Bismuth nanoparticles electrooxidation: theory and experiment

The article presents the findings of microscopic and electrochemical studies of electrooxidation of bismuth particle of varying sizes. Bismuth particles were immobilized on the surface of indifferent carbon containing screen-printed electrodes. The calculations and experimental studies demonstrated that the transition from macroparticles to nanoparticles caused a shift of the maximum current potential of bismuth oxidation into the area with more negative potentials. A positive correlation between experimental and calculated data confirms once again a relevant application of the earlier proposed mathematical model and the possible use of the shift of the maximum current potential of electrooxidation to describe electrochemical activity and energy properties of metal nanoparticles.

     

Silver nanoparticles electrooxidation: theory and experiment

This article presents the findings of microscopic and electrochemical studies of electrooxidation of silver nanoparticles of varying sizes in comparison with “bulk” silver. Silver particles were immobilized on the surface of indifferent carbon-containing screen-printed electrodes. Vacuum-deposited silver represented the “bulk” electrode. The calculations and experimental studies demonstrated that the transition from macro- to nanostructural electrodes is followed by a shift of the maximum current potential of metal oxidation into the area with more negative potentials. A positive correlation between experimental and calculated data confirms once again a relevant application of the earlier proposed mathematical model and the possible use of the shift of the maximum current potential of electrooxidation to describe the electrochemical activity and surface energy properties of metal nanoparticles.     

Gold nanoparticles electrooxidation: comparison of theory and experiment

The article presents the findings of microscopic and electrochemical studies of size-dependent gold particles electrooxidation. Gold particles were immobilized on the surface of carbon-containing screen-printed electrodes. The experiment demonstrated that the transition from macroparticles to nanoparticles caused a shift of the maximum current potential of gold oxidation into the area with more negative potentials. A decrease in particle size resulted in an increase in the electrochemical activity of metal. A positive correlation between experimental and calculated curves confirms a mathematical model (2) and correctness of the calculations. Measured parameters of voltammograms, in particular, maximum current potential, can be used to describe the electrochemical activity and energy properties of nanoparticles.     

Electrochemistry of metal nanoparticles: the effect of substrate

It is shown that nanoparticles localized on a foreign solid electrode may display two opposite shifts of dissolution potential, namely, a shift toward either more positive or more negative values as compared with the equilibrium potential of M ⁿ⁺/M ⁰ or the potential of bulk metal electrooxidation. The observed phenomena are interpreted in view of three energy states of substance, which are realized depending on contribution of the surface Gibbs free energy (ΔG°) to the energy of the system. Literature data concerning different metal-substrate pairs and specially conducted experimental investigations of electrooxidation of gold nanoparticles (radius equal to 10 and 150?nm), which are localized on the surface of glassy carbon, bulk gold, and platinum electrodes are presented and discussed. A shift of maximum current potential of small nanoparticles oxidation toward more positive values is observed in this series. The oxidation potential of large nanoparticles is not affected by the nature of the substrate. In all cases, electrooxidation of gold nanoparticles occurs at the more negative potentials than those of the bulk gold electrooxidation. It is shown that depending on the nature of the substrate and nanoparticle size, the dominating effect is either interaction of nanoparticles with the substrate (ΔG°?<?0) and electrochemical potential shifts toward positive values or impact of surface Gibbs free energy of nanoparticles (ΔG°?>?0) into energy of the system and electrochemical potential shifts toward negative values. The validity of the proposed assumptions is confirmed by good correlation of literature and our experimental data with calculated ones.     

Study of electrooxidation of binary electrolytic deposit palladium–bismuth deposited on graphite electrode surface

The phase structure of palladium–bismuth binary electrolytic deposit was studied. The electrodeposition of deposit components on the surface of a graphite electrode (GE) was carried out in situ. On current–voltage curves, the peak of bismuth electrooxidation, the peak of palladium electrooxidation and an additional peak at 0.15 V vs. Ag/AgCl are observed. The peak current at 0.15 V depends both on the concentration of palladium(II) ions and on that of bismuth(III) ions. The thermodynamic theory of alloys in the approximation of the theory of regular solutions was used for calculations. The mixing heat of the binary alloy components and the equilibrium potential of bismuth in the bismuth–palladium alloy are calculated. The calculated equilibrium potential of bismuth in an alloy with palladium is 0.12 V vs. Ag/AgCl which corresponds to the Bi₂Pd intermetallic compound (IMC). Investigation of the surface of a GE with a palladium–bismuth deposit with use of scanning electron microscope showed that the electrolytic deposit contains bismuth, palladium and the Bi₂Pd IMC. Peak at the potential of plus 0.15 V vs. Ag/AgCl is due to selective bismuth electrooxidation from the Bi₂Pd IMC.     

Pd Nanostructures with High Tolerance to CO Poisoning in the Formic Acid Electrooxidation Reaction

Pd architectures such as nanobars and nanoparticles were synthetized by the polyol method using di-ethylene glycol as reaction media. The morphology, composition and electrocatalytic properties were investigated by transmission electronmicroscopy (TEM), thermo-gravimetric analysis (TGA), X-ray diffraction (XRD) and electrochemical measurements. The electrocatalytic activity of Pd nanostructures was tested in terms of formic acid electrooxidation reaction (FAOR) in acid media (0.5 M H₂SO₄) and compared with commercial Pd/XC-72 (Pd/C). Results from the electrochemical studies showed that Pdnanobars (PdNB/C) presented higher tolerance to the CO and CO₂ poisoning effect compared with Pd nanoparticles (PdNP/C) and commercial Pd/C. Furthermore, the onset potential toward formic acid electrooxidation at high concentration (1 M) on PdNB/C exhibited a negative shift ca. 100 mV compared with commercial Pd/C. Finally, PdNB/C in the presence of 1 M FA showed a lower poisoning degree compared with commercial Pd/C and PdNP/C.     

Preparation of Nano‐bismuth with Different Particle Sizes and the Size Dependent Electrochemical Thermodynamics

Nano‐bismuth has excellent electrochemical properties. However, it is still unclear how the particle size of nano‐bismuth influences its electrochemical thermodynamic properties. In this paper, spherical bismuth nanoparticles with different particle sizes were prepared by solvothermal method; the electrode potentials, the temperature coefficients of the electrode potentials and the thermodynamic functions of reaction for nano‐bismuth electrodes with different particle sizes at different temperatures were determined; and the effects of particle size on the electrode potential, the temperature coefficient and the thermodynamic functions were discussed. The experimental results show that particle size of bismuth nanoparticles has a significant influences on the electrochemical thermodynamic properties. The standard electrode potential of the nano‐bismuth electrode with a diameter of 39.9 nm was 0.009 V lower than that of the ordinary standard electrode (0.308 V); the temperature coefficient of the electrode potential with a diameter of 39.9 nm was nearly double that of 85.9 nm. With the particle sizes decrease, the standard molar Gibbs energy of reaction, the standard molar enthalpy of reaction, the standard molar entropy of reaction, the molar reversible reaction heat and the temperature coefficient increase; and these quantities are linearly related to the reciprocal of the particle diameter.     

Electrochemical infrared characterization of CO comains on ruthenium-decorated platinum nanoparticles

Spectra obtained by electrochemical infrared reflection absorption spectroscopy (EC-IRAS) for carbon monoxide (CO) adlayers formed by partial CO dosing on various ruthenium-decorated platinum nanoparticle films are reported. The need to achieve a well distributed rather than aggregated metal nanoparticle array is demonstrated, given that such nanoparticle aggregates induce complex dielectric behavior. The strategy here is to use an "organic glue matrix" (short chain SAMs) between the nanoparticles and the gold substrates. The observed promotion in CO electrooxidation by the existence of a Ru island on Pt nanoparticles, of interest to fuel-cell catalysis, showed a strong relationship with Ru surface concentrations, consistent with previous studies on single crystal or polycrystalline bimetallic surfaces. Two distinctive CO infrared bands, one for the Pt-CO and one for Ru-CO domain were found after the dipole coupling of CO within the two CO domains was minimized. Interestingly, those two CO bands showed independent electrooxidation behavior with electrode potential changes. Also, it is shown that the electrooxidation of CO on large Ru islands is less facile than on small Ru islands. In addition, the activity of commercial Pt/Ru alloy nanoparticles to CO stripping was tested and IRAS spectra were reported as a comparison to our Ru-decorated Pt nanoparticles.     

Electrocatalytic properties of platinum nanoparticles supported on fluorine tin dioxide/multi-walled carbon nanotube composites for methanol electrooxidation in acidic medium

Fluorine tin oxide (FTO) and multi-walled carbon nanotube (MWCNT) composites synthesized by a sol-gel process followed by a hydrothermal treatment process have been explored as a support for Pt nanoparticles (Pt-FTO/MWCNTs). X-ray diffraction analysis and high resolution transmission electron microscopy show that the Pt and FTO nanoparticles with crystallite size of around 4-8 nm are highly dispersed on the surface of MWCNTs. Pt-FTO/MWCNT catalyst is evaluated in terms of the electrochemical catalytic activity for methanol electrooxidation using cyclic voltammetry, steady state polarization experiments, and electrochemical impedance spectroscopy technique in acidic medium. The Pt-FTO/MWCNT catalyst exhibits a higher intrinsic catalytic activity for methanol electrooxidation with high stability during potential cycling than Pt nanoparticles supported on tin dioxide/multi-walled carbon nanotube composites. The results suggest that FTO/MWCNT composites could be considered as an alternative support for Pt-based electrocatalysts in direct alcohol fuel cells.     

Shrinking nanowires by kinetically controlled electrooxidation

Nanowires composed of antimony, gold, and bismuth telluride (Bi2Te3) were reduced in diameter by electrooxidation in aqueous solutions. When electrooxidation was carried out using low current densities (Jox < 150 microA cm(-2)), the mean wire diameter decreased in direct proportion to the oxidation time, as expected for a kinetically controlled process. Under these conditions, the diameter uniformity of nanowires remained constant as wires were shrunk from initial diameters of more than 120 nm to less than 40 nm, for Sb and Bi2Te3, and less than 60 nm for Au. Oxidized nanowires remained continuous for more than 100 microm. Electrooxidation at higher current densities rapidly introduced breaks into these nanowires. Electrochemical wire growth and shrinking by electrooxidation were integrated into a single electrochemical experiment that allowed the final mean diameter of nanowires to be specified with a precision of 5-10 nm.     

Enhancement of activity of PtRh nanoparticles towards oxidation of ethanol through modification with molybdenum oxide or tungsten oxide

Electrocatalytic systems utilizing carbon (Vulcan)-supported PtRh nanoparticles (PtRh/Vulcan) admixed with either molybdenum oxide or tungsten oxide were tested and compared during electrooxidation of ethanol. The systems' performance was diagnosed using electrochemical techniques such as voltammetry and chronoamperometry. The proposed electrocatalytic materials were also characterized with X-ray diffraction (XRD), transmission and scanning electron microscopies (TEM and SEM), as well as SEM-coupled energy dispersive X-ray spectroscopy (SEM-EDX). For both systems containing molybdenum and tungsten oxides, enhancements in catalytic activities (relative to the behavior observed at bare PtRh/Vulcan nanoparticles) were found during ethanol electrooxidation at room temperature (22?°C). Further, it was from chronoamperometric current (density)–time responses that anodic electrocatalytic currents measured at 0.3?V (vs. RHE) were more than 20% higher in the case of the MoO₃-containing PtRh/Vulcan system relative to that utilizing WO₃. The diagnostic “CO-stripping” experiments were consistent with the view that addition of molybdenum oxide or tungsten oxide to PtRh/Vulcan tended to shift potential for the oxidation of inhibiting CO-adsorbate ca. 80 or 40?mV towards less negative values in comparison to the analogous but oxide-free system. The fact that carbon (Vulcan)-supported PtRu nanoparticles exhibited higher electrocatalytic reactivity observed phenomena may be attributed to specific interactions between noble metal centers and the oxides in addition to chemical reactivity of metal oxo groups in the vicinity of PtRh/Vulcan at the electrocatalytic interface.     

Ethanol electrooxidation on Pd/C nanoparticles in alkaline media

Carbon-supported Pd nanoparticles were prepared by microwave heating-glycol reduction method, and characterized by a wide array of experimental techniques including X-ray diffraction spectroscopy(XRD) and transmission electron microscopy(TEM). The electrooxidation behaviors of ethanol on the Pd/C electrode in alkaline media were investigated using cyclic voltammetry(CV), chronoamperometry(CA), electrochemical impedance spectroscopy(EIS) and single cell performance methods. Pd/C electrode for ethanol oxidation showed high electro-catalytic activity and long term stability. However, it is observed that the current density decreases with the increasing of the potential and negative impedance presents in the potential from-0.1 to0.1 V. The decreasing current density and the negative impedance could be due to the adsorbed intermediates species that inhibited the further oxidation of ethanol. Based on the chemical reaction analysis and EIS spectra, equivalent circuits relating to various potential zones have been obtained. These results reveal the dynamic adsorption of intermediates species on Pd surfaces. Significantly, it is clarified that the adsorption behavior begins from the maximum catalysis of electro-catalysis and ends in the formation of the palladium(II) oxide layer on the electrode surface.     

Methanol Electrooxidation on Smooth Platinum Modified with Ru：the Influence of Ru Coverage and Potentials on Oxidative Current and Products

Methanol oxidation on smooth Pt electrode modified with differ-ent coverage of Ru was studied using cyclic voltammetry and potential step combined with differential electrochemical mass spectroscopy. The current efficiency of formed CO2 was calcu-lated from faraday current and ion current of m/z = 44. The results show that Ru modified Pt electrode with the coverage of ca. 0.3 has the highest catalytic activity for methanol electroox-idation, i. e. faraday current and the current efficiency of CO2 at the low potentials reach to the maximum. In addition, Ru loses its co-catalytic properties at the high potentials.     

Stripping voltammetric determination of bismuth in raw gold ores

Stripping voltammetry was used to determine bismuth(III) in raw gold ores. The effect of some matrix elements, Cu(II), Au(III), Pt(IV), Pd(II), etc. on the current of bismuth(III) electrooxidation was studied. The conditions the extraction of bismuth(III) dithizonate with chloroform from a complex matrix are found. A procedure is developed for determining bismuth(III) in raw gold ores.     

一维/二维复合碳载体组成对Pd催化剂甲醇氧化性能的影响

采用固相-液相两步混合法制备了由碳纳米管（CNTs）和石墨烯纳米片（GNPs）组成的CNTs-GNPs复合载体。以乙二醇还原法将Pd纳米粒子沉积于复合碳载体上,制得Pd/CNTs-GNPs催化剂。以透射电子显微镜、X射线衍射及X射线光电子能谱表征催化剂的形貌、组成和结构;以电化学方法考察催化剂的甲醇电氧化性能。结果表明,Pd/CNTs-GNPs（1/4）（GNPs质量分数为1/4）催化剂具有较大的电化学表面积和较高的甲醇电氧化活性,其甲醇氧化峰电流密度可达Pd/CNTs催化剂的1.97倍。催化剂的高活性得益于CNTs-GNPs载体的一维/二维复合结构使Pd纳米粒子具有良好的分散性能。计时电流实验表明,与单一载体负载Pd催化剂相比,复合载体负载Pd催化剂具有较强的抗中毒能力。     

A voltammetric sensor on the basis of bismuth nanoparticles prepared by the method of gas condensation

A procedure is developed for the immobilization of bismuth nanoparticles prepared by the method of gas condensation on inert supports manufactured by the screen printing method using carbon-containing inks. The electrochemical behavior of the immobilized bismuth nanoparticles is investigated, and the conditions of their electrochemical activation are found. The composition of the modifying suspension “bismuth nanoparticles-liquid” is optimized. The elaborated thick-film carbon-containing electrode modified by bismuth nanoparticles is shown to be similar in its analytical parameters to the commercially available thick-film carbon-containing electrode premodified by calomel, and substantially exceeds carbon-containing electrodes with electrolytically deposited bismuth films in its properties. The limits of detection for heavy metals by stripping voltammetry are as follows (μg/L): 0.38 for Zn(II), 0.40 for Cd(II), and 0.55 for Pb(II) at the preconcentration time 180 s.     

形貌可控的钯纳米粒子的电化学制备及电催化性质

以NaPdCl4为前驱体, 以柠檬酸钠为包裹剂, 通过两步恒电势法在氧化铟锡(ITO)导电玻璃基底上沉积得到不同形貌的钯纳米粒子(PdNPs). 通过调节晶种沉积电势和粒子生长电势、柠檬酸根和溴离子的浓度及反应温度等因素, 可以控制PdNPs的形貌、尺寸及在ITO基底上的生长密度; 制备出了钯纳米锥阵列及球形、花状和多面体形的PdNPs. 研究结果表明, 钯纳米锥阵列与其它形状的PdNPs相比, 在单位面积ITO基底上具有更大的表面积, 表现出对甲醇更强的电化学氧化能力.     

Nanostructured Pt/GC model electrodes prepared by the deposition of metal-salt-loaded micelles

Novel, nanostructured, carbon-supported Pt model electrodes with homogeneously distributed Pt nanoparticles of uniform size were fabricated and analyzed with respect to their electrochemical properties. For this purpose, Pt-salt-loaded micelles were deposited on a glassy carbon substrate and subsequently exposed to an oxygen plasma and a H2 atmosphere for removal of the polymer carriers and reduction of the Pt salt. The morphology of the resulting nanoparticles and their electrochemical/electrocatalytic properties were characterized by high-resolution scanning electron microscopy, X-ray photoelectron spectroscopy, cyclic voltammetry, and differential electrochemical mass spectrometry for CO electrooxidation. The data demonstrate that this method is generally suited to the production of nanostructured model electrodes with well-defined and independently adjustable particle size and interparticle distance distributions, which are specifically suited for quantitative studies of transport processes in electrocatalytic reactions.     

炭载Pd-Ni合金纳米粒子对甲酸的电催化氧化

通过液相还原法制备了具有不同原子比例的Pd-Ni/C催化剂,并且使用X射线衍射（XRD）、透射电子显微镜(TEM)和X射线光电子能谱(XPS) 等表征手段对制备的催化剂进行了表征,总结了Ni的掺杂对Pd-Ni合金纳米粒子的尺寸及晶体结构的影响。电化学测试结果表明：适量的Ni的掺杂不但能够增强催化剂对甲酸催化氧化的活性,而且还能够提高催化剂的稳定性。因此,Pd-Ni/C催化剂是一类具有潜在应用前景的直接甲酸燃料电池阳极催化剂     

甘油在氧化物/钯复合催化剂上的电氧化研究

应用交替微波加热法制备碳载氧化物和Pd的复合催化剂,并以电化学方法研究这一新型催化剂在碱性条件下对甘油的氧化性能.实验表明,Pd/C催化剂对甘油的电化学氧化有较好活性,但氧化物复合的非铂催化剂对甘油的电化学氧化显示出更高的活性,相对于Pd/C催化剂,其氧化起始电位发生负移及峰电流大幅度提高.本工作还优化了氧化物与Pd的比例.结果证明,氧化物的加入使复合催化剂对甘油氧化产生了协同效应.