On the Origin of the Efficient Nanoparticle Mediated Electron Transfer across a Self-Assembled Monolayer

Chazalviel, Jean-No € el; Allongue, Philippe

doi:10.1021/ja109295x

Cited by 192 publications

(255 citation statements)

References 17 publications

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“…In fact studies by us [2] and Fermin and co-workers [3] have shown that for self-assembled monolayers ranging in length between 3 and 11 carbons, the rate of electron transfer appears to be independent of the thickness of the otherwise insulating organic layer. This, somewhat unexpected observation, was very recently explained theoretically by Chazalviel and Allongue [4]. The explanation was that in the presence of the nanoparticles on top of the organic layer, the much higher density of states provided by the nanoparticle, relative to the density of states when the nanoparticles are absent, meant the exchange current density across the organic layer was many orders of magnitude higher than when the nanoparticles were absent.…”

Section: Introductionmentioning

confidence: 70%

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A Molecule with Dual Functionality 4‐Aminophenylmethylphosphonic Acid: A Comparison Between Layers Formed on Indium Tin Oxide by In Situ Generation of an Aryl Diazonium Salt or by Self‐Assembly of the Phosphonic Acid

et al. 2011

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4-Aminophenylmethylphosphonic acid was grafted on ITO surfaces by 1) electrochemical reductive adsorption of the corresponding aryl diazonium salt and 2) by self-assembly via the phosphonic acid moiety. The aryl diazonium salt derived surfaces are reasonably stable within a wide potential range from À600 mV to 600 mV compared to a very narrow stable range between À40 mV and 40 mV for the self-assembled layers. The different surface stabilities were assessed with a view to forming ITO-organic layer-gold nanoparticle (AuNPs) constructs. As expected the ITO-organic layer-AuNPs construct formed by electrochemical adsorption (ITO-Ph-AuNP) was significantly more stable than the construct formed by self-assembly of phosphonates (ITO-PO 3 Ph-AuNPs).

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Section: Introductionmentioning

confidence: 70%

“…AuNPs were synthesized using a 1 mM solution of HAuCl 4 in MilliQ water that was boiled prior to adding tri-sodium citrate with constant stirring. A colour change started to occur 10 s after the addition of citrate solution according to the method of Frens [14].…”

Section: Preparation Of Ito-organic Layer-aunps Constructsmentioning

confidence: 99%

A Molecule with Dual Functionality 4‐Aminophenylmethylphosphonic Acid: A Comparison Between Layers Formed on Indium Tin Oxide by In Situ Generation of an Aryl Diazonium Salt or by Self‐Assembly of the Phosphonic Acid

et al. 2011

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“…This implies that the resistance of each BPT molecule is far below the quantum conductance, as previously suggested 17 . However this disagrees with [19][20][21][22].…”

mentioning

confidence: 77%

Tracking Nanoelectrochemistry Using Individual Plasmonic Nanocavities

et al. 2017

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We study in real time the optical response of individual plasmonic nanoparticles on a mirror, utilized as electrodes in an electrochemical cell when a voltage is applied. In this geometry, Au nanoparticles are separated from a bulk Au film by an ultrathin molecular spacer. The nanoscale plasmonic hotspot underneath the nanoparticles locally reveals the modified charge on the Au surface and changes in the polarizability of the molecular spacer. Dark-field and Raman spectroscopy performed on the same nanoparticle show our ability to exploit isolated plasmonic junctions to track the dynamics of nanoelectrochemistry. Enhancements in Raman emission and blue-shifts at a negative potential show the ability to shift electrons within the gap molecules.

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“…In addition to direct electrical connection between the buried AuNPs and HOPG, [26] this behavior may be due to fast ET between the electrode and metal NPs across an insulating film. [29] Even higher spatial resolution can be attained by using a smaller SECM tip. A constant height image of a 10 nm AuNP in Figure 4 a was obtained with a 3 nm-radius polished Pt tip.…”

Section: Np (Symbols Inmentioning

confidence: 99%

Scanning Electrochemical Microscopy of Individual Catalytic Nanoparticles

Sun

Zacher

et al. 2014

Angewandte Chemie

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Electrochemistry at individual metal nanoparticles (NPs) can provide new insights into their electrocatalytic behavior. Herein, the electrochemical activity of single AuNPs attached to the catalytically inert carbon surface is mapped by using extremely small (! 3 nm radius) polished nanoelectrodes as tips in the scanning electrochemical microscope (SECM). The use of such small probes resulted in the spatial resolution significantly higher than in previously reported electrochemical images. The currents produced by either rapid electron transfer or the electrocatalytic hydrogen evolution reaction at a single 10 or 20 nm NP were measured and quantitatively analyzed. The developed methodology should be useful for studying the effects of nanoparticle size, geometry, and surface attachment on electrocatalytic activity in real-world application environment.Electrochemistry of metal nanoparticles (NPs) has been subject of numerous recent studies because of their extensive applications in electrocatalysis and sensing. [1][2][3] The catalytic activity of NPs and the reaction pathway often depend strongly on the NP shape, size, and orientation on the surface. [4][5][6] To investigate the effects of these factors, one has to visualize and measure electrochemical activity at the level of single NPs and crystal-surface facets of a particle. Optical techniques, including surface plasmon resonance imaging, [7] and single-molecule fluorescence imaging [8] were employed recently to map the catalytic activity distribution on a single NP level. One electrochemical approach to single NP experiments is to measure the current at a metal NP either landing at or attached to a small electrode. [9][10][11][12][13][14][15] The landing experiments provided more information about transport processes and collision dynamics, the size distribution and concentration of NPs than electron transfer (ET) or catalytic activities. The problems in NP immobilization experiments [13][14][15] include difficulties in characterizing the geometry of the nanoelectrode/NP system, significant background current produced by the underlying electrode surface, and poorly defined NP shape if it is formed in situ by electrodeposition.

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On the Origin of the Efficient Nanoparticle Mediated Electron Transfer across a Self-Assembled Monolayer

Cited by 192 publications

References 17 publications

A Molecule with Dual Functionality 4‐Aminophenylmethylphosphonic Acid: A Comparison Between Layers Formed on Indium Tin Oxide by In Situ Generation of an Aryl Diazonium Salt or by Self‐Assembly of the Phosphonic Acid

A Molecule with Dual Functionality 4‐Aminophenylmethylphosphonic Acid: A Comparison Between Layers Formed on Indium Tin Oxide by In Situ Generation of an Aryl Diazonium Salt or by Self‐Assembly of the Phosphonic Acid

Tracking Nanoelectrochemistry Using Individual Plasmonic Nanocavities

Scanning Electrochemical Microscopy of Individual Catalytic Nanoparticles

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