One-pot synthesis and characterization of subnanometre-size benzotriazolate protected copper clusters

Salorinne, Kirsi; Chen, Xi; Troff, Ralf W.; Nissinen, Maija; Häkkinen, Hannu

doi:10.1039/c2nr30444a

Cited by 36 publications

(41 citation statements)

References 26 publications

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“…22 For this reason, copper clusters are currently a hot subject of research, 23,24 and several quantum chemical studies concerning the structure and electronic nanoparticles are placed in a unit cell that is periodically repeated in the three dimensions of space, and that employ plane wave basis sets within a reciprocal space representation that lead to a reduction in the computational scaling to N 2 or even N. [44][45][46] A key advantage of this approach is that small, intermediate size and large transition metal clusters or nanoparticles, as well as the upper size limit represented by extended surfaces, can be studied using a single methodology. [47][48][49] However, since this method was initially conceived for solids, its accuracy when describing molecular systems might be less than that of DFT methods using atom-centered functions as basis sets.…”

Section: Introductionmentioning

confidence: 99%

Trends in the Reactivity of Molecular O₂ with Copper Clusters: Influence of Size and Shape

2015

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The adsorption and dissociation of molecular O 2 on copper clusters of varying size and morphology (Cu n with n=3-8, 13, and 38 atoms) has been systematically investigated using several DFT approaches. Different modes of adsorption of molecular O 2 are found for each atomicity of the copper clusters, with their relative stability depending on the cluster morphology: bridge conformations are stabilized on planar clusters, while hollow h-100 and h-111 modes are preferentially formed on 3D clusters. O 2 adsorption energies correlate with the HOMO energy of the isolated copper clusters, but not with their atomicity. On the other hand, the degree of activation of the O-O bond, and therefore the activation energy barrier necessary to break it, depends on the charge transferred to the π* MO of O 2 , which in turn is determined by the mode of adsorption of O 2 on the metal. Cluster morphology appears then as the key factor determining the catalytic activity of copper, since the most activating h-111 and h-100adsorption modes leading to lower barriers are preferentially stabilized on 3D clusters, no matter their size.All computational levels considered, including periodic and molecular calculations, lead to similar trends and conclusions.properties of small copper clusters, in some cases combined with photoelectron spectroscopy measurements, can be found in the literature. [25][26][27][28][29] The reactivity of copper clusters, and its evolution with the number of atoms in the cluster, has been less investigated. The interaction of CO and O 2 with Cu n clusters with n ≤ 10 atoms and the dissociative chemisorption of H 2 on Cu n clusters of up to 15 atoms have been explored in detail, and a higher reactivity of copper clusters with an odd number of atoms has been reported with few exceptions. [30][31][32][33][34][35][36] As regards mechanistic studies, only the dissociation of H 2 O on Cu 7 37 and the mechanism of CO oxidation on Cu 6 and Cu 7 clusters 38 have been reported in the literature.We present now a systematic theoretical study of O 2 adsorption and dissociation on Cu n clusters with n=3-8, 13, and 38 atoms, this last model being considered here the size limit between clusters and nanoparticles. Different modes of adsorption of molecular O 2 have been considered for each atomicity of the copper clusters, and the transition states for dissociation of the O-O bond have been calculated with the objective of finding a trend with particle size in the reactivity of copper clusters.There is, however, a methodological issue in the systematic study of metal clusters of increasing size, which is mainly related to the scaling of the computational cost with the number of electrons in the system. Density functional theory (DFT) 39, 40 based methods are usually chosen because they provide reasonable accuracy at a relatively moderate computational cost. However, the cost of a DFT calculation based on atom-centered Gaussian orbitals scales with N 3 , being N the number of functions in the basis set. [41][42][43] This means that e...

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Section: Introductionmentioning

confidence: 99%

Trends in the Reactivity of Molecular O₂ with Copper Clusters: Influence of Size and Shape

2015

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“…In the negative mode only the smaller species, such as, CuL 2 and BTA anions were present and clusters were no longer found. 32 One more Cu cluster protected by 2-phenylethanethiol (PET) was reported in 2013. 45 It was prepared by following the solid -state route.…”

Section: Cu Clustersmentioning

confidence: 99%

“…rRSC Publishing. Reproduced with permission 32. (C) a) MALDI MS of the PET protected Cu clusters measured in linear negative ion mode, measured using DCTB matrix.…”

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confidence: 99%

Evolution of atomically precise clusters through the eye of mass spectrometry

Bhat¹,

Chakraborty²,

Baksi³

et al. 2016

Nanoscience

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Enormous developments in the area of soluble noble metal clusters protected with monolayers are discussed. Mass spectrometry has been the principal tool with which cluster growth has been examined. The composition and chemistry of clusters have been examined extensively by mass spectrometry. Besides gold, silver, platinum, copper and iron clusters have been examined. Clusters have also been examined by tandem mass spectrometry and the importance of ligands in understanding closed shell electronic structure is understood from such studies. Protein protected noble metal clusters belong to a new group in this family of materials. Naked metal clusters bearing the same core composition as that of monolayer protected clusters is another class in this area, which have been discovered by laser desorption ionization from protein templates.

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“…Nowadays, there is a growing demand on nonprecious‐metal catalysts due to a limited amount of precious metals, and the catalytic activity of copper nanoclusters has emerged as one of the promising candidates in various areas of sensing, biolabeling, and catalysis . This is apparent reason that copper clusters are currently the hot topics in research.…”

Section: Introductionmentioning

confidence: 99%

“…The previous studies have shown that bimetallic nanoalloys are better catalyst than pure metals and they are in demand in various commercial electrocatalytic and catalytic processes . Therefore, researchers envisioned that copper clusters doped with different transition‐metal atoms will be a new kind of molecular architecture to provide the desired structural, electronic, magnetic, optical and catalytic properties for potential applications in nanotechnology, materials science, microelectronics, biology, medicine, and solid‐state chemistry …”

Section: Introductionmentioning

confidence: 99%

Insights into geometries, stabilities, electronic structures, reactivity descriptors, and magnetic properties of bimetallic Ni_mCu_n–m (m = 1, 2; n = 3–13) clusters: Comparison with pure copper clusters

2018

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A long-range corrected density functional theory (LC-DFT) was applied to study the geometric structures, relative stabilities, electronic structures, reactivity descriptors and magnetic properties of the bimetallic NiCu and Ni Cu (n = 3-13) clusters, obtained by doping one or two Ni atoms to the lowest energy structures of Cu , followed by geometry optimizations. The optimized geometries revealed that the lowest energy structures of the NiCu and Ni Cu clusters favor the Ni atom(s) situated at the most highly coordinated position of the host copper clusters. The averaged binding energy, the fragmentation energies and the second-order energy differences signified that the Ni doped clusters can continue to gain an energy during the growth process. The electronic structures revealed that the highest occupied molecular orbital and the lowest unoccupied molecular orbital energies of the LC-DFT are reliable and can be used to predict the vertical ionization potential and the vertical electron affinity of the systems. The reactivity descriptors such as the chemical potential, chemical hardness and electrophilic power, and the reactivity principle such as the minimum polarizability principle are operative for characterizing and rationalizing the electronic structures of these clusters. Moreover, doping of Ni atoms into the copper clusters carry most of the total spin magnetic moment. © 2018 Wiley Periodicals, Inc.

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One-pot synthesis and characterization of subnanometre-size benzotriazolate protected copper clusters

Cited by 36 publications

References 26 publications

Trends in the Reactivity of Molecular O₂ with Copper Clusters: Influence of Size and Shape

Trends in the Reactivity of Molecular O₂ with Copper Clusters: Influence of Size and Shape

Evolution of atomically precise clusters through the eye of mass spectrometry

Insights into geometries, stabilities, electronic structures, reactivity descriptors, and magnetic properties of bimetallic Ni_mCu_n–m (m = 1, 2; n = 3–13) clusters: Comparison with pure copper clusters

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One-pot synthesis and characterization of subnanometre-size benzotriazolate protected copper clusters

Cited by 36 publications

References 26 publications

Trends in the Reactivity of Molecular O2 with Copper Clusters: Influence of Size and Shape

Trends in the Reactivity of Molecular O2 with Copper Clusters: Influence of Size and Shape

Evolution of atomically precise clusters through the eye of mass spectrometry

Insights into geometries, stabilities, electronic structures, reactivity descriptors, and magnetic properties of bimetallic NimCun–m (m = 1, 2; n = 3–13) clusters: Comparison with pure copper clusters

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Trends in the Reactivity of Molecular O₂ with Copper Clusters: Influence of Size and Shape

Trends in the Reactivity of Molecular O₂ with Copper Clusters: Influence of Size and Shape

Insights into geometries, stabilities, electronic structures, reactivity descriptors, and magnetic properties of bimetallic Ni_mCu_n–m (m = 1, 2; n = 3–13) clusters: Comparison with pure copper clusters