Modulation of the Work Function in Layer‐by‐Layer Assembly of Metal Nanoparticles and Poly‐<scp>L</scp>‐lysine on Modified Au Surfaces

Carrara, Michel; Kakkassery, Joseph J.; Abid, Jean‐Pierre; Fermı́n, David J.

doi:10.1002/cphc.200301212

Cited by 41 publications

(60 citation statements)

References 33 publications

(31 reference statements)

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“…[29] The lower rates and stronger distance dependence of PdNPs compared with both AuNPs and PtNPs are therefore more likely associated with smaller broadening factors and weaker bonding. The observation that the work function of metallic NP-terminated surfaces after layer-by-layer assembly on a Au substrate varies with the nature of the NPs [30] offers some support for this view. In particular, the work function of the AuNP-terminated surface is closer to that of the bare Au substrate than the PtNP-terminated surface in these electrochemical and SAM environments (as opposed to vacuum conditions), which agrees with the results of the present work.…”

mentioning

confidence: 77%

On the Hopping Efficiency of Nanoparticles in the Electron Transfer across Self‐Assembled Monolayers

et al. 2013

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Redox reactions of solvated molecular species at gold-electrode surfaces modified by electrochemically inactive self-assembled molecular monolayers (SAMs) are found to be activated by introducing Au nanoparticles (NPs) covalently bound to the SAM to form a reactive Au-alkanedithiol-NP-molecule hybrid entity. The NP appears to relay long-range electron transfer (ET) so that the rate of the redox reaction may be as efficient as directly on a bare Au electrode, even though the ET distance is increased by several nanometers. In this study, we have employed a fast redox reaction of surface-confined 6-(ferrocenyl) hexanethiol molecules and NPs of Au, Pt and Pd to address the dependence of the rate of ET through the hybrid on the particular NP metal. Cyclic voltammograms show an increasing difference in the peak-to-peak separation for NPs in the order Au

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confidence: 77%

On the Hopping Efficiency of Nanoparticles in the Electron Transfer across Self‐Assembled Monolayers

et al. 2013

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“…29,30 Some previous works have reported a successful use of PE/NPs multilayers as electrochemical sensors 31 as well as their possible interest in designing junctions with rectifying properties. 32 Another previous work was focused on the characterization of PE/NPs assemblies in the optical domain. 33 These novel systems incorporate new and rich functionalities as well as other physical features, compared to PEMUs, such as electron transport through hopping or tunneling between neighboring NPs 29,34 or dynamic flocculation processes in the aggregation between NPs and the polyelectrolytes.…”

Section: Introductionmentioning

confidence: 99%

Electrochemical Characterization of Polyelectrolyte/Gold Nanoparticle Multilayers Self-Assembled on Gold Electrodes

et al. 2005

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Polyelectrolyte/gold nanoparticle multilayers composed of poly(L-lysine) (pLys) and mercaptosuccinic acid (MSA) stabilized gold nanoparticles (Au NPs) were built up using the electrostatic layer-by-layer self-assembly technique upon a gold electrode modified with a first layer of MSA. The assemblies were characterized using UV-vis absorption spectroscopy, cyclic and square-wave voltammetry, electrochemical impedance spectroscopy, and atomic force microscopy. Charge transport through the multilayer was studied experimentally as well as theoretically by using two different redox pairs [Fe(CN) 6 ] 3-/4-and [Ru(NH 3 ) 6 ] 3+/2+ . This paper reports a large sensitivity to the charge of the outermost layer for the permeability of these assemblies to the probe ions. With the former redox pair, dramatic changes in the impedance response were obtained for thin multilayers each time a new layer was deposited. In the latter case, the multilayer behaves as a conductor exhibiting a strikingly lower impedance response, the electric current being enhanced as more layers are added for Au NP terminated multilayers. These results are interpreted quite satisfactorily by means of a capillary membrane model that encompasses the wide variety of behaviors observed. It is concluded that nonlinear slow diffusion through defects (pinholes) in the multilayer is the governing mechanism for the [Fe(CN) 6 ] 3-/4-species, whereas electron transfer through the Au NPs is the dominant mechanism in the case of the [Ru(NH 3 ) 6 ] 3+/2+ pair.

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“…Chemical analyses of the solution by introduction of the ligands Fe(CN) 6 3À and thiocyanate SCN À pointed to the presence of Fe 2+ and Fe 3+ , respectively (complex formed: Fe 3 {Fe(CN) 6 } 2 , l = 465 nm and Fe(SCN) 3 , l = 706 nm). Prior to each measurement, pyrite powder was washed with the moving phase for 8 h. Data were recorded after introduction of the solute into the column.…”

Section: Chromatography/speciation Measurementsmentioning

confidence: 99%

“…[1][2][3][4][5][6][7][8] The popularity of this method is mainly due to its simplicity, its versatility and in some cases to the establishment of high-level order on a nanometric scale (molecular self-assembly). [1][2][3][4][5][6][7][8] The popularity of this method is mainly due to its simplicity, its versatility and in some cases to the establishment of high-level order on a nanometric scale (molecular self-assembly).…”

Section: Introductionmentioning

confidence: 99%

On the use of electrokinetic phenomena of the second kind for probing electrode kinetic properties of modified electron-conducting surfaces

Duval¹,

Sorrenti²,

Waldvogel³

et al. 2007

Phys. Chem. Chem. Phys.

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The electrokinetic features of electron-conducting substrates, as measured in a conventional thin-layer electrokinetic cell, strongly depend on the extent of bipolar faradaic depolarisation of the interface formed with the adjacent electrolytic solution. Streaming potential versus applied pressure data obtained for metallic substrates must generally be interpreted on the basis of a modified Helmholtz-Smoluchowski equation corrected by an electronic conduction term-non linear with respect to the lateral potential and applied pressure gradient-that stems from the bipolar electrodic behavior of the metallic surface. In the current study, streaming potential measurements have been performed in KNO(3) solutions on porous plugs made of electron-conducting grains of pyrite (FeS(2)) covered by humic acids. For zero coverage, the extensive bipolar electronic conduction taking place in the plug-depolarized by concomitant and spatially distributed oxidation and reduction reactions of Fe(2+) and Fe(3+) species-leads to the complete extinction of the streaming potential over the entire range of applied pressure examined. For low to intermediate coverage, the local electron-transfer kinetics on the covered regions of the plug becomes more sluggish. The overall bipolar electronic conduction is then diminished which leads to an increase in the streaming potential with a non-linear dependence on the pressure. For significant coverage, a linear response is observed which basically reflects the interfacial double layer properties of the humics surface layer. A tractable, semi-analytical model is presented that reproduces the electrokinetic peculiarities of the complex and composite system FeS(2)/humics investigated. The study demonstrates that the streaming potential technique is a fast and valuable tool for establishing how well the electron transfer kinetics at a partially or completely depolarised bare electron-conducting substrate/electrolyte solution interface is either promoted (catalysis) or blocked (passivation) by the presence of a discontinuous surface layer.

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Modulation of the Work Function in Layer‐by‐Layer Assembly of Metal Nanoparticles and Poly‐L‐lysine on Modified Au Surfaces

Cited by 41 publications

References 33 publications

On the Hopping Efficiency of Nanoparticles in the Electron Transfer across Self‐Assembled Monolayers

On the Hopping Efficiency of Nanoparticles in the Electron Transfer across Self‐Assembled Monolayers

Electrochemical Characterization of Polyelectrolyte/Gold Nanoparticle Multilayers Self-Assembled on Gold Electrodes

On the use of electrokinetic phenomena of the second kind for probing electrode kinetic properties of modified electron-conducting surfaces

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