Theoretical investigations on stable structures of C60-nNn (n=2–12): Symmetry, model interaction, and global optimization

Cheng, Yong; Liao, Ji-Hai; Zhao, Yue; Ni, Jun; Yang, Xiao‐Bao

doi:10.1016/j.carbon.2019.07.086

Cited by 5 publications

(3 citation statements)

References 60 publications

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“…Graphitic nitrogen dopants were introduced into the graphene structure by replacing one to three carbon atoms with nitrogen atoms, corresponding to the atomic content of nitrogen from 0% to 3.06%. Multiple configurations are possible when more than one nitrogen atom is introduced into the supercell, which can be determined using the SAGAR package previously developed. , In this work, 19 and 298 nonduplicated configurations are modeled in the cases of introducing 2 and 3 nitrogen atoms, respectively, allowing for an unbiased evaluation. All the models are visualized in Table S1, denoted as C n N m _ i , where n , m are the numbers of carbon and nitrogen atoms in the supercell, respectively, and i is the serial number of the models.…”

Section: Methodsmentioning

confidence: 99%

“…Here, we present a density functional theory (DFT) study on the ORR over nitrogen-doped graphene to reveal the configuration-specific reactivity. By applying a searching algorithm with the package of Structures of Alloy Generation And Recognition (SAGAR), , we generated all nonduplicate configurations. A large graphene supercell of 98 atoms was used for calculations allowing us to investigate the configuration with low nitrogen concentrations in the range from 0% to 3%, which covers the most frequent nitrogen content in the carbon materials synthesized by conventional CVD or thermolysis methods. , By doing so, the configuration-reactivity relationship of N dopants in graphene was established, which may inspire the rational experimental synthesis of carbon catalysts and, more importantly, provide a deeper insight into the active sites of metal-free carbon catalyst.…”

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confidence: 99%

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Configuration Sensitivity of Electrocatalytic Oxygen Reduction Reaction on Nitrogen-Doped Graphene

Zhang

et al. 2022

J. Phys. Chem. Lett.

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As one of the most promising nonprecious metal catalysts for the oxygen reduction reaction (ORR), the structure of the active site on nitrogen-doped carbon materials is still under debate. Here, we report that the sensitivity of the ORR on the local configuration of multiple nitrogen dopants may be overlooked. Combining global structure searching with density functional theory calculations, we established the structure−activity relationship for 19 and 298 possible configurations of graphitic nitrogen-doped graphene with N content of 2 and 3%, respectively. It was revealed that the stability cannot be a screener to determine the major contributor to the activity. 77.5% of current density is contributed by the active configuration with 4.59% population on the graphene containing 3% nitrogen. It unambiguously demonstrates the configuration sensitivity of N-doped graphene for ORR and opens a new window to identifying the optimal structure of N-doped carbons for various applications.C atalysis is a structure-sensitive phenomenon heavily depending on the local coordination of applied catalyst, which has been validated for heterogeneous catalysis over metals 1,2 and metal oxides, 3,4 single-atom catalysts, 5,6 and enzymic catalysts. 7,8 For instance, the reactivity for a certain reaction over a well-defined metal crystal has been demonstrated to be very different at terrace, steps, kinks, corners, edges, or adatoms for various reactions, which has triggered tremendous efforts to explore the size and shape effects of nanoparticle catalysts. 9−11 Metal-free carbons with heteroatom dopants have been discovered as an effective catalyst for electrocatalytic oxygen reduction reaction (ORR), 12−14 CO 2 reduction, 15−17 and diverse chemical synthesis 18,19 during the recent decades. Experimental and theoretical studies suggest that the incorporation of heteroatoms redistributes electrons between dopants and surrounding carbon atoms and changes the spin density, thereby endowing carbon with catalytic reactivity. 20−22 Since the nonmetallic dopants are usually in the form of isolated atoms rather than in the forms of crystals or clusters, it is natural that the active sites on doped carbons are highly sensitive to the local coordination, namely, being structuresensitive. Taking the most investigated nitrogen-doped carboncatalysts as an example, it has been widely accepted that different nitrogen moieties, that is, graphitic/quaternary, pyridinic, and pyrrolic nitrogen, have very different reactivities in ORR. Numerous efforts have been devoted to discriminate those nitrogen species as candidates of active sites. Nevertheless, it is still heavily controversial to identify graphitic 23−26 or pyridinic 27−29 nitrogen as the active site.

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Section: Methodsmentioning

confidence: 99%

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confidence: 99%

Configuration Sensitivity of Electrocatalytic Oxygen Reduction Reaction on Nitrogen-Doped Graphene

Zhang

et al. 2022

J. Phys. Chem. Lett.

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“…The C 60 has good acceptor capacity similar to other organic molecules such as benzo and naphthoquinones. Theoretical calculations predict low energy triple degenerate LUMO for the C 60 molecule, so you would expect it to accept a maximum of 6 e - [61] .…”

Section: Introductionmentioning

confidence: 99%

Activation of a C60 Fullerene Molecule by Inserting a FCC Pt4 Platinum Surface

Mora-Zarco,

Novoa-Ramírez,

Maya-Yescas

2024

JHSR

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The present study focused on the activation of C 60 fullerene molecule by attacking it with an FCC Pt 4 platinum surface around the outer surface. The calculations are carried out on DFT-Quantum Molecular Dynamics level of theory as implemented in Biovia Materials Studio modeling and simulation software. DMol 3 is used to calculate total energies, electronic charge density, HOMO-LUMO energies for the treatment of global reactivity under Koopmans scheme, where energies are obtained by single point calculations. In addition, we calculate global electronic parameters that explain the reactive behavior of C 60 Pt 4 complex. Based on these results: i) The binding energy 80.872 eV of the Pt 4 C 60 (AC) indicates that this system strongly chemisorbed. ii) Global electronic parameters shown indicate reactivity of activated complex. iii) The C 60 (AC) exhibit an increase area of 37.39% respect to pure C 60 molecule. iv) Through RDF is pore radius of 21.98 Å obtained for C 60 (AC), which corresponds to mesoporous material for diffusion of chemical species is excellent candidate for catalytic support with applications to fuel cells.

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Fullerene Stability by Geometrical Thermodynamics

Parker

Jeynes

2020

ChemistrySelect

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This work proves that stability of C60 is a geometrical property of the thermodynamics of the system: a significant methodological advance since a detailed treatment of the energetics may be avoidable. This approach may be fruitful, not only for fullerenes but also for general problems of molecular stability and in other applications of conformational chemistry. For the non‐chiral C60, C384, and the weakly‐chiral C28, C76 and C380 (of these, C380 and C384 are classed as “unspirallable”), Schlegel projections are used to show that these fullerenes can all be represented by pairs of spirals counter‐propagating in anti‐parallel (C2) symmetry. For C60, the high symmetry is used to construct an analytical approximation for the spherical double‐spirals, shown mathematically to be Maximum Entropy (MaxEnt) using the formalism of Quantitative Geometrical Thermodynamics (QGT). Therefore C60 is necessarily stable. This MaxEnt stability criterion is general, depending only on the geometry and not the kinematics of the system. The sense and degree of chirality for C76 and C380 is also quantified using a Shannon entropy‐based fragmentation metric.

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Theoretical investigations on stable structures of C60-nNn (n=2–12): Symmetry, model interaction, and global optimization

Cited by 5 publications

References 60 publications

Configuration Sensitivity of Electrocatalytic Oxygen Reduction Reaction on Nitrogen-Doped Graphene

Configuration Sensitivity of Electrocatalytic Oxygen Reduction Reaction on Nitrogen-Doped Graphene

Activation of a C60 Fullerene Molecule by Inserting a FCC Pt4 Platinum Surface

Fullerene Stability by Geometrical Thermodynamics

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