The formation and behavior of Ag adsorbates at Pd electrodes and their influence on electrocatalytic oxidation of formic acid at Pd

The electrochemical behavior of Ag ions at smooth Pd electrodes and Pd/Pt deposits is investigated. At adsorption potentials, which are more anodic than the reversible potential of the Ag⁺/Ag electrode, an underpotential deposition of Ag⁺ ions occur.We can distinguished two types of Ag ad-atoms at Pd. The first type of Ag is irreversibly adsorbed. The second, which exists only in the presence of Ag ions in the solution, is reversibly adsorbed.The influenced of various coverages of Ag ad-atoms at smooth Pd and Pd/Pt deposits on the electrocatalytical oxidation of formic acid was investigated. Even small coverages of Ag ad-atoms lower the rate of formic acid oxidation. With higher coverages this inhibiting influence grows continously.     

The treatment of Ag,Pd, Au and Pt electrodes with OH<Superscript>•</Superscript> radicals reveals information on the nature of the electrocatalytic centers

The treatment of Ag, Pd, Au and Pt electrodes with OH^• radicals can be used to get information on the nature of the electrocatalytic sites. Atomic force microscopy (AFM) measurements, various electrochemical techniques, and chemical solution analysis show a more or less effective surface dissolution of these metals upon OH^• treatment. The effect of the surface alterations on the electrocatalytic activity with respect to the quinone/hydroquinone system revealed distinct differences between Ag and Au (previous studies) on one side, and Pt and Pd on the other side. Whereas, in case of Pt and Pd, the electrocatalytic properties are obviously related to the regular surface atoms, in case of Ag and Au the active centers are highly reactive surface atoms which can be removed by OH^• radicals.     

Adsorption of n-pentanol from KPF6 aqueous solution on the (100) and (110) faces of Ag single crystal electrodes

The potential dependence of the adsorption of n-pentanol (NP) on the (100) and (110) faces of Ag single crystal electrodes from aqueous KPF₆ solutions has been studied at 10 mV s⁻¹ potential scan rate by measuring the impedance both at constant frequency (f) and by sweeping f from 11 kHz to 0.1 Hz. The adsorption of NP has been found to be strongly dependent on crystal orientation. The results have been compared with those obtained on Ag(111) with the same kind of single crystal preparation, as well as with Ag(100) electrolytically grown in a Teflon capillary [A. Popov, O. Velev, T. Vitanov, J. Electroanal. Chem. 256 (1988) 405].     

Neutron activation analysis of platinum metals in airborne particulate matter

A method is described for the determination of Au, Pt, Pd, Ag and Ir in two atmospheric aerosol samples, namely in Ghent and in the Milanese intercomparison sample. After neutron irradiation the samples are fused with Na₂O₂. Gold is extracted with ethylacetate, Pt precipitated as (NH₄)₂PtCl₆ Pd as dimethylglyoximate, Ag as chloride and Ir separated by anion-exchange adsorption and batch extraction. Ge(Li) gamma-spectrometry is applied for all determinations. The concentrations in ng·g⁻¹ in the samples are respectively: Au: 49 and 3000; Pt: below 100 for both samples; Pd: 7 and 28; Ag: 6000 and 14 000; Ir: 2.5 and 1.3.     

Electrochemical impedance of microelectrodes

The influence of the radius (10 <a < 1500 μm) of a Pt disk electrode on the impedance frequency spectrum of the [Fe(CN)₆]^3-/4- reversible system is studied in the frequency range 5 × 10^-3 to 10³ Hz. The impedance is calculated by applying the Fourier transform to potential and current pulses of various lengths obtained when imposing a step potential. For electrodes witha < 100 μm, the spectrum in the complex plane has the form characteristic of microelectrodes, while for electrodes of higher radii, it corresponds to a finite Warburg impedance. The main impedance parameters, such as the charge transfer resistance, the diffusion resistance, and the frequency in the maximum of the imaginary constituent are determined. The latter decreases with an increase ina by the lawf* ∼ 1/a² at lowa and is independent ofa on electrodes witha > 100 μm, which agrees with the impedance theory for microelectrodes     

Electrooxidation of Several Organic Compounds on Simply Prepared Metallic Nanoparticles: A Comparative Study

The electrooxidation of several fuel compounds was studied using metallic nanoparticles of Au, Pd, Pt, AuPd and AuPt synthesized by direct electrodeposition by applying a constant potential of ‐200 mV (vs. Ag/AgCl) to pencil graphite in an acidic medium. Scanning electron microscope (SEM) images and X‐ray diffraction (XRD) data show that monometallic (Au, Pd and Pt) and alloys of bimetallic nanoparticles of AuPd and AuPt have been formed. The catalytic performance of the prepared electrodes was investigated in a neutral medium (100 mM phosphate buffer, pH 7) by cyclic voltammetry. Amongst all fuels, the highest current densities were obtained by the electrooxidation of formic acid (ca. 9.8 mA cm^?2) and formaldehyde (ca. 9.7 mA cm^?2) on the AuPt catalyst.     

Surface Changes at Platinized Platinum Based Hydrogen Gas Electrodes Following Use in Highly Saline Aqueous Solutions

Platinized platinum based hydrogen gas electrodes, Pt(Pt)|H₂(g)|H⁺(aq), and silver‐silver chloride electrodes, Ag|AgCl|Cl^? (aq), make up the Harned cell, without transfer, working in the potentiometric mode at Cl^? concentrations and ionic strengths, I, below 0.1 mol kg^?1, for assigning primary pH values to reference pH buffer solutions. This work reports on experiments performed at higher I and Cl^? solutions up to 0.7 mol kg^?1, aiming at addressing seawater conditions with results of equally high quality. In the course of measurements, the occasional occurrence of highly unstable potentials denoted electrode malfunction; Pt metal surfaces observed by SEM/EDS and XRD exhibit strong Ag and Cl peaks corresponding to the presence of AgCl crystals deposited at both surfaces.     

Synthesis of Au, Au/Ag, Au/Pt and Au/Pd nanoparticles using the microwave-polyol method

Gold, Au/Ag, Au/Pt and Au/Pd bimetallic nanoparticles with varying mol fractions were synthesized in ethylene glycol and glycerol, using the microwave technique in the presence of a stabilizer poly(N-vinylpyrrolidone) (PVP). It was found that bimetallic colloids of Au/Ag, Au/Pd and Au/Pt form an alloy either on co-reduction of respective metal ions or on mixing individual sols.     

A study of samarium ions electroreduction at various electrodes in KCl-NaCl-CsCl melt at <Emphasis Type="Italic">T</Emphasis> = 823 K

Samarium ions electroreduction mechanism was studied on the supporting of KCl-NaCl-CsCl eutectic melt at 823 K on various electrodes (W, Mo, Al, Ni, Pt, and Ag). The diffusion coefficients of SmCl₆³⁻ chloride complexes and Sm³⁺ → Sm²⁺ heterogeneous recharge stage rate constant K _fh⁰ were calculated in KCl-NaCl-CsCl melt at T = 823 K.     

Oxygen reduction reaction on the low index planes of palladium electrodes modified with a monolayer of platinum film

Oxygen reduction reaction (ORR) has been studied on the low index planes of Pd modified with a monolayer of Pt (Pt/Pd(hkl)) in 0.1 M HClO₄ with the use of hanging meniscus rotating disk electrode. The activity for ORR on bare Pd(hkl) electrode depends on the surface structure strongly, however, voltammograms of ORR on Pt/Pd(hkl) electrodes do not depend on the crystal orientation. The specific activities of Pt/Pd(hkl) electrodes at 0.90 V (RHE) are higher than that on Pt(1 1 0) which has the highest activity for ORR in the low index planes of Pt. The mass activity on Pt/Pd(hkl) electrode is 7 times as high as a commercial Pt/C catalyst.     

Electrocatalytic activity of platinum—polyaniline and palladium—polyaniline systems obtained by cycling the electrode potential

Steady-state current densities of electrooxidation of CH₃OH, HCOOH, and CO at the Pt-PAN-GC electrodes (where PAN and GC stand for polyaniline and glassy carbon, respectively) and those of electrooxidation of HCOOH at the Pd-PAN-GC electrodes are measured (per cm₂ of the true metal-catalyst surface area). The found higher activity of Pt and Pd particles incorporated in PAN, as compared with Pt/Pt and Pd/Pt, is attributed to interaction between metal-catalyst particles and the polymeric matrix. The activation effect is the most pronounced for the HCOOH electrooxidation at Pd-PAN-GC. The data concerning hydrogen evolution testify in favor of a decrease in exchange currents of this reaction upon going from Pt to Pt-PAN-GC electrodes     

Structural effects of electrochemical oxidation of formic acid on single crystal electrodes of palladium

Structural effects on the rates of formic acid oxidation have been studied on Pd(111), Pd(100), Pd(110), and Pd(S)-[n(100) x (111)] (n = 2-9) electrodes in 0.1 M HClO4 containing 0.1 M formic acid with use of voltammetry. On the low index planes of Pd, the maximum current density of formic acid oxidation (jP) increases in the positive scan as follows: Pd(110) < Pd(111) < Pd(100). This order differs from that on the low index planes of Pt: Pt(111) < Pt(100) < Pt(110). Pd(S)-[n(100) x (111)] electrodes with terrace atomic rows n > or = 3 have almost the same jP as Pd(100), except Pd(911) n = 5. The value of jP on Pd(911) n = 5 is 20% higher than those of the other surfaces. Pd(311) n = 2, of which the first layer is composed of only step atoms, has the lowest jP in the Pd(S)-[n(100) x (111)] series. The adsorption geometry of the reaction intermediate (formate ion) is optimized by using density functional theory.     

Determination of silver,gold, palladium,and platinum on milligram scale: m-(mercaptoacetamido)phenol as gravimetric reagent

Summary A method for the gravimetric determination of milligram quantities of Ag(I), Au(III), Pd(II), and Pt(IV) is presented. It is based on precipitation of the respective chelates withm-(mercaptoacetamido)phenol. Procedures for the analysis of binary and ternary mixtures are described.

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Zusammenfassung Die gravimetrische Bestimmung von Milligrammengen Ag(I), Au(III), Pd(II) und Pt(IV) durch Fällung ihrer Chelate mit m-Merkaptoacetamidophenol wird vorgeschlagen. Arbeitsvorschriften für die Analyse binärer oder ternärer Gemische wurden angegeben.

     

Harmonious Heterointerfaces Formed on 2D-Pt Nanodendrites by Facet-Respective Stepwise Metal Deposition for Enhanced Hydrogen Evolution Reaction

The performance of nanocrystal (NC) catalysts could be maximized by introducing rationally designed heterointerfaces formed by the facet- and spatio-specific modification with other materials of desired size and thickness. However, such heterointerfaces are limited in scope and synthetically challenging. Herein, we applied a wet chemistry method to tunably deposit Pd and Ni on the available surfaces of porous 2D−Pt nanodendrites (NDs). Using 2D silica nanoreactors to house the 2D-PtND, an 0.5-nm-thick epitaxial Pd or Ni layer ( e - Pd or e -Ni ) was exclusively formed on the flat {110} surface of 2D−Pt, while a non-epitaxial Pd or Ni layer ( n - Pd or n -Ni ) was typically deposited at the {111/100} edge in absence of nanoreactor. Notably, these differently located Pd/Pt and Ni/Pt heterointerfaces experienced distinct electronic effect to influence unequally in electrocatalytic synergy for hydrogen evolution reaction (HER). For instance, an enhanced H₂ generation on the Pt{110} facet with 2D-2D interfaced e -Pd deposition and faster water dissociation on the edge-located n -Ni overpowered their facet-located counterparts in respective HER catalysis. Therefore, a feasible assembling of the valuable heterointerfaces in the optimal 2D n -Ni/e-Pd/Pt catalyst overcame the sluggish alkaline HER kinetics, with a catalytic activity 7.9 times higher than that of commercial Pt/C.     

High‐accuracy bulk metallic glass mold insert for hot embossing of complex polymer optical devices

Metallic glasses (MGs) have been reported to be excellent mold insert materials for hot embossing of polymers, but limited by the simple shape of the embossed polymer devices and the high cost resulted by the application of Pt‐ and Pd‐based MGs. The development of inexpensive MG mold inserts with complex shape as well as high accuracy is of great importance. In present work, polymethylmethacrylate optic devices with complex micro structures and excellent grating performance have been hot embossed precisely by using newly developed centimeter‐sized Ni₆₂Pd₁₉Si₂P₁₇ MG molds. The Ni₆₂Pd₁₉Si₂P₁₇ MG exhibits high fracture strength of 1840 MPa, distinctive plastic strain of 4% and high thermal‐stability. The die imprinted MG microstructures exhibit very low linear shrinkage (0.002 μm) and relative linear shrinkage rate (0.033%). It indicates that the Ni₆₂Pd₁₉Si₂P₁₇ MG could serve as inexpensive and durable mold inserts for precise embossing of polymer micro devices in large scale. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 463–467     

Electrocatalytic Reduction and Determination of Dissolved Oxygen at a Preanodized Screen‐Printed Carbon Electrode Modified with Palladium Nanoparticles

Efficient and stable electrocatalytic activity for the reduction of O₂ at activated screen‐printed carbon electrodes modified with palladium nanoparticles (SPE*‐Pd) was demonstrated in this study. X‐ray photoelectron spectroscopy confirmed the formation of >C?O functional group on electrode surface during the preanodization procedure at 2.0 V (vs. Ag/AgCl). The existence of chloride moieties was also identified possibly from the organic binder of carbon ink used in SPE fabrication. Both >C?O and chloride functional groups were essential for the excellent stability of the SPE*‐Pd. Electrochemical impedance spectroscopy verified the enhanced kinetic rate of oxygen reduction reaction at the as‐prepared Pd nanoparticles. The SPE*‐Pd showed ca. 250 mV positive shift in peak potential together with twice increase in peak current compared to those observed at a SPE‐Pt. The calibration plot was linear up to 8 ppm of DO with sensitivity and regression coefficient of 4.49 μA/ppm and 0.9936, respectively. The variation coefficient of i_pc for 7 DO determinations with O₂‐saturated pH 7.4 PBS was 2.1%. Real sample assays for ground and tap waters gave consistent values to those measured by a commercial dissolved oxygen meter.     

Controlled Aqueous Solution Synthesis of Platinum–Palladium Alloy Nanodendrites with Various Compositions Using Amphiphilic Triblock Copolymers

In a recent study, we demonstrated that Pluronic F127 triblock copolymer plays a critical role in the formation of dendritic Pt nanostructures (L. Wang, Y. Yamauchi, J. Am. Chem. Soc. 2009 , 131, 9152–9153). Herein, we expand this concept to produce novel dendritic Pt–Pd alloy nanoparticles. In this paper, a very simple, one‐step and efficient route is proposed to directly produce dendritic Pt–Pd alloy nanoparticles with high surface area in high yield, which is carried out simply by stirring an aqueous solution that contains K₂PtCl₄ and Na₂PdCl₄ binary precursors in the presence of Pluronic F127 block copolymer and ascorbic acid at room temperature within 30 min without the need for any template, seed‐mediated growth, or additive. By simply changing the compositional ratios of the Pt and Pd sources in the precursor solutions, Pt–Pd nanodendrites with various compositions can be easily produced. Because of its unique simplicity, the proposed approach can be considered as a powerful strategy for producing Pt–Pd alloy nanoparticles with unique nanoarchitectures for commercial devices.     

Electrochemical Impedance Spectroscopy and Cyclic Voltammetry of <Emphasis Type="Italic">cis</Emphasis>-[Cr(bipy)<Subscript>2</Subscript>(SCN)<Subscript>2</Subscript>]I (where bipy: 2,2′-Bipyridine) in Polar Solvents

Cyclic voltammetric studies (CV) on the complex cis-bis(2,2′-bipyridine)bis(thiocyanate)chromium(III) iodide [Cr(bipy)₂(SCN)₂]I (where bipy: 2,2′-bipyridine, C₁₀H₈N₂) were recorded on platinum (Pt) and glassy carbon (GC) electrodes in either acetonitrile (ACN) or acetone (ACE) solvent media including n-tetrabutylammonium hexafluorophosphate (NBu₄PF₆) as supporting electrolyte, at scan rates (v) ranging from 0.05 to 0.12 V⋅s⁻¹. In addition, electrochemical impedance spectroscopic (EIS) measurements in the frequency (f) range from 0.1 Hz to 50 kHz were carried out on GC and Pt electrodes. The half-wave potential (E _1/2) of the redox couple Cr(III)/Cr(II) was determined as −0.84 V and −0.79 V (versus Ag/AgCl) in ACN and ACE, respectively. The heterogeneous electron transfer rate constant (k _s) corresponding to the couple Cr(III)/Cr(II) was found to be greater on GC compared to the Pt electrode. The nature of the solvent medium also affects the kinetics of the investigated couple, to be exact, k _s increases remarkably upon replacement of ACE by ACN. The EIS results indicate that the GC electrode is a better capacitor and provides the smaller charge transfer resistance in ACN.     

CO和SCN~-在高分散Pt及Pd表面异常红外光学行为的电化学现场FTIR反射光谱研究

在玻碳基底上沉积Pt和Pd，在以CO和SCN-为探针分子的电化学现场FTIR反射光谱研究中，首次观察到异常红外光学行为，其中包括吸附物种的谱带方向倒反以及谱峰强度显著增强等．     

Heteropolymetallic Architectures as Snapshots of Transmetallation Processes at Different Degrees of Transfer

Novel heteropolymetallic architectures have been built by integrating Pd, Au and Ag systems. The dinuclear [(CNC)(PPh₃)Pd-^G11M(PPh₃)](ClO₄) (^G11M=Au ( 3 ), Ag ( 4 ); CNC=2,6-diphenylpyridinate) and trinuclear [{(CNC)(PPh₃)Pd}₂^G11M](ClO₄) (^G11M=Au ( 6 ), Ag ( 5 )) complexes have been accessed or isolated. Structural and DFT characterization unveil striking interactions of one of the aryl groups of the CNC ligand(s) with the ^G11M center, suggesting these complexes constitute models of transmetallation processes. Further analyses allow to qualitatively order the degree of transfer, proving that Au promotes the highest one and also that Pd systems favor higher degrees than Pt. Consistently, Energy Decomposition Analysis calculations show that the interaction energies follow the order Pd−Au > Pt−Au > Pd−Ag > Pt−Ag. All these results offer potentially useful ideas for the design of bimetallic catalytic systems.