Polynitrogen clusters encapsulated inside B24N24 fullerene-like nanocages: Nanoscale high energy materials studied by density functional theory

Su, Bo; Feng, Xiaohui; Guo, Xueyong; Li, Nan

doi:10.1016/j.ica.2016.10.039

Cited by 4 publications

(3 citation statements)

References 51 publications

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“…Su et al 777 have studied encapsulation of polynitrogen clusters in B 24 N 24 cages with both S 8 and O symmetries (Figure 88d, e) as prospective nanoscale high energy materials. Polynitrogen molecules can release a large amount of energy when decomposed into N 2 molecules, but these are not stable in free space.…”

Section: Endohedral Bn Cagesmentioning

confidence: 99%

“…Inspired by the experimental success, endohedral doping of a single atom or very small clusters (up to tetramers) in different B n N n ( n = 12, 16, 20, 24, 28, 36, 48) cages has been explored by numerous ab initio calculations. − The geometries of these BN cages are depicted in Figure . Intuitively, the smallest possible BN cage to contain a dopant atom is B 12 N 12 consisting of 6 tetragonal and 8 hexagonal BN rings with T h symmetry (Figure a).…”

Section: Endohedrally Doped Cages Of Compoundsmentioning

confidence: 99%

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Endohedrally Doped Cage Clusters

2020

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The discovery of carbon fullerene cages and their solids opened a new avenue to build materials from stable cage clusters as “artificial atoms” or “superatoms” instead of atoms. However, cage clusters of other elements are generally not stable. In 2001, ab initio calculations showed that endohedral doping of Zr and Ti atoms leads to highly stable Zr@Si16 fullerene and Ti@Si16 Frank–Kasper polyhedral clusters with large HOMO–LUMO gaps. In 2002, Zr@Ge16 was shown to form a Frank–Kasper polyhedron, suggesting the possibility of designing novel clusters by tuning endohedral and cage atoms. These results were subsequently confirmed from experiments. In the past nearly two decades, many experimental and theoretical studies have been carried out on different clusters, and many very stable cage clusters with possibly high abundance have been found by endohedral doping. Indeed in 2017, Ta@Si16 and Ti@Si16 cage clusters have been synthesized in bulk quantity of about 100 mg using a dry-chemistry method, giving rise to a new hope of developing cluster-based materials in macroscopic quantity besides the well-known C60 fullerene solid. Also, wet-chemistry methods have been used to synthesize endohedrally doped clusters as well as ligated clusters and their solids, which auger well for the development of novel nanostructured materials using atomically precise clusters with unique properties. In this comprehensive review, we present results of many such developments in this fast-growing field including (i) endohedrally doped Al, Ga, and In clusters, (ii) small endohedral carbon fullerene cages with ≤ 28 carbon atoms, (iii) metal doped boron cages, (iv) endohedrally doped cages of group 14 elements (Si, Ge, Sn, and Pb), (v) coinage metal (Cu, Ag, Au) cages doped with a transition metal atom as well as their ligated clusters and crystals, (vi) endohedrally doped cages of compound semiconductors, and (vii) multilayer Matryoshka cages and core–shell structures. In a large number of cases, we have performed ab initio calculations to present updated results of the most stable atomic structures and fundamental electronic properties of the endohedrally doped cage clusters. We discuss electronic, magnetic, optical, and catalytic properties in order to shed light on their potential applications. The stability of the doped cage clusters has been correlated to the concept of filling the electronic shells for superatoms such as within a spherical potential model and also using various electron counting rules including Wade–Mingos rules, systems with 18 and 32 electrons, and the spherical aromaticity rule. We also discuss cluster–cluster interaction in cluster dimers and assemblies of some of the promising doped cage clusters in different dimensions. Finally, we give a perspective of this field with a bright future.

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Section: Endohedral Bn Cagesmentioning

confidence: 99%

Section: Endohedrally Doped Cages Of Compoundsmentioning

confidence: 99%

Endohedrally Doped Cage Clusters

2020

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“…These types of fullerenes have proved to be extremely interesting, both for medical applications and for their possible applications in material sciences [4][5][6][7][8]. With respect to heterofullerenes, the substitution of carbon atoms by boron, nitrogen and silicon has been proposed; in the case of the first two, these have regularly been as -BN-pairs, thus ensuring that isoelectronic species are obtained, although this has not necessarily been the only purpose; in the case of silicon, the main motive has been to search for useful applications in electronics [9][10][11][12][13][14][15][16][17][18][19][20][21]. Last but not least, endohedral fullerenes exist because of the fact that they are hollow; so they have the potential application of confining or protecting molecules, thus acting as carriers or stabilizers.…”

Section: Types Of Fullerenesmentioning

confidence: 99%

Reactivity Indexes and Structure of Fullerenes

Jiménez¹,

Tenorio²,

AlejandroHernández-Velázquez³

et al. 2018

Fullerenes and Relative Materials - Properties and Applications

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The discovery of fullerenes and their production in measurable quantities launched many studies about their reactivity and possible applications. Their peculiar structure opened possibilities for their study, initially replacing carbon atoms with alternative atoms. The surface also offers the possibility of attaching several species and the interior of their hollow structure represents a challenge because of the possibility of confining elements or molecules that may become less stable when attached to the exterior of the cage. These modifications may considerably affect both chemical and physical properties. In this chapter, we propose the encapsulation of 3-10 nitrogen atoms as aggregates inside the C 70 cage. We also study the structures and reactivity indexes and the stabilization conferred as a result of being part of the fullerene. These aggregates are mainly of interest because of their possible application as energetic materials.

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