Cyclic control of the surface properties of a monolayer-functionalized electrode by the electrochemical generation of Hg nanoclusters

Hg(2+) ions are bound to a 1,4-benzenedimethanethiol (BDMT) monolayer assembled on a Au electrode. Electrochemical reduction of the Hg(2+)-BDMT monolayer to Hg(+)-BDMT (at E degrees =0.48 V) and subsequently to Hg(0)-BDMT (at E degrees =0.2 V) proceeds with electron-transfer rate constants of 8 and 11 s(-1), respectively. The Hg(0) atoms cluster into aggregates that exhibit dimensions of 30 nm to 2 microm, within a time interval of minutes. Electrochemical oxidation of the nanoclusters to Hg(+) and further oxidation to Hg(2+) ions proceeds with electron-transfer rate constants corresponding to 9 and 43 s(-1), respectively, and the redistribution of Hg(2+) on the thiolated monolayer occurs within approximately 15 s. The reduction of the Hg(2+) ions to the Hg(0) nanoclusters and their reverse electrochemical oxidation proceed without the dissolution of mercury species to the electrolyte, implying high affinities of Hg(2+), Hg(+), and Hg(0) to the thiolated monolayer. The electrochemical transformation of the Hg(2+)-thiolated monolayer to the Hg(0)-nanocluster-functionalized monolayer is characterized by electrochemical means, surface plasmon resonance (SPR), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), atomic force microscopy (AFM), and contact-angle measurements. The Hg(0)-nanocluster-modified surface reveals enhanced hydrophobicity (contact angle 76 degrees ) as compared to the Hg(2+)-thiolated monolayer (contact angle 57 degrees ). The hydrophobic properties of the Hg(0)-nanocluster-modified electrode are further supported by force measurements employing a hydrophobically modified AFM tip.     

Switchable surface properties through the electrochemical or biocatalytic generation of Ag0 nanoclusters on monolayer-functionalized electrodes

The electroswitchable and the biocatalytic/electrochemical switchable interfacial properties of a Ag(+)-biphenyldithiol (BPDT) monolayer associated with a Au surface are described. Upon the application of a potential corresponding to -0.2 V the Ag(+)-BPDT is reduced to the Ag(0)-BPDT interface, and silver nanoclusters are generated on the interface. The application of a potential that corresponds to 0.2 V reoxidizes the monolayer to the Ag(+)-BPDT monolayer. The reversible electrochemical transformation of the Ag(+)-BPDT monolayer and of the Ag(0)-BPDT surface was followed by electrochemical means and surface plasmon resonance spectroscopy (SPR). The SPR experiments enabled us to follow the kinetics of nanoclustering of Ag(0) on the surface. The hydrophobic/hydrophilic properties of the surface are controlled by the electrochemically induced transformation of the interface between the Ag(+)-BPDT and Ag(0)-BPDT states. The Ag(0)-BPDT monolayer reveals enhanced hydrophilicity. The hydrophobic/hydrophilic properties of the interface were probed by contact angle measurements and force interactions with a hydrophobically-functionalized AFM tip. The Ag(0)-BPDT interface was also biocatalytically generated using alkaline phosphatase, AlkPh, and p-aminophenyl phosphate as substrate. The biocatalytically generated p-aminophenol reduces Ag(+) ions associated with the surface to Ag(0) nanoclusters. This enables the cyclic biocatalytic/electrochemical control of the surface properties of the modified electrode.     

Scanning electrochemical microscopy as a probe of Ag+ binding kinetics at Langmuir phospholipid monolayers

A new method has been developed for measuring local adsorption rates of metal ions at interfaces based on scanning electrochemical microscopy (SECM). The technique is illustrated with the example of Ag+ binding at Langmuir phospholipid monolayers formed at the water/air interface. Specifically, an inverted 25 microm diameter silver disc ultramicroelectrode (UME) was positioned in the subphase of a Langmuir trough, close to a dipalmitoyl phosphatidic acid (DPPA) monolayer, and used to generate Ag+ via Ag electro-oxidation. The method involved measuring the transient current-time response at the UME when the electrode was switched to a potential to electrogenerate Ag+. Since the Ag+/Ag couple is reversible, the response is highly sensitive to local mass transfer of Ag+ away from the electrode, which, in turn, is governed by the interaction of Ag+ with the monolayer. The methodology has been used to determine the influence of surface pressure on the adsorption of Ag+ ions at a phospholipid (dipalmitoyl phosphatidic acid) Langmuir monolayer. It is shown that the capacity for metal ion adsorption at the monolayer increased as the density of surface adsorption sites increased (by increasing the surface pressure). A model for mass transport and adsorption in this geometry has been developed to explain and characterise the adsorption process.     

硅电极/溶液界面开路电位-时间谱和原子力显微镜在化学镀Ag中的应用研究

用开路电位-时间谱技术,表征了在硅（100）表面化学镀银的硅电极/溶液界 面吸附态。所得结果与原子力显微镜在纳米尺寸上的面结构信息分析结果作了对比 。同时也将该结果与循环伏安法（CV）结果作了比较。证明当硅电极表面具有单层 吸附Ag~+离子、表面单层吸附Ag~+离子发生沉积反应、Ag~+离子发生本体沉积时的 开路电位-时间曲线有完全不同的特征。     

Cysteamine monolayer inducing the formation of platinum nanoclusters for methanol electrocatalytic oxidation

Platinum nanoclusters (Pt-NCs) were synthesized on the surface of a gold electrode that was modified with cysteamine to form a kind of self-assembled monolayer via in-situ cyclic voltammetry (CV). Scanning electron microscopy, electrochemical impedance spectroscopy, and CV were used to characterize the properties of the electrode. The Cys monolayer induces the aggregation of platinum nanoparticles due to electrostatic interaction between the positive amino groups of the cystein monolayer and the negative charge of the hexachloroplatinate ions and causes the formation of Pt-NCs on the surface of the electrode. The resulting electrode exhibits high elecrocatalytic activity towards the oxidation of methanol.     

Formation of bimetallic Ag-Pd nanoclusters via the reaction between Ag nanoclusters and Pd2+ ions

We have investigated systematically the mechanistic aspects of the Ag-Pd bimetallic cluster formation within sodium bis(2-ethylhexyl)sulfosuccinate (AOT) reverse micelles by using in-situ X-ray absorption spectroscopy (XAS). A two-step sequential reduction method is employed for the synthesis of Ag-Pd bimetallic clusters. The first step involves preparation of Ag nanoclusters, by mixing the Ag+ ions containing the AOT microemulsion system with a reducing agent hydrazine (N2H4) containing the AOT microemulsion system. In the second step, the addition of Pd2+ ions to Ag nanoclusters led to the formation of Ag-Pd bimetallic clusters via the reaction between Ag nanoclusters and Pd2+ ions in AOT reverse micelles. The reduction of silver ions and the formation of corresponding Ag nanoclusters are monitored as a function of the dosage of the reducing agent, hydrazine. In-situ XAS allowed probing of the reaction between Ag nanoclusters and Pd2+ ions during the formation of Ag-Pd bimetallic clusters. Analysis of Ag and Pd K-edge XAS spectra reveals that in the final stage Ag-Pd clusters, in which "Ag" atoms prefer to be surrounded by "Pd" and "Pd" atoms prefer to be surrounded by "Pd", were formed. On the basis of XAS results presented here, we are able to propose a structural model for each step so that this work provides a detailed insight into the mechanism of nucleation and growth of Ag-Pd bimetallic clusters. We also discussed the atomic distribution of Ag and Pd atoms in Ag-Pd bimetallic clusters based on the calculated XAS structural parameters.     

Photochemically and electrochemically triggered Au nanoparticles "sponges"

Stimuli-triggered wettability of surfaces and controlled uptake and release of substrates by "smart" materials are essential for drug delivery and microfluidic control. A composite "sponge" consisting of bis-aniline-bridged Au nanoparticles (NPs), functionalized with photoisomerizable nitrospiropyran/nitromerocyanine that includes selective imprinted molecular recognition sites for N,N'-bis(3-sulfonatopropyl)-4,4'-bipyridinium (PVS) was electropolymerized on a Au electrode. The system is triggered by photonic and/or electrical signals to yield four different states exhibiting variable binding/release capacities for PVS and controlled wettability of the surface. The electrical/optical uptake and release of PVS to and from the Au NPs "sponge", respectively, is followed by CdSe/ZnS quantum dots, acting as an auxiliary photonic label.     

In situ sensing of metal ion adsorption to a thiolated surface using surface plasmon resonance spectroscopy

The kinetics of the adsorption of metal ions onto a thiolated surface and the selective and quantitative sensing of metal ions were explored using surface plasmon resonance (SPR) spectroscopy. The target metal ion was an aqueous solution of Pt2+ and a thin-gold-film-coated glass substrate was modified with 1,6-hexanedithiol (HDT) as a selective sensing layer. SPR spectroscopy was used to examine the kinetics of metal ion adsorption by means of the change in SPR angle. The selectivity of the thiolated surface for Pt2+ over other divalent metal ions such as Cu2+, Ni2+, and Cd2+ was evident by the time-resolved SPR measurement. SPR angle shift, deltatheta(SPR), was found to increase logarithmically with increasing concentration of Pt2+ in the range of 1.0 x 10(-5)-1.0 mM. The rate of Pt2+ adsorption on HDT observed at both 0.1 and 1 mM Pt2+ accelerates until the surface coverage reaches approximately 17%, after which the adsorption profile follows Langmuirian behavior with the surface coverage. The experimental data indicated that heavy metal ions were adsorbed to the hydrophobic thiolated surface by a cooperative mechanism. A mixed self-assembled monolayer (SAM) composed of HDT and 11-mercaptoundecanoic acid was used to reduce the hydrophobicity of the thiol-functionalized surface. The addition of hydrophilic groups to the surface enhanced the rate of adsorption of Pt2+ onto the surface. The findings show that the adsorption of metal ions is strongly dependent upon the hydrophilicity/hydrophobicity of the surface and that the technique represents an easy method for analyzing the adsorption of metal ions to a functionalized surface by combining SPR spectroscopy with a SAM modification.     

Molecular self-assembled monolayers of ruthenium(II)-terpyridine dithiol complex on gold electrode and nanoparticles

We describe the formation of stable dithiol-bifunctionalized Ru(II)-terpyridine monolayer onto gold electrode. The coverage-dependent behavior onto gold electrode has been studied by electrochemical technique. The stability, surface charge coverage, and electron-transfer kinetics were assessed by cyclic voltammetry. Functionalized monolayer-protected Au clusters (MPCs) were also prepared. The spectroscopic characterization data of MPCs using UV-Vis and TEM techniques are discussed. TEM images showed that functionalized spherical nanoclusters of 4.7 ± 0.3 and 4.3 ± 0.2 nm were produced. The particle sizes are uniform with a narrow size distribution. The morphology of Au(1 1 1) metal surface modified with MPCs was imaged using atomic force microscopy (AFM). The nanoparticle layer exhibits a distinct surface morphology, irregularly shaped domains with dimensions from 20 to 60 nm and root mean square heights of 2.401 nm.     

Anodic dissolution of the mercury electrode by the CH3O− ions formed during the reduction of organic compounds in methanol

Anodic dissolution of the HMDE from CH₃O^? ions formed during the electrochemical reduction of organic compounds in methanol arises only if the electroreduction is non-reversible. When, however, the organic substances undergo a reversible reduction, the CH₃O^? ions formed during the reduction are neutralized by the protons released during reoxidation. The anodic dissolution of the mercury electrode is attributed to the formation of insoluble Hg₂(OCH₃)₂, as with many other ions which depolarize the mercury electrode in aqueous solution with the formation of insoluble salts.     

A general route to synthesize water-dispersive noble metal-iron oxide bifunctional hybrid nanoparticles

This communication describes a simple, general route for preparing bifunctional hybrid nanoparticles based on direct adsorption and spontaneous reduction of Ag(+) and Pd(2+) onto the surface of carbon-encapsulated superparamagnetic colloidal nanoclusters. Because of the existence of carbon coating and surface hydrophilic carboxyl, the bifunctional hybrid nanoparticles show excellent water-dispersity. In addition, the size (35 nm-86 nm) and number of Ag nanocrystals can be tuned by changing the molar ratios and reaction concentration between Ag(+) and nanoclusters.     

Study on coordination of selenoamino acids with Ag+ at silver nitrate-modified carbon paste electrode

Surface Ag+ ions forming complexes with the amino (selenoamino) acids compounds have been studied at a silver nitrate-modified carbon paste electrode (AgNO3/CPE). The carboxyl, amidogen and selenium of selenoamino acids could coordinate with Ag+. The coordinating sites of Ag+-SeCys and Ag+-SeMet on electrode surface have been studied in the range of pH value from 1.0 to 12.0. The coordinating sites of Ag+-SeCys and Ag+-SeMet are due to the different configuration and electronegative charge of amino acids in different acidity. Increase of the coordination number of adsorbed species increases the average lifetime of these species on the surface, and hence causes that stronger bonded molecules more effectively prevent the depletion of the surface layer from the Ag+ ions. The voltammetric signals of Ag+-selenoamino acid and Ag+-sulfur-containing amino acid are stronger than those of Ag+-alanine due to the coordinating sites of AgS and AgSe bonds. Moreover, the adsorption of Ag+-selenoamino acid on electrode surface relates to different acidity.     

Co-adsorption of CO onto a Ag-modified Pt(111)--restructuring of a Ag UPD layer monitored by EC-STM

The effect of co-adsorption of CO on an underpotentially deposited (UPD) silver monolayer on a Pt(111) single crystal electrode in 0.05 M sulfuric acid is investigated for the first time by means of electrochemical scanning tunneling microscopy (EC-STM). Pure electrochemical experiments suggest that the co-adsorption of CO onto Pt single crystal electrodes previously modified by a monolayer of Ag, forces Ag atoms of the first UPD monolayer into a second adlayer. The present EC-STM studies reveal the formation of a large-area Ag network after the co-adsorption of CO. The resulting Ag nanostructures formed on wide Pt(111) terraces are approximately 0.5 nm high and 10 nm wide. The desorption of the newly formed second Ag adlayer, the oxidation of CO and the desorption of Ag atoms from the first adlayer are monitored by EC-STM and simultaneously detected in the corresponding CVs in three different oxidation peaks. EC-STM images recorded afterwards show the unchanged Pt surface. The presence of Ag on the surface leads to a downward shift of the onset of oxygen adsorption on the Pt(111) surface.     

In situ depositing silver nanoclusters on silk fibroin fibers supports by a novel biotemplate redox technique at room temperature

Evolvement of bioinspired approaches for the construction of well-ordered nanostructures is a crucial intersection of branches of materials science and biotechnology. In this paper, floriated clusters of silver nanocrystallites, which consist of polycrystalline grains about 5 nm in diameter, have been successfully prepared on silk fibroin fibers (SFFs) through an in situ biotemplate redox approach at room temperature. The reductive amino acid tyrosine of SFFs mainly provided both reduction and location functions under alkaline conditions and could reduce Ag(I) ions to Ag(0). Finally, stable silver nanoclusters were generated on SFF substrates. The morphologies of silver nanoclusters were mostly attributed to the concentration of silver nitrate solution as well as special configurations and structures of silk fibroin macromolecules. A possible mechanism was explored intensively for tyrosine-residue-based silver nanocrystal formation.     

Colorimetric detection of iron ions (III) based on the highly sensitive plasmonic response of the N-acetyl-l-cysteine-stabilized silver nanoparticles

We report here a facile colorimetric sensor based on the N-acetyl-l-cysteine (NALC)-stabilized Ag nanoparticles (NALC–Ag NPs) for detection of Fe³⁺ ions in aqueous solution. The Ag NPs with an average diameter of 6.55 ± 1.0 nm are successfully synthesized through a simple method using sodium borohydride as reducing agent and N-acetyl-l-cysteine as protecting ligand. The synthesized silver nanoparticles show a strong surface plasmon resonance (SPR) around 400 nm and the SPR intensity decreases with the increasing of Fe³⁺ concentration in aqueous solution. Based on the linear relationship between SPR intensity and concentration of Fe³⁺ ions, the as-synthesized water-soluble silver nanoparticles can be used for the sensitive and selective detection of Fe³⁺ ions in water with a linear range from 80 nM to 80 μM and a detection limit of 80 nM. On the basis of the experimental results, a new detection mechanism of oxidation–reduction reaction between Ag NPs and Fe³⁺ ions is proposed, which is different from previously reported mechanisms. Moreover, the NALC–Ag NPs could be applied to the detection of Fe³⁺ ions in real environmental water samples.     

Optically activated uptake and release of Cu2+ or Ag+ ions by or from a photoisomerizable monolayer-modified electrode

Di-(N-butanoic acid-1,8-naphthalimide)-piperazine dithienylethene was covalently linked to a cysteamine monolayer associated with a Au surface to yield a photoisomerizable monolayer composed of the open or closed dithienylcyclopentene isomers (3a or 3b), respectively. Electrochemical and XPS analyses reveal that the association of metal ions to the monolayer is controlled by its photoisomerization state. We find that Cu(2+) ions reveal a high affinity for the open (3a) monolayer state, K(a) = 4.6 × 10(5) M(-1), whereas the closed monolayer state (3b) exhibits a substantially lower binding affinity for Cu(2+), K(a) = 4.1 × 10(4) M(-1). Similarly, Ag(+) ions bind strongly to the 3a monolayer state but lack binding affinity for the 3b state. The reversible photoinduced binding and dissociation of the metal ions (Cu(2+) or Ag(+)) with respect to the photoisomerizable monolayer are demonstrated, and the systems may be used for the photochemically controlled uptake and release of polluting ions. Furthermore, we demonstrate that the photoinduced reversible binding and dissociation of the metal ions to and from the photoisomerizable electrode control the wettability properties of the surface.     

Processing of nanoporous Ag layers by potential-controlled displacement (PCD) of Cu

A cementation-like process taking place under potential control and introduced in this work as a "potential-controlled displacement" (PCD) is developed as a new method for processing of nanoporous Ag structures with controlled roughness (porosity) length scales. Most of the development work is done in a deoxygenated electrolyte containing 1 x 10(-3) M AgClO(4 )+ 5 x 10(-2) M CuSO(4) + 1 x 10(-1) M HClO(4) using a copper rotating disk electrode at 50 rpm. At this electrolyte concentration, the Ag deposition is under diffusion limitations whereas the Cu dissolution displays a typical Butler-Volmer anodic behavior. Thus, a careful choice of the operational current density enables strict control of the ratio between the dissolving and depositing metals as ascertained independently by atomic absorption spectrometry (AAS). The roughness length scale of the resulting surfaces is controlled by a careful selection of the current density applied. The highest surface area and finest morphology is obtained when the atomic ratio of Ag deposition and Cu dissolution becomes 1:1. Preseeding of uniform Ag clusters on the Cu surface made by pulse plating of Ag along with complementary plating and stripping of Pb monolayer is found to yield finer length scale resulting in up to a 67% higher surface area. An electrochemical technique using as a reference value the charge of an underpotentially deposited Pb layer on a flat Ag surface is used for measuring the real surface area. Scanning electron microscopy (SEM) studies are conducted to examine and characterize the deposit morphology of Ag grown by PCD on Cu substrates.     

Polymer-initiated photogeneration of silver nanoparticles in SPEEK/PVA films: direct metal photopatterning

Cross-linking of sulfonated poly(ether-ether)ketone-poly(vinyl alcohol) (SPEEK-PVA) materials yields flexible polymer films, possessing high light-sensitivity and ion-exchange capabilities. Adsorbed Ag+ ions are photoreduced in the film under illumination (lambda = 350 nm), leading to metal nanoparticle formation in places where the film has been exposed to the light. Nanoparticles form via reduction of Ag+ by the polymeric alcohol radicals, generated in the system as a result of photochemical H-abstraction from PVA molecules by the excited carbonyl triplet state of SPEEK. Use of the films for direct metal photopatterning is demonstrated.     

X-ray-induced production of gold nanoparticles on a SiO(2)/Si system and in a poly(methyl methacrylate) matrix

Prolonged exposure to X-rays of HAuCl(4) deposited from an aqueous solution onto a SiO(2)/Si substrate or into a poly(methyl methacrylate) (PMMA) matrix induces reduction of the Au(3+) ions to Au(0) and subsequent nucleation to gold nanoclusters as recorded by X-ray photoelectron spectroscopy. The corresponding major oxidation product is determined as chlorine {HAuCl(4)(ads) + X-rays --> Au(ads) + (3/2)Cl(2)(ads) + HCl(ads)}, which is initially adsorbed onto the surface but eventually diffuses out of the system into the vacuum. The reduced gold atoms aggregate (three-dimensionally) into gold nanoclusters as evidenced by the variation in the binding energy during X-ray exposure, which starts as 1.3 eV but approaches a value that is 0.5 eV higher than that of the bulk gold. The disappearance of the oxidation product (Cl2p signal) and the growth of the nanoclusters (related to the measured binding energy difference between the Si2p of the oxide and Au4f of the reduced gold) exhibit first-order kinetics which is approximately 3 times slower than the reduction of Au(3+), indicating that both of the former processes are diffusion controlled. Similarly, gold ions incorporated into PMMA can also be reduced and aggregated to gold nanoclusters using 254 nm deep UV irradiation in air evidenced by UV-vis-NIR absorption spectrocopy.     

Au/Ag核一壳结构复合纳米粒子形成机制的研究

在已制备好的Au纳米粒子表面,通过化学还原的方法沉积生长Ag包覆层,通过 控制Au, Ag的比列,制备了粒度均匀且粒径可控的Au/Ag核-壳结构纳米粒子。利用 UV-vis吸收光谱和透射电子显微镜（TEM）对SAu, Ag摩尔比为1：10的复合纳米粒 子的光学性质和形态进行随时监测,直接观察了核-壳结构纳米粒子的生长过程： 一部分Ag+在Au核表面还原生长,溶液中其余Ag+还原形成银的纳米团簇向粒子表面 的继续沉积生长,壳层增厚。