Redox Properties of Self-Assembled Gold Nanoclusters

Su, Bin

doi:10.1021/jp055229l

Cited by 30 publications

(37 citation statements)

References 22 publications

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“…More elaborate models that explicitly account for this effect are available and support our conclusion [30]. Comparison with literature data, however, is difficult, as in most measurements at surface-confined MPCs, quantised double layer charging features were less well-defined than in the present case [23,26,31], or showed a 'rectified' pattern [18,32,33], making the determination of the z = 0 spacing impossible.…”

Section: Resultsmentioning

confidence: 47%

“…Certainly, irregularities in the charging pattern are often symptomatic of residual size dispersity in the sample [24], but strong indications exist that the detailed peak spacing pattern reveals information about the MPC electronic structure [21]. In addition, several refinements have been proposed that account for contributions from the diffuse double layer around the particles and from possible ion and solvent penetration into the ligand shell [12,25,26]. For our current purpose, however, we limit ourselves to observing 15 quantised charging states, equalling the to-date maximum number reported [12].…”

Section: Resultsmentioning

confidence: 99%

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Quantised double layer charging of monolayer-protected clusters in a room temperature ionic liquid

Mertens

Blech

Sologubenko

et al. 2009

Electrochimica Acta

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Section: Resultsmentioning

confidence: 47%

Section: Resultsmentioning

confidence: 99%

Quantised double layer charging of monolayer-protected clusters in a room temperature ionic liquid

Mertens

Blech

Sologubenko

et al. 2009

Electrochimica Acta

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mentioning

confidence: 99%

“…[58] Su identified one transition state for addition of singlet dimethylcarbene and thus describes the reaction as a concerted process. [58] However, these computations did not probe for spin-unrestricted solutions of the Kohn-Sham equations and were thus inappropriate for locating diradicaloid structures. Note that the investigation described here is restricted to singlet dichlorocarbene, while the influence of substituents bound to the carbene center on the reaction mechanism has not been investigated.…”

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confidence: 99%

Addition of Carbenes to the Sidewalls of Single‐Walled Carbon Nanotubes

Bettinger

2006

Chemistry A European J

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The addition of carbenes CX(2) (X=H, Cl) to single-walled carbon nanotubes (SWNTs) was investigated by density functional theory and finite, hydrogen-terminated nanotube clusters or periodic boundary conditions in conjunction with basis sets of up to polarized triple-zeta quality. For armchair [(3,3) to (12,12)] and zigzag tubes [(3,0) to (18,0)], reaction of CH(2) with the C--C bond oriented along the tube axis (A) is less exothermic than with those C--C bonds having circumferential (C) orientation. This preference decreases monotonically with increasing tube diameter for armchair, but not for zigzag tubes; here, tubes with small band gaps have a very low preference for circumferential addition. Axial addition results in cyclopropane products, while circumferential addition produces "open" structures for both armchair and zigzag tubes. The barriers for addition of dichlorocarbene to a (5,5) SWNT, studied for a finite C(90)H(20) cluster, are higher than that for addition to C(60), in spite of similar diameters of the carbon materials. Whereas addition of CCl(2) to [60]fullerene proceeds in a concerted fashion, addition to a (5,5) armchair SWNT is predicted to occur stepwise and involve a diradicaloid intermediate according to B3LYP, PBE, and GVB-PP computations. Addition to C bonds of (5,5) armchair tubes resulting in the thermodynamically more stable insertion products is kinetically less favorable than that to A bonds yielding cyclopropane derivatives.

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“…Interestingly, the peak potentials for a given cluster changed in an approximately linear manner with the variation in its core-charge state, as predicted by the theory; [18] this could also help to determine the values of the "absolute standard redox potential", [E 0 z/z+1 ] abs with respect to various charge states. [22] The value of [E 0 z/z+1 ] abs , that is, the potential with respect to the vacuum (absolute scale), can also be evaluated using ferrocene as an internal reference.…”

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confidence: 99%

Quantized Double‐Layer Charging of Rhodium₂₀₅₇(Tridecylamine)₃₂₁ Clusters Using Differential Pulse and Cyclic Voltammetry

et al. 2007

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Metallic and semiconducting nanoclusters stabilized by a variety of organic monolayers of thiols, amines, and carboxylic acids have received considerable attention in the past decade because of their size-and shape-dependent electronic, chemical, and electrochemical properties, especially because of the ease with which they show discrete single-electron-transfer behavior, also known as quantized double-layer (QDL) charging. [1][2][3][4] This phenomenon has been extensively studied for some systems, using techniques such as scanning tunneling microscopy (STM), cyclic voltammetry (CV), and differential pulse voltammetry (DPV), within a narrow size domain (ca. 1-2 nm). [1][2][3][4] In addition, earlier reports have demonstrated QDL-charging behavior of larger-core clusters (e.g., Au 1400 , Au 2869 ), where surface adsorption plays an important role. [5][6][7] Also, much of the effort aimed at observing the QDL charging of smaller monolayer-protected clusters (MPCs) (1-2 nm) has involved the use of gold particles, with a few exceptions such as Ag, [8] Pd, [9] and Cu, [10] and semiconducting systems such as Si [11] and CdTe.[12]Most of the reports have discussed the synthesis of smaller metal particles and their electrochemical properties, suggesting a tiny-capacitor model for metal nanoclusters that show multiple peaks in voltammetric experiments, corresponding to QDL charging (a single-electron-transfer phenomenon in this size regime). STM studies under high vacuum at 83 K also reveal a reversible "Coulomb blockade" (CB) phenomenon, with multiple equidistant charging steps with different bias. [1] However, so far no report is available that shows both solution phase and solid-state CB effects in the case of transition metal nanoclusters such as Pt and Rh, despite their significance. Consequently, there is an urgent need to explore synthetic procedures in order to obtain monodispersed nanoclusters of Rh: being able to tune their size-and shape-dependent properties is important. More significantly, soluble Rh catalysts would be especially useful for many industrial catalytic processes. For example, polyoxo-anion-stabilized Rh(0) clusters have shown excellent performance, as illustrated by a total turnover (TTO) of 193 000 and 2600 for the hydrogenation of olefin and arenes, respectively.[13] However, their stability is limited because the capping agent is not robust and, more significantly, none of them have indicated a singleelectron-transfer phenomenon.To fill this lacuna, we report here for the first time discrete single-electron-transfer behavior of Rh MPCs stabilized by tridecylamine (TDA) in the (4.9 ± 0.2) nm size regime. A series of evenly spaced redox peaks have been observed at room temperature (298 K), which correspond to the limiting currents controlled by the diffusion of smaller particles towards the electrode surface, thus also facilitating the adsorption of Rh MPCs.The core diameter of the MPCs was calculated by using transmission electron microscopy (TEM) and also confirmed by using DPV, utilizing the...

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Redox Properties of Self-Assembled Gold Nanoclusters

Cited by 30 publications

References 22 publications

Quantised double layer charging of monolayer-protected clusters in a room temperature ionic liquid

Quantised double layer charging of monolayer-protected clusters in a room temperature ionic liquid

Addition of Carbenes to the Sidewalls of Single‐Walled Carbon Nanotubes

Quantized Double‐Layer Charging of Rhodium₂₀₅₇(Tridecylamine)₃₂₁ Clusters Using Differential Pulse and Cyclic Voltammetry

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Redox Properties of Self-Assembled Gold Nanoclusters

Cited by 30 publications

References 22 publications

Quantised double layer charging of monolayer-protected clusters in a room temperature ionic liquid

Quantised double layer charging of monolayer-protected clusters in a room temperature ionic liquid

Addition of Carbenes to the Sidewalls of Single‐Walled Carbon Nanotubes

Quantized Double‐Layer Charging of Rhodium2057(Tridecylamine)321 Clusters Using Differential Pulse and Cyclic Voltammetry

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Quantized Double‐Layer Charging of Rhodium₂₀₅₇(Tridecylamine)₃₂₁ Clusters Using Differential Pulse and Cyclic Voltammetry