Preparation of multilayer films containing pt nanoparticles on a glassy carbon electrode and application as an electrocatalyst for dioxygen reduction

In this paper, a simple route for the preparation of Pt nanoparticles is described. PtCl62- and [tetrakis-(N-methylpyridyl)porphyrinato] cobalt (CoTMPyP) were assembled on a 4-aminobenzoic acid modified glassy carbon electrode through the layer-by-layer method. The three-dimensional Pt nanoparticle films are directly formed on an electrode surface by electrochemical reduction of PtCl62- sandwiched between CoTMPyP layers. Regular growth of the multilayer films is monitored by UV-vis spectroscopy. X-ray photoelectron spectroscopy verifies the constant composition of the multilayer films containing Pt nanoparticles. Atomic force microscopy proves that the as-prepared Pt nanoparticles are uniformily distributed with average particle diameters of 6-10 nm. The resulting multilayer films containing Pt nanoparticles on the modified electrode possess catalytic activity for the reduction of dissolved oxygen. Rotating disk electrode voltammetry and rotating ring-disk electrode voltammetry confirm that Pt nanoparticle containing films can catalyze an almost four-electron reduction of O-2 to water in 0.5 M H2SO4 solution.

Synthesis and self-assembly of cetyltrimethylammonium bromide-capped gold nanoparticles

In this article, cetyltrimethylammonium bromide (CTAB)-capped gold nanoparticles were synthesized successfully by using CTAB as a phase-transfer catalyst and stabilizer simultaneously in a two-phase toluene/water system. The as-prepared gold nanoparticles were characterized and analyzed by virtue of X-ray photoelectron spectroscopy, UV-visible absorbance spectroscopy, and infrared spectroscopy. The particle size information and collective self-assembling properties of the CTAB-capped gold nanoparticles on carbon-coated copper grid and mica were evaluated by transmission electron microscopy and atomic force microscopy, respectively. As a result it is demonstrated that the 3-D CTAB monolayers on a gold cluster are in the disordered liquid state. The interparticle spacing can be controlled either physically by the inherent particle-to-particle interactions or chemically by molecular linker. The assembly of both nanoparticles and linker-bridged nanonetworks on mica follows a hydrophobic interaction mechanism.

Simple preparation method of Pd nanoparticles on an Au electrode and its catalysis for dioxygen reduction

A simple method for the fabrication of Pd nanoparticles is described. The three-dimensional Pd nanoparticle films are directly formed on a gold electrode surface by simple electrodeposition at -200 mV from a solution of 1 M H2SO4+0.01 mM K2PdCl4. X-Ray photoelectron spectroscopy verifies the constant composition of the Pd nanoparticle films. Atomic force microscopy proves that the as-prepared Pd nanoparticles are uniformly distributed with an average particle diameter of 45-60 nm. It is confirmed that the morphology of the Pd nanoparticle films are correlated with the electrodeposition time and the state of the Au substrate. The resulting Pd-nanoparticle-film-modified electrode possesses high catalytic activity for the reduction of dissolved oxygen in 0.1 M KCl solution. Freshly prepared Pd nanoparticles can catalyze the reduction of O-2 by a 4-electron process at -200 mV in 0.1 M KCl, but this system is not very stable. The cathodic peaks corresponding to the reduction of O-2 gradually decrease with potential cycling and at last reach a steady state. Then two well-defined reduction peaks are observed at -390 and -600 mV vs. Ag/AgCl/KCl (sat.). Those two peaks correspond to a 2-step process for the 4-electron reduction pathway of O-2 in this neutral medium.

Electrochemical behavior of alpha-Keggin-type nanoparticles, Co(en)(3)(PMo12O40), in polyethylene glycol

The electrochemical behavior of alpha-Keggin-type nanoparticles, Co(en)(3)(PMo12O40) (abbreviated as PMo12-Co), have been studied in poly(ethylene glycol) for four different molecular weights (PEG, average MW 400, 600, 1000, and 2000 g mol(-1)) and containing LiClO4 (O/Li=100/1) supporting electrolyte. The diffusion coefficients of the PMo12-Co nanoparticles were determined using a microelectrode by chronoamperometry for PEG of different molecular weights that were used to describe the diffusion behavior of PMo12-Co nanoparticles in different phase states. Moreover, the conductivity of the composite system increases upon addition of PMo12-Co nanoparticles, which was measured by an a.c. impedance technique. FT-IR spectra and DSC were used to follow the interactions of PEG-LiClO4-PMo12-Co, and well described the reason that the PMo12-Co nanoparticles could promote the conductivity of the PEG-LiClO4-PMo12-Co system.

Preparation of gold nanoparticles protected with polyelectrolyte

Gold nanoparticles were synthesized through the reduction of tetrachlorauric acid (HAuCl4) by NaBH4, with polyethyleneimine(PEI) as stabilizer. The nanoparticles were characterized by LTV-vis spectroscopy and atomic. force microscopy(AFM).

One-step synthesis and size control of dendrimer-protected gold nanoparticles: A heat-treatment-based strategy

Dendrimer-protected gold nanoparticles have been facilely obtained by heating an aqueous solution containing third generation poly(propyleneimine) dendrimers and HAuCl4 without the additional step of introducing other reducing agents. Transmission electron microscopy (TEM) and UV vis data indicate the size the nucleation and growth kinetics of gold nanoparticles thus formed which can be tuned by changing the initial molar ratio of dendrimer to gold.

Synthesis of barium fluoride nanoparticles from microemulsion

The cetyltrimethylammonium bromide (CTAB)/2-octanol/water microemulsion system was used to synthesize barium fluoride nanoparticles. X-ray powder diffraction (XRD) analysis showed that the products were single phase. The results of scanning electron microscopy and calculations using the Scherrer equation from the line widths of the XRD have been used to estimate the average particle sizes of the powder products. The results showed that the nanoparticle size was affected by water content and surfactant (CTAB) concentration. As water content decreases from 14.2 to 9.47% (w/w), the particle size decreases from 75 to 40 rim. In addition, increasing the reaction times from 5 to 120 min increases the particle size from 75 to 150 rim, and increasing the amount of surfactant decreases the size of the particle. Luminescence spectra of the BaF2:Ce nanoparticles are also discussed.

Chitosan mediated assembly of gold nanoparticles multilayer

We initiate a systematic exploration of a natural polymer, chitosan, as a structural material for designing functional layers on electrode surfaces in this work. Au colloid films are organized on chitosan layer by adsorption. We have successfully constructed a multilayer An nanoparticle assembly through electrostatic interactions on chitosan functionalized quartz substrates by the alternate treatment of the substrate with solution of citrate-stabilized gold nanoparticles (negatively charged) and chitosan solution (positively charged). The resulting substrates were characterized by UV-Vis spectrometry, atomic force microscopy (AFM), and electrochemical impedance spectroscopy (EIS) measurements. These assemblies of colloid An multilayer are highly stable, and can be kept for a long time in distilled water, only being removed by scratching or extreme electrochemical conditions.

In situ controllable synthesis of polyoxometalate nanoparticles in polyelectrolyte multilayers

Size-controlled Ag3PW12O40 nanoparticles have been synthesized in situ in polyelectrolyte multilayer thin films via layer-by-layer self-assembly.

Gold nanoparticles as fine tuners of electrochemical properties of the electrode/solution interface

Recently, a novel approach for preparing SERS and SPR substrates was developed, which indicates a potential application in tailoring the interfacial structure of an electrode surface. In this study, (3-mercaptopropyl)trimethoxysilane (MPTMS) was selected as a polymeric adhesive layer, and a low concentration of colloid Au solution was used to achieve a more accurate control over interface morphology at nanoscale dimensions due to slow self-assembling kinetics of gold nanoparticle's. Subsequent seeding growth of these MPTMS-supported submonolayers of gold nanoparticles in Au3+/NH2OH aqueous solution enlarges particle size and eventually results in the generation of conductive gold films (similar to previous (3-aminopropyl)trimethoxysilane-supported gold films). Such tunable interface structure was evaluated by atomic force microscopy (AFM). Also, ac impedance spectroscopy (ACIS) and cyclic voltammograms were performed to evaluate electrochemical properties of the as-prepared interfaces by using Fe(CN)(6) (3-/4-) couples as a probe. Furthermore, relevant theories of microarray electrodes were introduced into this study to explain the highly tunable electrochemical properties of the as-prepared interfaces. As a result, it is concluded that the electrochemical properties toward Fe(CN)(6) (3-/4-) couples are highly dependent on the active nanoelectrode (nanoparticles) area fraction and nanoparticles are fine-tuners of interfacial properties because the number density. (numbers/unit area) and size of nanoparticles are highly tunable by self-assembling and seeding growth time scale control. This is in agreement with the theoretical expectations for a microarray electrode if a single nanoparticle tethered to a blocking SAM is taken as a nanoelectrode and 2-D nanoparticle assemblies are taken as nanoelectrode arrays.

Direct electron transfer between hemoglobin and a glassy carbon electrode facilitated by lipid-protected gold nanoparticles

We synthesized a kind of gold nanoparticle protected by a synthetic lipid (didodecyidimethylammonium bromide, DDAB). With the help of these gold nanoparticles, hemoglobin can exhibit a direct electron transfer (DET) reaction. The formal potential locates at -169 mV vs. Ag/AgCl. Spectral data indicated the hemoglobin on the electrode was not denatured. The lipid-protected gold nanoparticles were very stable (for at least 8 months). Their average diameter is 6.42 nm. It is the first time to use monolayer-protected nanoparticles to realize the direct electrochemistry of protein.

Silicon dioxide coating of CeO2 nanoparticles by solid state reaction at room temperature

The synthesis Of SiO2 coated CeO2 nanoparticles by humid solid state reaction at room. temperature is described. Transmission electron microscope results show that CeO2 Particles were coated with a layer Of SiO2. Binding energy of Ce 3d(5/2) was shifted from 883.8 to 882.8 eV after coating in the XPS Ce 3d spectra. This confirms the chemical bond formation between SiO32- and Ce4+. Because the surface photovoltage property of CeO2 nanoparticles that were used as core materials in the experiment approaches to that of CeO2 macroparticles, peak P2 (electron transition from 0 2p on surface to Ce 4f) disappeared in the surface photovoltage spectrum of CeO2 nanoparticles. Also, the effect Of SiO2 on the electron transition from 0 2p to Ce 4f results in the lowering of surface photovoltage response intensity of P1 peak (electron transition from 0 2p in bulk to Ce 4f).

Investigation of electrochemical charging behaviors of "naked" gold nanoparticles ensembles in aqueous media

Gold nanopartides were Immobilized onto the electrode surface by simple self-assembly technique. Interestingly, the ensembles of these nanopartides exhibit quantized charging behaviors in aqueous solution. Possible mechanism for such behaviors was proposed.

Carbon ceramic electrodes bulk-modified with nanoparticles of ferrocenebutyrate-intercalated Mg-Al layered double hydroxide

Ferrocenebutyrate-intercalated layered double hydroxide (FcLDH) was prepared by the coprecipitation method and characterized by PXRD, FTIR, TEM and elemental analysis. FcLDH nanoparticles in deionized water were deposited onto the surface of graphite powder to yield graphite powder-supported FcLDH, which was subsequently dispersed into methyltrimethoxysilane-derived gels to fabricate surface-renewable, stable, rigid carbon ceramic electrodes containing the electroactive ferrocenyl group. Cyclic voltammetric study revealed that peak currents of the FcLDH-modified electrode were diffusion-con trolled in 0.1 mol l(-1) KCl aqueous solution. In addition, the formal potential of the modified electrode is related to the activity of chloride ion with a Nernst slope of 56 mV per decade.

Incorporation of surface-derivatized gold nanoparticles into electrochemically generated polymer films

Stable colloidal solutions of gold nanoparticles surface-derivatized with a thiol monolayer have been prepared using two-phase (water-nitrobenzene) reduction of AuCl4- by sodium borohydride in the presence of 2-mercapto-3-n-octylthiophene (MOT). This kind of surface-functionalized gold nanoparticles can be easily incorporated into the poly(3-octylthiophene) (POT) films on electrode in the process of electrochemical polymerization leading to POT-gold nanoparticle (POT-Au) composite films. Scanning probe microscopy (SPM) and X-ray photoelectric spectroscopy (XPS) have been employed to characterize the surface-derivatized particles and the resulting films. The method of incorporation of nanoparticles into polymer by surface-derivatization and in situ polymerization can also be employed to prepare many other polymer-nanoparticle compostie materials.