First-principles investigation on dimerization of metal-encapsulated gold nanoclusters

Park, Sora; Kim, Gunn; Kwon, Young–Kyun

doi:10.1039/c3ra45742g

Cited by 8 publications

(3 citation statements)

References 51 publications

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“…855 However, it turns out that most of the aforementioned doped clusters with cage-like structures and closed electronic shells, such as Si@Al 12 , W@Si 12 , Zr@Si 16 , Ti@Au 14 , Mo@Au 12 , and W@Au 12 , still interact strongly with each other by forming chemical bonds (with intercluster binding energy larger than 1 eV). 695,869,870,872,875 Consequently, the structural identity and unique electronic properties of each of these clusters cannot be well retained in the cluster dimers.…”

Section: Dimers and Aggregates Of Endohedrally Doped Cagesmentioning

confidence: 99%

“…In the literature, many ab initio calculations have been conducted to explore dimers of various endohedrally doped cage clusters, including [Si@Al 12 ] 2 , [B@Al 12 ][P@Al 12 ], [Al@Al 12 –P@Al 12 ], [Zr@Si 16 ] 2 , [Ti@Ge 16 ] 2 , [Ta@Si 16 F] 2 , [W@Si 12 ] 2 , [Cr@Si 12 ] 2 , [Ti@Si 16 ] 2 , , [Sc@Si 16 K] 2 and [V@Si 16 F] 2 , [Sc@Si 16 –V@Si 16 ], [Ta@Si 16 ] 2 , [V 2 Si 20 ] 2 , [Mn@Sn 12 ] 2 , , [MPb 10 ] 2 (M = Fe, Co, Ni), [Ti@Au 14 ] 2 , [Mo@Au 12 ] 2 , [W@Au 12 ] 2 , [M@Cd n S n ] 2 (M = Y, Zr, Nb, Mo, Tc, Ru, Rh, Rh, Pd, Ag, Cd; n = 12, 16), and [A@X 12 @A 20 ] 2 (A = Sn, Pb; X = Mg, Zn, Cd, Mn) . However, it turns out that most of the aforementioned doped clusters with cage-like structures and closed electronic shells, such as Si@Al 12 , W@Si 12 , Zr@Si 16 , Ti@Au 14 , Mo@Au 12 , and W@Au 12 , still interact strongly with each other by forming chemical bonds (with intercluster binding energy larger than 1 eV). ,,,, Consequently, the structural identity and unique electronic properties of each of these clusters cannot be well retained in the cluster dimers.…”

Section: Assemblies Of Endohedrally Doped Cage Clustersmentioning

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: Dimers and Aggregates Of Endohedrally Doped Cagesmentioning

confidence: 99%

Section: Assemblies Of Endohedrally Doped Cage Clustersmentioning

confidence: 99%

Endohedrally Doped Cage Clusters

2020

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“…To improve their low intrinsic electronic conductivity and enhance catalytic activity toward the electrochemical reaction, combining perovskite-structured materials with advanced catalyst supports, such as low-cost and high-conductivity carbonaceous materials, has been considered as an attractive method. Different carbon-based materials, including carbon nanocubes, graphene oxide, and carbon quantum dots, have been successfully combined with perovskite oxides via physical mixing or chemical one-pot synthesis methods. − However, carbon supports and perovskite oxides are usually synthesized separately without componential fusing, giving rise to heterogeneous distribution of perovskite oxides and weakly coupled interfaces between the hybrid components. In this regard, two-dimensional (2D) MXene is an ideal alternative to support perovskite oxides.…”

Section: Introductionmentioning

confidence: 99%

Vacancy Defect-Rich Perovskite SrTiO₃/Ti₃C₂ Heterostructures In Situ Derived from Ti₃C₂ MXenes with Exceptional Oxygen Catalytic Activity for Advanced Zn–Air Batteries

Hui

Zhang

Wang

et al. 2022

ACS Appl. Energy Mater.

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The electrochemical performance enhancement for Zn−air batteries (ZABs) based on a perovskite SrTiO 3 electrocatalyst is seriously obstructed by sluggish oxygen reduction and evolution reaction (ORR/OER) kinetics. Herein, we develop an in situ phase transformation strategy to synthesize Ti 3 C 2 @SrTiO 3 MXene nanocomposites as a bifunctional electrocatalyst for ZABs. The Ti 3 C 2 @SrTiO 3 heterostructures guarantee excellent structural stability and promote interfacial charge transfer to accelerate the electrocatalytic redox kinetics. Ti 3 C 2 MXene not only promotes fast electronic/ionic transfer but also stably anchors SrTiO 3 nanocubes without aggregation to provide abundant catalytic active sites and prominent structural stability. Advantageous oxygen vacancies introduced in SrTiO 3 nanocrystals could effectively regulate the electronic structure of active sites, triggering higher intrinsic electrocatalytic activity. Furthermore, Ti vacancies in the MXene display an important synergetic effect to promote the electron transfer in Ti 3 C 2 @SrTiO 3 heterostructures. Theory calculations reveal that abundant vacancy defects substantially strengthen the oxygen intermediates' adsorption ability on the Ti 3 C 2 @SrTiO 3 catalyst, essentially lowering the energy barrier for the ORR/OER process. As expected, the ZABs based on the Ti 3 C 2 @SrTiO 3 catalyst exhibit exceptional electrochemical performance, an extraordinary open-circuit voltage of 1.44 V, and an essentially improved power density of 122 mW cm −2 . The in situ transformation and defect modulation strategies provide enlightening clues to design a highperformance ZAB cathode catalyst.

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Direct assembly between closed-shell coinage metal superatoms

Zhu

Wang

et al. 2022

Nano Res.

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First-principles investigation on dimerization of metal-encapsulated gold nanoclusters

Cited by 8 publications

References 51 publications

Endohedrally Doped Cage Clusters

Endohedrally Doped Cage Clusters

Vacancy Defect-Rich Perovskite SrTiO₃/Ti₃C₂ Heterostructures In Situ Derived from Ti₃C₂ MXenes with Exceptional Oxygen Catalytic Activity for Advanced Zn–Air Batteries

Direct assembly between closed-shell coinage metal superatoms

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First-principles investigation on dimerization of metal-encapsulated gold nanoclusters

Cited by 8 publications

References 51 publications

Endohedrally Doped Cage Clusters

Endohedrally Doped Cage Clusters

Vacancy Defect-Rich Perovskite SrTiO3/Ti3C2 Heterostructures In Situ Derived from Ti3C2 MXenes with Exceptional Oxygen Catalytic Activity for Advanced Zn–Air Batteries

Direct assembly between closed-shell coinage metal superatoms

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Vacancy Defect-Rich Perovskite SrTiO₃/Ti₃C₂ Heterostructures In Situ Derived from Ti₃C₂ MXenes with Exceptional Oxygen Catalytic Activity for Advanced Zn–Air Batteries