CCFs, a B-modified rectangular-shaped expanded phthalocyanine bimetallic atomic catalyst is proposed. Because both the TM-d orbital and the B-sp 3 hybrid orbital can accept the lone pair and feedback electrons of N 2 , and there are significantly different valence electron distributions between the two different metals and boron, this catalyst not only keep the advantages of metal catalysts but also play the role of the B atom to further increase the polarity of nitrogen and activate N 2 . In order to evaluate the catalytic performance of this catalyst, its stability, activity, selectivity, reactivity, and other aspects are screened and analyzed by density functional theory calculation. Among them, the FeNb-BPc CCF catalyst has better N 2 adsorption capacity under ambient conditions, exhibits excellent catalytic activity through a continuous mechanism, and has a lower limiting potential of −0.24 V. We believe that this work opens a new path for the rational design of efficient N 2 reduction reaction catalysts and also provides a theoretical basis for experimental development.

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“…Finally, the U L data of VRu-NC that have been reported in six theoretical calculation studies (including SACs, homonuclear and heteronuclear DACs) were compared. 12,18,26,27,29,46 As shown in Fig. 5(d), the colours of the different points represent the different studies.…”

Section: Origin Of the Activity And Selectivity On M 1 M 2 -Ncmentioning

confidence: 99%

“…23 DACs have shown high NRR electrocatalytic activities via a synergistic effect between the two adjacent metal atoms. 24,25 DACs anchored to nitrogen-doped graphene for the NRR have been reported recently, 26–29 demonstrating that DACs are favourable for the NRR. Although DFT simulations have yielded encouraging results for the utilization of DACs as NRR catalysts, industrially-ready DACs with ultra-low U L values remain rarely reported.…”

Section: Introductionmentioning

confidence: 96%

Mixture screening strategy of efficient transition metal heteronuclear dual-atom electrocatalysts toward nitrogen fixation

Zhu

Chen

Sun

et al. 2022

Phys. Chem. Chem. Phys.

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Dual transition metal atoms embedded in N-doped graphene for electrochemical nitrogen fixation under ambient conditions

Abstract: A systematic study on the catalytic performance of dual transition metal atoms (3d, 4d and 5d) embedded three types of N-doped graphene (DV, TV, QV) for electrocatalytic nitrogen reduction reaction...

Cited by 42 publications

References 47 publications

Screening of the Transition Metal Single Atom Anchored on α-Borophene Catalysts as a Feasible Strategy for Electrosynthesis of Urea

Screening of the Transition Metal Single Atom Anchored on α-Borophene Catalysts as a Feasible Strategy for Electrosynthesis of Urea

Embedding Double Transition Metal Atoms in B-Modified Two-Dimensional Carbon-Rich Conjugated Frameworks for Efficient Ammonia Synthesis

Mixture screening strategy of efficient transition metal heteronuclear dual-atom electrocatalysts toward nitrogen fixation

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