Systematic exploration of N, C configurational effects on the ORR performance of Fe–N doped graphene catalysts based on DFT calculations

Liu, Fan; Gong, Zhu; Yang, Dongzi; Dong, Jia; Jin, Fengmin; Wang, Wei

doi:10.1039/c9ra02822f

Cited by 42 publications

(30 citation statements)

References 57 publications

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“…This naturally leads to adsorption interaction of O 2 molecule on the metal active sites via the interaction of the bonding d‐p (π and σ) orbitals, and the PDOS of the π orbital is located at the energy level near the Fermi level (the DOS of σ orbital is at the lower energy level). [ 346‐348 ] For the *OH and *OOH species, the introduction of H 1s orbital results in the hybridization of p ‐ s , for example, the hybridization of p z + s of *OH. When OH is adsorbed on the transition metal sites via the on‐top configuration, the bonding interactions include the π orbitals formed by TM ( d xz , d yz ) and OH ( p x , p y ) and σ orbital formed by TM (

d_{z^{2}}

) and OH (

p_{z} + s

).…”

Section: Tools For Theoretical Analysismentioning

confidence: 99%

Density Functional Theory for Electrocatalysis

Liao

Xia

et al. 2021

Energy & Environ Materials

114

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With the increase in energy demand and worldwide natural environment crises, it is imperative to develop green and sustainable energy systems to produce clean fuels and chemicals, which can replace fossil fuels and reduce carbon dioxide emissions. [1][2][3] A promising strategy is to develop advanced electrochemical technologies that can convert some common molecules (e.g., water, carbon dioxide, and nitrogen) into high-value chemical products (e.g., hydrogen, hydrocarbons, oxygenates, ammonia, and carbonates). [4][5][6][7] The important energy-related electrocatalytic reactions, including hydrogen evolution reaction (HER), oxygen evolution reaction (OER), oxygen reduction reaction (ORR), nitrogen reduction reaction (NRR), carbon dioxide reduction reaction (CO 2 RR), are the key conversion routes. In the complex processes for the electrocatalytic reactions, an efficient, highly selective, and stable electrocatalyst plays a pivotal role in speeding up the reaction kinetics and decreasing the overpotential, [5,8,9] which can enhance the sustainable energy conversion efficiency. Over the past few decades, tremendous progresses have been made in the establishment of electrocatalysts preparation and fundamental catalytic mechanisms. [6,7,[9][10][11][12][13][14][15][16][17][18] Nevertheless, those breakthroughs still stay at the stage of experimental synthesis and lack of indepth understanding of fundamental principles of the active site on the catalyst surface and catalytic reactions mechanisms, which seriously limits the development of efficient catalysts. Researchers are full of enthusiasm about preparation of advanced catalysts with ideal properties, expecting to establish the composition-structure-function relationships. Density functional theory (DFT) calculations are based on quantum mechanics, which can calculate the electronic structure of the whole catalytic system. It is probably the most powerful computational approach to investigate the structure-activity relationships of electrocatalysts at atomic level. With the rapid advances of computer technology, DFT calculations have created tremendous opportunities in shedding light on the electrocatalytic mechanisms and predicting promising catalysts. [19,20] Identification of the active sites and understanding of the reaction mechanisms are the two key aspects for the study of electrocatalytic reactions. [21] For the former, the experimental approach for identifying active sites is indirect by prepared specified catalysts and establishing definite correlations between catalytic performances and controllable factors. [22,23] Actually, many intermediate states of electrocatalytic

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d_{z^{2}}

) and OH (

p_{z} + s

).…”

Section: Tools For Theoretical Analysismentioning

confidence: 99%

Density Functional Theory for Electrocatalysis

Liao

Xia

et al. 2021

Energy & Environ Materials

114

View full text Add to dashboard Cite

show abstract

“…The V‐based oxide species, with strong OH binding energy (OHBE, about 190 kcal mol −1 for V−OH bond strength), which can facilitate the production of hydrogen intermediates as water dissociation promoters. Accordingly, molecular hydrogen can be produced by the hydrogen intermediates adsorbed at neighboring Ni sites with optimized hydrogen binding energy (HBE) . The strong electronic interactions between V 2 O 3 and Ni can also aid the HER performance by changing the surface electronic state of electrocatalysts .…”

Section: Figurementioning

confidence: 85%

“…Accordingly,m olecular hydrogen can be produced by the hydrogenintermediates adsorbed at neighboring Ni sites with optimized hydrogen binding energy (HBE). [48,49] The strong electronic interactions between V 2 O 3 and Ni can also aid the HER performance by changing the surfacee lectronic state of electrocatalysts. [50] Highly intimate interfaces between the Ni active speciesa nd V 2 O 3 ,w hich can be ensuredb yi ns itu synthesis, minimize the interfacial resistanceb etween the hybrid species, further synergistically boosting the alkaline HER activity.…”

mentioning

confidence: 99%

Boosting Alkaline Hydrogen Evolution Electrocatalysis over Metallic Nickel Sites through Synergistic Coupling with Vanadium Sesquioxide

et al. 2019

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For renewable and sustainable energy, developing cut‐price and high‐efficiency electrocatalysts for the hydrogen evolution reaction (HER) by alkaline water electrolysis is of paramount importance. In this study, a compound electrocatalyst composed of nickel–vanadium sesquioxide nanoparticles supported on porous nickel foam (Ni‐V2O3/NF) is found to exhibit electrocatalytic performance towards HER that is superior to that of the commercial Pt/C catalyst, with nearly zero onset overpotential, an extremely low overpotential of 25 mV to obtain a current density of −10 mA cm−2, a Tafel slope of 58 mV dec−1, and a good durability for 24 h in 1.0 m KOH. Theoretical calculations reveal that the presence of V2O3 optimizes the electronic structure of active Ni components and continuously accelerates the dissociation of water molecules, which in turn improves the HER kinetics. The present work will advance the development of highly efficient nanocomposite electrocatalysts for alkaline water electrocatalysis.

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“…Apart from N 2 ‐fixation, SAC is also widely employed in other reduction reactions [22] . For instance, the oxygen reduction reaction (ORR) on Fe−N doped graphene catalysts [23] . Furthermore, by combining DFT calculations with experiments, Chen et al [24] .…”

Section: Introductionmentioning

confidence: 99%

The Activation and Reduction of N₂ by Single/Double‐Atom Electrocatalysts: A First‐Principle Study

et al. 2021

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Developing low‐cost and highly efficient electrocatalysts for nitrogen reduction reaction (NRR) is one of the most attractive challenges. In this work, we systematically investigated the catalytic properties of the single atom catalysts (SAC) and the double atom catalysts (DAC) for NRR via First‐Principle calculations. The SAC and DAC were formed by single and double transition metal (TM) atoms anchored on N‐doped graphene monolayers (TMxN3x‐graphene, x=1, 2; TM=Mo, Fe, Co, Ni and Cu). It is shown that both the SAC and the DAC have exhibited high catalytic properties for NRR. Moreover, when N2 is absorbed by its side‐on sites, SAC even performs better than DAC. And in five kinds of TM atoms, Fe‐complexes exhibit significantly improved catalytic properties. Especially, Fe1N3‐graphene has the best catalytic activity for NRR with the lowest free energy change of 0.04 eV in the rate determining step (RDS). This work not only proposes the differences of SAC and DAC but also provides a new kind of single atom catalysts (SAC) for NNR.

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Systematic exploration of N, C configurational effects on the ORR performance of Fe–N doped graphene catalysts based on DFT calculations

Abstract: An optimum Fe–N–C ORR catalyst should exhibit a moderate surface stress property and an ideal N, C ligand configurations that results in a moderate interaction between the ORR intermediates and its surface sites.

Cited by 42 publications

References 57 publications

Density Functional Theory for Electrocatalysis

Density Functional Theory for Electrocatalysis

Boosting Alkaline Hydrogen Evolution Electrocatalysis over Metallic Nickel Sites through Synergistic Coupling with Vanadium Sesquioxide

The Activation and Reduction of N₂ by Single/Double‐Atom Electrocatalysts: A First‐Principle Study

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Systematic exploration of N, C configurational effects on the ORR performance of Fe–N doped graphene catalysts based on DFT calculations

Abstract: An optimum Fe–N–C ORR catalyst should exhibit a moderate surface stress property and an ideal N, C ligand configurations that results in a moderate interaction between the ORR intermediates and its surface sites.

Cited by 42 publications

References 57 publications

Density Functional Theory for Electrocatalysis

Density Functional Theory for Electrocatalysis

Boosting Alkaline Hydrogen Evolution Electrocatalysis over Metallic Nickel Sites through Synergistic Coupling with Vanadium Sesquioxide

The Activation and Reduction of N2 by Single/Double‐Atom Electrocatalysts: A First‐Principle Study

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The Activation and Reduction of N₂ by Single/Double‐Atom Electrocatalysts: A First‐Principle Study