Adsorption of Carbon Monoxide on Platinized Platinum Electrode with Preadsorbed Iodine and Iodide Anions

Adsorption of carbon monoxide in the presence of adlayers formed upon exposure of Pt/Pt to I^– anions and I₂ (0.5 M ₂SO₄ as the supporting electrolyte) is studied using the method of electrode washing. Transients of current and potentiodynamic curves show that the displacement of iodine adatoms from the Pt/Pt surface by CO is virtually complete when CO is adsorbed in the range of hydrogen adsorption potentials (E 0.35 V (RHE)) and incomplete at higher potentials. It is concluded that the bond formed by iodine adatoms with the surface strengthens with an increase in the potential. Possible reasons for the striking difference in the behavior of adatomic monolayers formed from KI and I₂ solutions is discussed. The surface charge of Pt/Pt is observed to drastically change as a result of the displacement of iodine adatoms by carbon monoxide.     

Comparison of catalytic activity of thallium and lead adatoms at the gold electrodeposition and dissolution in cyanide solutions

Catalytic activity of thallium and lead adatoms is compared in electrode processes involving gold in cyanide solutions. It is shown that in the presence of considered atoms on the interface, the gold dissolution is accelerated to the greater extent than its electrodeposition. Lead adatoms are shown to exert a substantially stronger effect on the anodic dissolution rate as compared with thallium adatoms, whereas the opposite trend is observed in the cathodic deposition. An explanation for the fact is proposed.     

A study of surface diffusion of ternary (Cu-Ag-Zr) adatoms clusters for applications in thin film formation

This study presents the diffusion of heterogeneous ternary (Cu-Ag-Zr) adatoms clusters on Ag(111) using molecular dynamics techniques which could be important for the surface phenomena's and helpful for the ternary cluster's growth and formation of ternary alloy-based thin films. The mechanism of nanoscale surface diffusion is investigated for 1Cu-1Ag-1Zr, 2Cu-2Ag-2Zr, 3Cu-3Ag-3Zr, and 4Cu-4Ag-4Zr clusters at temperatures 300, 500, and 700 K. The diffusion mechanism displays that the diffusion of trimer cluster exhibits hopping, sliding, and shearing at 300 K, whereas for hexamer, nonamer, and decamer, the diffusion rate is low; however, breathing, anchoring, and concentrated motion dominates. At 500 K, trimer and hexamer show the process of atomic exchange; however, the atomic exchange is not observed in the case of nonamer and decamer diffusion. The atomic exchange mechanism of Cu and Zr adatoms dominates at 700 K for all size clusters, except Ag adatoms, where Zr adatoms show a relatively more tendency. Separation and rejoining of the one and two adatoms (likely Zr adatom) are also witnessed at high temperature. The pop-up of Ag adatoms also occurs in very short intervals over the remaining adatoms of clusters. Interestingly, during trimer diffusion, the adsorption of the Zr- or Cu-adatom among the trimer cluster into the substitutional site is found. At 700 K, vacancy generation, filling of vacancies, and migration of vacancy, in the neighborhood of the adatoms cluster, also observed. Moreover, the rate of diffusion decreases with the size increase of the clusters and increases with the increase in temperature.     

Tailoring the Self-assembly of Melamine on Au (111) via Doping with Cu Atoms

The doping effect of Cu on the self-assembly film of melamine on an Au(111) surface has been investigated with scanning tunneling microscopy (STM). The evaporated Cu adatoms occupy the positions underneath the amino groups and change the hydrogen bonding pattern between the melamine molecules. Accordingly, the self-assembly structure has changed stepwise from a well-defined honeycomb into a track-like and then a triangular structure depending on the amount of Cu adatoms. The interaction between Cu adatom and melamine is moderate thus the Cu adatoms can be released upon mild heating to around 100℃. These findings are different from previous observations of either the coordination assembly or the physically trapped metal adatoms.     

Specific Features of the Adsorption of Carbon Monoxide on a Smooth Polycrystalline Platinum Electrode Modified with Adsorbed Silver Atoms

The adsorption of carbon monoxide at the surface of smooth polycrystalline platinum (smPt) is studied in conditions of a preliminary accumulation of various quantities of silver (θ_Ag) on the surface. A comparison with similar data obtained previously for Pt/Pt is conducted. It is discovered that on smPt, exactly as in the case of Pt/Pt, carbon monoxide undergoes adsorption at sites that are not occupied by adsorbed silver, without forcing the preliminarily adsorbed silver out. At small and intermediate Ag_ad, as opposed to Pt/Pt, a mere two peaks are observed in a voltametric curve in the region of electrodesorption of the mixed layer on smPt. It is shown that, in the region of potentials of the first peak, there occurs practically no transition of silver into solution in the course of oxidation of the mixed layer. Specific features that characterize the behavior of the CO_ads + Ag_ad mixed layer are discussed under the assumption about an “islet” character of the adsorption of silver.     

Carbon monoxide adsorption on palladium electrodes modified with silver adatoms

Adsorption of carbon monoxide on palladium deposits and smooth polycrystalline palladium is studied in conditions of preliminary accumulation of various amounts of adsorbed silver (?_Ag) on them. It is discovered that carbon monoxide undergoes adsorption on palladium as it does on platinum, i.e. at the sites free of adsorbed silver, virtually without forcing out preliminarily adsorbed silver. At small and medium values of ?_Ag in the region of electrodesorption of a mixed layer on palladium, as opposed to Pt/Pt, only two peaks are observed in an anodic voltammetric curve. The nature of the processes that are responsible for the presence of two peaks pertaining to the oxidation of a mixed adsorption layer is discussed.     

Potential transients on a renewed electrode as a source of information on the surface concentration of catalytically active adatoms

Potential transients on renewable gold and silver electrodes in cyanide solutions containing catalytically active ions of lead and thallium are measured. The transients are recorded both on freshly renewed electrodes and on renewed electrodes kept in solution for specified time periods t. The behavior of transients following a change in the concentration of lead and thallium ions, current density, and t qualitatively conforms to regularities that could be expected if the catalytically active adatoms were inserted into the deposit similarly to the admixtures. Methods for determining coefficients of capture of such adatoms by the growing metal deposit are suggested. Factors that hamper determination of these coefficients and make it worthwhile to select a method for their determination that would use potential transients are considered. The capture coefficient for the incorporation of lead adatoms in the growing silver deposit is nearly 20 times that for gold.__________Translated from Elektrokhimiya, Vol. 41, No. 4, 2005, pp. 460–467.Original Russian Text Copyright © 2005 by Bek, Shuraeva.     

Effect of cadmium and lead adatoms on the reduction kinetics of peroxodisulfate anions at platinized platinum in acid solutions

The reduction of peroxodisulfate anions on a rotating Pt/Pt disk electrode in solutions of sulfuric and perchloric acids with or without cadmium and lead salts is studied. At E _r > 0.2V (RHE) the reduction rate in HClO₄ exceeds that in H₂SO₄, but at E _r < 0.2V, the process in HClO₄ is strongly inhibited upon approaching E _r = 0. Lead adatoms catalyze the process, while cadmium adatoms inhibit it in H₂SO₄ and accelerate it at E _r < 0.2V in HClO₄. The results are interpreted by taking account of the specific adsorption of sulfuric-acid anions and their co-adsorption with cadmium cations, as well as the adsorption of peroxodisulfate anions on the Pt surface modified by lead and cadmium ions in perchlorate solutions.Translated from Elektrokhimiya, Vol. 41, No. 2, 2005, pp. 137–141.Original Russian Text Copyright © 2005 by Nikiforova, Petrii.This revised version was published online in April 2005 with corrections to the article note and article title and cover date.     

Application of the site blocking method to the investigation of the kinetics of carbon monoxide electrooxidation on nanostructured Pt

In this work, we apply a recently developed selective site blocking with gold adatoms (Kuznetsov et al. Electrocatal 3:211–220, 2012) for studying the electrooxidation of adsorbed carbon monoxide on electrodeposited Pt. The reaction is studied using chronoamperometry, and the obtained current transients are fitted with a nucleation-and-growth model in order to determine the characteristic kinetic parameters on defect and terrace (facet) sites. We conclude that Au selectively blocks defect sites up to very high coverages of 0.42 MLs, strongly slowing down the reaction kinetics. Blocking of defect sites with Au adatoms also results in an increase of the packing density of CO on terrace sites. The rate constant of CO oxidation on defects is higher than that on terraces and exhibits higher Tafel slope.     

Heterogeneous stages in the below-ignition-limit oxidation of hydrogen and carbon monoxide

It was demonstrated experimentally that, during the oxidation of hydrogen and carbon monoxide under stationary conditions (i.e., below the first ignition limit), the state of the reaction vessel surface experiences reversible changes, which, in turn, influence the kinetics of the gas-phase process. It was concluded that the reaction of molecular oxygen with hydrogen adatoms plays an important role in chain reactions below the first ignition limit.     

Determination of carbon monoxide in metal carbonyl complexes

Carbon monoxide is liberated from carbonyl-containing metal complexes by treatment with various reagents such as pyridinium hydrobromide perbromide in dichloromethane, hydrogen peroxide in acetone, or iodine in pyridine, and oxidized to carbon dioxide by the Schütze iodine pentoxide reagent. The carbon dioxide is determined gravimetrically following absorption on soda asbestos.     

The in-situ preparation of well-defined, single crystal electrodes

A new method of single crystal preparation for electrochemical application is described in this report. This method does not require the annealing-quenching procedure or ultra-high vacuum methodology. The crystal is annealed and cooled in iodine vapor, then transferred to an electrochemical cell where the chemisorbed iodine is replaced by carbon monoxide present in the electrolyte. The carbon monoxide is subsequently electrooxidized from the surface, leaving the clean, ordered surface exposed to the electrolyte. Thus, the crystal is obtained in situ. The ordered crystal is not subject to the strains imposed by quenching and at no time is the unprotected surface exposed to the atmosphere. The voltammetric evidence presented shows that this procedure is successful in the characterization of a clean and adsorbate-covered Pt(111) surface.     

Measuring the rate constant of the reaction between carbon monoxide and iodine oxide at 298–363 K by the resonance fluorescence method

The rate constant of the reaction between the IO radical and carbon monoxide has been measured by the iodine atom resonance fluorescence method in the temperature range from 298 to 363 K. The reaction mainly takes place on the wall of the reactor.     

钯原子修饰的金纳米颗粒乙醇氧化电催化剂

钯催化剂对碱性溶液的乙醇电催化氧化反应表现较好的催化活性. 本文通过简单的化学沉积法,将钯原子成功修饰到金纳米颗粒表面,制备的催化剂对乙醇电催化氧化反应表现出比钯更好的催化性能. 研究发现,钯原子不均匀地覆盖在金核表面,部分金原子暴露在外层. 制备的催化剂的峰电流密度是钯催化剂的4.6 倍,起始电势低100 mV. 该催化剂较好的催化性能可能归因于金核的电子效应和表面双功能电催化反应机制.     

Palladium Adatoms on Gold Nanoparticles as Electrocatalysts for Ethanol Electro-Oxidation in Alkaline Solutions; [钯原子修饰的金纳米颗粒乙醇氧化电催化剂]北大核心CSCD

Palladium (Pd) is a good catalyst for ethanol electro-oxidation in alkaline solutions.The activity of Pd is further improved in this study by modifying the gold (Au) nanoparticles with Pd adatoms using a simple spontaneous deposition process.The Pd overlayer on the Au core (Au@Pd) is un-uniform with some Au atoms exposed to the electrolyte.The activity of Au@Pd/C toward ethanol oxidation reaction (EOR) is much higher than that of Pd/C in an alkaline solution.The peak current density of Au@Pd/C is 4.6 times higher than that of Pd/C with a 100 mV lower onset potential.The enhanced activity may be due to the electronic effect from the Au core, and the bifunctional reaction mechanism. © 2018 Journal of Electrochemistry. All rights reserved.     

First principles study of CO oxidation on TiO2(110): the role of surface oxygen vacancies

The reactivities of the stoichiometric and partially reduced rutile TiO2(110) surfaces towards oxygen adsorption and carbon monoxide oxidation have been studied by means of periodic density functional theory calculations within the Car-Parrinello approach. O2 adsorption as well as CO oxidation are found to take place only in the presence of surface oxygen vacancies (partially reduced surface). The oxidation of CO by molecularly adsorbed O2 at the O-vacancy site is found to have an activation energy of about 0.4 eV. When the adsorbed O2 is dissociated, the resulting adatoms can oxidize incoming gas-phase CO molecules with no barrier. In all studied cases, once CO is oxidized to form CO2, the resulting surface is defect-free and no catalytic cycle can be established.     

Solid-state electrochemical detector for carbon monoxide at sub-ppm concentrations

Carbon monoxide reacts with iodine pentoxide at 42°C to produce iodine vapor, which is dtected by a solid-state electrochemical detector, essentially a Pt/AgI/Ag galvanic cell. The response begins to rise steeply 3.7 s after a 1.1-ml gas sample is introduce and reaches a maximum after a further 1.2 s. The response is linearly related to the concentration of carbon monoxide up to 2 ppm from the detection limit of 0.03 ppm. Interferences such as H₂S and C₂H₄ are removed by 5A molecuarl sieve; H₂ (1%), CH₄ (5%) and C₂H₄ (5%) are without effect.     

Copper Ion Catalyzed Electroreduction of Carbon Monoxide on Iridium Electrode

Substantial cathodic currents are observed on iridium electroplates in 0.5 M H₂SO₄ + (0.001–0.005 M) CuSO₄ + CO (sat) at potentials positive with respect to the Cu/Cu²⁺ equilibrium potential. These currents are shown to correspond to electroreduction of both CO and Cu²⁺ ions to Cu⁺, where the latter ions are formed in amounts indicating the formation of complexes. Among the products of CO reduction, methanol and formaldehyde are identified. A possible mechanism of CO reduction is discussed. It is assumed that both copper adatoms and Cu⁺ ions can play the role of intermediates in the mediator catalysis.__________Translated from Elektrokhimiya, Vol. 41, No. 7, 2005, pp. 804–809.Original Russian Text Copyright © 2005 by Podlovchenko, Gladysheva.     

贵金属原子与点缺陷石墨烯的键增强作用

通过密度泛函理论研究了Ag、Au、Pt原子在完美和点缺陷(包括N掺杂、B掺杂、空位点缺陷)石墨烯上的吸附以及这些体系的界面性质.研究表明Ag、Au不能在完美的石墨烯上吸附,N、B掺杂增强了三种金属与石墨烯之间的相互作用.而空位点缺陷诱发三种金属在石墨烯上具有强化学吸附作用.通过电子结构分析发现,N掺杂增强了Au、Pt与C形成的共价键,而Au、Ag与B形成了化学键.空位点缺陷不仅是金属原子的几何固定点,同时也增加了金属原子和碳原子之间的成键.增强贵金属原子和石墨烯相互作用的顺序是:空位点缺陷>>B掺杂>N掺杂.