Chemically Induced Metal-to-Insulator Transition in<mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML" display="inline"><mml:mrow><mml:msub><mml:mrow><mml:mi>Au</mml:mi></mml:mrow><mml:mrow><mml:mn>55</mml:mn></mml:mrow></mml:msub></mml:mrow></mml:math>Clusters: Effect of Stabilizing Ligands on the Electronic Properties of Nanoparticles

Boyen, Hans‐Gerd; Kästle, G.; Weigl, F.; Ziemann, P.; Schmid, Günter; Garnier, M. G.; Oelhafen, P.

doi:10.1103/physrevlett.87.276401

Cited by 66 publications

(37 citation statements)

References 19 publications

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“…[45] This critical finding vividly illustrates the subtlety, and importance, of surface chemical effects in effecting-or indeed enhancing-any SIMIT. [46] A striking feature of thiol-stabilized gold colloids is their tendency to spontaneously form highly ordered 2D and 3D thin-film arrays of metal particles simply by slow evaporation of the host organic solvent on a suitable substrate (Figure 8). [47,48] In recent years this has become a field of intense research worldwide.…”

Section: Methodsmentioning

confidence: 99%

Gold in a Metallic Divided State—From Faraday to Present‐Day Nanoscience

2007

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“Very minute in their dimensions” is how Faraday described the metal particles present in a fine dispersion of colloidal gold upon observing its interaction with red light 150 years ago (see picture for a laser‐light version of his experiment). This observation would come to serve as the basis for the modern nanoscience and nanotechnology of gold, including the use of gold nanoparticles in catalytic processes and the formation of self‐assembled monolayers.

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Section: Methodsmentioning

confidence: 99%

Gold in a Metallic Divided State—From Faraday to Present‐Day Nanoscience

2007

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“…Although the number of configurations is finite, it provides a good representation to study the evolution of the structural, energetic, electronic, and magnetic properties as a function of composition for nanoalloys with diameter of 0.9 Å to 1.3 Å, which can be accessed by experimental techniques nowadays. [75][76][77][78][79] …”

Section: B Nanocluster Atomic Configurationsmentioning

confidence: 98%

Structure, Electronic, and Magnetic Properties of Binary Pt_nTM_55–n (TM = Fe, Co, Ni, Cu, Zn) Nanoclusters: A Density Functional Theory Investigation

et al. 2015

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Bimetallic platinum-based transition-metal (PtTM, TM = Fe, Co, Ni, Cu, and Zn) nanoclusters are potential candidates to improve and reduce the cost of Pt-based catalysts; however, our current understanding of the binary PtTM nanoclusters is far from satisfactory compared with binary surfaces. In this work, we report a density functional theory investigation of the structural, energetic, and electronic properties of binary PtTM nanoclusters employing 55-atom model systems (Pt n TM 55−n ). We found that the formation of the binary PtTM nanoclusters is energetically favorable for all systems and compositions. Except small deviations at the icosahedron (ICO) core−shell configuration, Pt 42 TM 13 , we found that the excess energy, which measures the relative stability, and the chemical order parameter follow nearly a parabolic behavior as a function of the Pt concentration with a minimum at nearly 50% for both properties and all systems. From our structural analysis, the difference in the atomic size of the Pt and TM chemical species contributes to increase the segregation, which reaches its maximum for the ICO core−shell configuration, and hence, an ideal homogeneous distribution cannot be reached. Except for PtZn, we found that the average bond lengths increase almost linearly by replacing TM by Pt atoms in the Pt n TM 55−n systems, and hence, it follows approximately the Vegard's law. We found that the center of gravity of the occupied d-states of the surface atoms changes almost linearly for PtCo, PtNi, and PtZn; hence, the d-band center can be tuned by controlling the composition of the chemical species, while there are deviations from the linear behavior for PtFe and PtCu.

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“…Ultimately this can even lead to such dramatic effects as a ligand-induced metal-to-insulator transition as shown recently for Au nanoparticles. [17] In this section detailed studies of the plasma process will be presented. Emphasis is placed on the cleanliness of the method, the formation of nanoparticles, and their final chemical state.…”

Section: Formation and Chemical State Of The Nanoparticlesmentioning

confidence: 99%

Micellar Nanoreactors—Preparation and Characterization of Hexagonally Ordered Arrays of Metallic Nanodots

Kästle

Boyen

Weigl

et al. 2003

Adv Funct Materials

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220

217

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The preparation of hexagonally ordered metallic nanodots was studied in detail with emphasis on the chemical state of the resulting particles. To obtain these dots, in a first step micellar structures were formed from diblock copolymers in solution. The reverse micelles themselves are capable of ligating defined amounts of a metal salt within their cores, acting as nanoreactors. After transfer of the metal‐loaded reverse micelles onto a substrate, the polymer was removed by means of different plasmas (oxygen and/or hydrogen), which also allow the metal salt to be reduced to the metallic state. In this way, ordered arrays of metallic nanodots can be prepared on various substrates. By adjusting the appropriate parameters, the separation and the size of the dots can be varied and controlled. To determine their purity, chemical state, and surface cleanliness—all of which are crucial for subsequent experiments since nanoscale structures are intrinsically surface dominated—in‐situ X‐ray photoelectron spectroscopy (XPS) and ex‐situ transmission electron microscopy (TEM) were applied, also giving information on the formation of the nanodots.

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Chemically Induced Metal-to-Insulator Transition inAu55Clusters: Effect of Stabilizing Ligands on the Electronic Properties of Nanoparticles

Cited by 66 publications

References 19 publications

Gold in a Metallic Divided State—From Faraday to Present‐Day Nanoscience

Gold in a Metallic Divided State—From Faraday to Present‐Day Nanoscience

Structure, Electronic, and Magnetic Properties of Binary Pt_nTM_55–n (TM = Fe, Co, Ni, Cu, Zn) Nanoclusters: A Density Functional Theory Investigation

Micellar Nanoreactors—Preparation and Characterization of Hexagonally Ordered Arrays of Metallic Nanodots

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Chemically Induced Metal-to-Insulator Transition inAu55Clusters: Effect of Stabilizing Ligands on the Electronic Properties of Nanoparticles

Cited by 66 publications

References 19 publications

Gold in a Metallic Divided State—From Faraday to Present‐Day Nanoscience

Gold in a Metallic Divided State—From Faraday to Present‐Day Nanoscience

Structure, Electronic, and Magnetic Properties of Binary PtnTM55–n (TM = Fe, Co, Ni, Cu, Zn) Nanoclusters: A Density Functional Theory Investigation

Micellar Nanoreactors—Preparation and Characterization of Hexagonally Ordered Arrays of Metallic Nanodots

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Structure, Electronic, and Magnetic Properties of Binary Pt_nTM_55–n (TM = Fe, Co, Ni, Cu, Zn) Nanoclusters: A Density Functional Theory Investigation