Formaldehyde interaction with adsorbed oxygen on open-circuit platinum electrodes in aqueous sulfuric acid solutions

The open circuit potential transients and cathodic potentiodynamic pulses were measured upon formaldehyde (methylene glycol) interaction with pre-adsorbed oxygen (O_ads) on Pt/Pt and pc Pt electrodes in aqueous sulfuric acid solutions. The slowest interaction of CH₂(OH)₂ with O_ads was observed in the high coverage range of the electrode surface (θ_O ～ 0.2 0.8 to 1). The process rate in this range is determined by the direct reaction of O_ads with CH₂(OH)₂ molecules from the bulk solution. In the middle surface oxygen coverage range (θ_O 0.2 to 0.8), CH₂(OH)₂ interaction with O_ads takes place by the mechanism of “conjugated reactions”. The kinetic parameters of reactions for CH₂(OH)₂, HCOOH, and CH₃ OH were compared. The rate of CH₂(OH)₂-O_ads interaction on Pt electrodes in the high oxygen coverage range was found higher by an order of magnitude than that of HCOOH and by two orders of magnitude than in the case of CH₃OH.     

Transients of the Open-Circuit Potential Observed during the Interaction of Formic Acid with Preliminarily Adsorbed Oxygen on a Platinized Platinum Electrode

Transients of the open-circuit potential, which are observed during the interaction of formic acid with preliminarily adsorbed oxygen (O_ads) on a Pt/Pt electrode in 0.5 M H₂SO₄, are measured. It is established, by means of the method of cathodic potentiodynamic pulses, that the slowest interaction of formic acid with O_ads occurs in the region of large coverages of the electrode surface by oxygen (θ_O ∼1–0.8). A presumption is put forward that the process rate in this region is defined by a direct reaction of O_ads with molecules of formic acid from the bulk solution. It is shown that the interaction of formic acid with O_ads in the region of intermediate coverages (θ_O ∼ 0.8–0.2) proceeds via a mechanism of “conjugated reactions.” Transients of the open-circuit potential for formic acid are compared to transients for carbon monoxide obtained in analogous conditions. The substantially shorter overall time of potential decay in the case of CO (at the same concentrations) is caused by a faster reaction of CO with adsorbed oxygen in the region of large θ_O. The difference is explained by assuming that the HCOOH adsorption as opposed to CO bears a dissociative character.__________Translated from Elektrokhimiya, Vol. 41, No. 8, 2005, pp. 936–942.Original Russian Text Copyright © 2005 by Manzhos, Maksimov, Podlovchenko.     

Transients of the Open-Circuit Potential during Carbon Monoxide Interaction with Oxygen Preliminarily Adsorbed on Smooth and Platinized Platinum Electrodes

Variations of potential E in time , observed during the carbon monoxide interaction with preliminarily-adsorbed oxygen O_ads on smooth and platinized platinum electrodes under open-circuit conditions (supporting electrolyte 0.5 M H₂SO₄), are measured. The potential decay rate on smooth Pt is more than ten times that on Pt/Pt; there are some differences in the transients as well. The obtained data suggest that CO interacts with O_ads on smooth Pt and Pt/Pt via different mechanisms. Two models for the process on smooth platinum are considered. In one model, the interaction of O_ads with CO from solution is accepted as the rate-determining step; in the other, the interaction of O_ads with CO_ads. A comparison of theoretical E vs. dependences with experimental data using the MathCad program suggests that CO interacts with O_ads via both mechanisms.     

Kinetics and mechanism of interaction between methanol and adsorbed oxygen on a smooth polycrystalline platinum electrode: Transients of the open-circuit potential

The method of transients of the open-circuit potential, combined with cathodic potentiodynamic pulses, is used for studying the methanol interaction with preliminarily adsorbed oxygen (O_ads) in 0.5 M H₂SO₄. It is established that, for the larger part of the time period required for a full reduction of a monolayer of O_ads in solutions of methanol on polycrystalline platinum, the process occurs at large coverages of the surface by O_ads (?_O). In the region of medium coverages, transients of the open-circuit potential are accurately described by the equation that corresponds to the mechanism of “conjugated reactions.” The mechanism of the methanol interaction with O_ads happens to be close to that for formic acid, which is explained by a dissociative character of these HCO compounds. Kinetic parameters characterizing the methanol reaction with O_ads in the region of large and medium coverages are determined and analyzed.     

Specific features of interaction between formic acid and oxygen adsorbed on smooth polycrystalline platinum: Transients of the open-circuit potential

Transients of the open-circuit potential, which are observed when formic acid is interacting wit adsorbed oxygen (O_ads) preliminarily accumulated on polycrystalline “smooth” platinum (pcPt), are measure in an aqueous solution of sulfuric acid. It is shown that, as with platinized platinum (Pt/Pt), at large coverage by adsorbed oxygen (θ_O = 1?0.8), adsorbed oxygen interacts directly with molecules of formic acid from solution. In the region of medium coverages (θ_O = 0.8?0.2), on the other hand, a mechanism of “conjugated reactions” is realized. It is established that, in the case of pcPt, the direct interaction of O_ads with molecules of HCOOH from solution proceeds slower by nearly three times and the interaction via the mechanism of “conjugated reactions,” faster by about three times, as compared with Pt/Pt.     

The effect of hydrocarbon chain length in normal aliphatic alcohols on their reaction with oxygen adsorbed on polycrystalline platinum electrode

The reaction of adsorbed oxygen (O_ads) with aliphatic alcohols n-C _n H_{2n + 1}OH with n = 2–5 is studied by the method of transients of open-circuit potential in combination with potentiodynamic pulses. It is shown that these alcohols react with O_ads by a mechanism the same as for CH₃OH. Kinetic parameters of these reactions are determined in ranges of high and medium surface coverages with O_ads. These data together with analogous results obtained earlier for CH₃OH were studied with the aim of elucidating how the length of the hydrocarbon chain affects the kinetics of interaction of alcohols with O_ads. The complex variations of the reaction rate with n (with a maximum) are explained by several factors among which the energy of the C–H bond at α-carbon atom and the degree hydration of alcohols should be singled out.     

On the DAPS Capability for Testing the Chemisorbed Species Location

The DAPS can properly indicate the surface layer of platinum atoms that is mostly affected in the course of H₂, O₂ adsorption, H₂+O_ads and NO+H_ads interactions on the Pt(100)-(1×1) single crystal surface.     

Experimental study of intermediates and wave phenomena in co oxidation on platinum metal (Pt,Pd) surfaces

The mechanism of catalytic CO oxidation on Pt(100) and Pd(110) single-crystal surfaces and on Pt and Pd sharp tip (～10³ Å) surfaces has been studied experimentally by temperature-programmed reaction, temperature desorption spectroscopy, field electron microscopy, and molecular beam techniques. Using the density functional theory the equilibrium states and stretching vibrations of oxygen atoms adsorbed on the Pt(100) surface have been calculated. The character of the mixed adsorption layer was established by high resolution electron energy loss spectroscopy—molecular adsorption (O_2ads, CO_ads) on Pt(100)-hex and dissociative adsorption (O_ads, CO_ads) on Pt(100)-(1×1). The origin of kinetic self-oscillations for the isothermal oxidation of CO in situ was studied in detail on the Pt and Pd tips by field electron microscopy. The initiating role of the reversible phase transition (hex) ? (1 × 1) of the Pt(100) nanoplane in the generation of regular chemical waves was established. The origination of self-oscillations and waves on the Pt(100) nanoplane was shown to be caused by the spontaneous periodical transition of the metal from the low-active state (hex) to the highly active catalytic state (1 × 1). A relationship between the reactivity of oxygen atoms (O_ads) and the concentration of CO_ads molecules was revealed for the Pd(110) surface. Studies using the isotope label ¹⁸O_ads demonstrated that the low-temperature formation of CO₂ at 150 K is a result of the reaction of CO with the highly reactive state of atomic oxygen (O_ads). The possibility of the low-temperature oxidation of CO via interaction with the so-called “hot” oxygen atoms (O_hot) appearing on the surface at the instant of dissociation of O_2ads molecules was studied by the molecular beam techniques.     

Effect of ionic composition of solutions on the methanol reaction with adsorbed oxygen on smooth polycrystalline platinum electrodes: Transients of the open-circuit potential

Transients of the open-circuit potential observed in the reaction of methanol with oxygen (O_ads) preliminarily adsorbed on smooth polycrystalline platinum (pcPt) are measured in 0.05 M HClO₄, 0.5 M HClO₄, 0.05 M H₂SO₄, 0.05 M H₂SO₄ + 0.45 M Na₂SO₄, and 0.05 M H₂SO₄ + 0.45 M Cs₂SO₄. It is shown that the solution pH has a weak effect on the transient characteristics (when the reversible hydrogen electrode potential scale is used). This confirms the chemical nature of rate-controlling stages in the reaction mechanism. The changes in the reaction rate, observed upon going from one electrolyte to another, are preferentially associated with the involvement of solution ions in the formation of activated surface complexes that include CH₃OH, O_ads, and supporting-electrolyte components.     

Mathematical modeling of wave phenomena in the oxidation of CO on the Pt(l00) surface

CO oxidation on Pt(l00) is studied by the Monte Carlo method using a model that accounts for the phase transition (lxl) ai (hex). The influence of surface diffusion of CO_ads on the velocity of wave propagation of O_ads and CO_ads and the distribution of the species in the reaction zone is studied Deceased.     

Nonlinear chemical reaction between Na2S2O3 and Peroxide compound

Kinetics of reaction between Na₂S₂0₃ and peroxide compound (H₂0₂ or Na₂S₂O₃) in a batch reactor and in a continuous stirring tank reactor (CSTR) were studied. Steady oscillations in uncatalyzed reactions in a CSTR were first discovered. In Na₂S₂0₃-H₂O₂-H₂S0₄ reaction system, Pt potential and pH of higher and lower flow rates beyond oscillation flow rates were in around the same extreme values. The reaction catalyzed by Cu²⁺ consists of the catalyzed oscillation process and the uncatalyzed osciliation one. On the basis of experiment, a reaction mechanism consisting of three stages was put forward. The three stages are H⁺ positive-feedback reactions, proton negative-feedback (uncatalyzed negative-feedback and catalyzed negative-feedback) reactions and transitional reactions. The mechanism is able to explain reasonably the nonlinear chemical phenomena appearing in the thiosulfate oxidation reaction by peroxide compounds. Project supported by the National Natural Science Foundation of China.     

Reaction mechanism of methanol decomposition on Pt‐based model catalysts: A theoretical study

The decomposition mechanisms of methanol on five different Pt surfaces, the flat surface of Pt(111), Pt‐defect, Pt‐step, Pt(110)(1 × 1), and Pt(110)(2 × 1), have been studied with the DFT‐GGA method using the repeated slab model. The adsorption energies under the most stable configuration of the possible species and the activation energy barriers of the possible elementary reactions involved are obtained in this work. Through systematic calculations for the reaction mechanism of methanol decomposition on these surfaces, we found that such a reaction shows the same reaction mechanism on these Pt‐based model catalysts, that is, the final products are all H (H_ads) and CO (CO_ads) via O? H bond breaking in methanol and C? H bond scission in methoxy. These results are in general agreement with the previous experimental observations. © 2010 Wiley Periodicals, Inc. J Comput Chem, 2010.     

Adsorption and electrooxidation of dimethyl ether on platinized platinum electrode in sulfuric acid solution

Adsorption and oxidation of dimethyl ether (DME) on the Pt/Pt electrode from 0.5 M H₂SO₄ is studied by measuring transients of current and potential, charging curves, and curves of electrooxidation in the adsorbed layer and also by cyclic voltammetry and steady-state polarization measurements. The DME adsorption is accompanied by dehydrogenation and destruction of its molecules to form a chemisorbed adsorbate that mainly consists of C1 species (HCO_ads and/or CO_ads) with (under certain conditions) a small amount of species that desorb at cathodic polarization. The adsorption and electrooxidation of DME are inhibited by adsorbed oxygen. The possible schemes of DME oxidation, where the reaction of DME chemisorption products with adsorbed oxygen-containing species is the limiting stage, are discussed.     

Intercalation-etching of graphene on Pt(111) in H<Subscript>2</Subscript> and O<Subscript>2</Subscript> observed by <Emphasis Type="Italic">in-situ</Emphasis> low energy electron microscopy

Graphene layers are often exposed to gaseous environments in their synthesis and application processes, and interactions of graphene surfaces with molecules particularly H₂ and O₂ are of great importance in their physico-chemical properties. In this work, etching of graphene overlayers on Pt(111) in H₂ and O₂ atmospheres were investigated by in-situ low energy electron microscopy. Significant graphene etching was observed in 10^-5 Torr H₂ above 1023 K, which occurs simultaneously at graphene island edges and interiors with a determined reaction barrier at 5.7 eV. The similar etching phenomena were found in 10^-7 Torr O₂ above 973 K, while only island edges were reacted between 823 and 923 K. We suggest that etching of graphene edges is facilitated by Pt-aided hydrogenation or oxidation of edge carbon atoms while intercalation-etching is attributed to etching at the interiors at high temperatures. The different findings with etching in O₂ and H₂ depend on competitive adsorption, desorption, and diffusion processes of O and H atoms on Pt surface, as well as intercalation at the graphene/Pt interface.     

Kinetics of the Electrocatalytic Oxidation of 2,2-Dimethylolpropionaldehyde

A new method of synthesis 2,2-dimethylolpropionic acid from 2,2-dimethylolpropionaldehyde was put forward. The electrochemical oxidation behavior of 2,2-dimethylolpropionaldehyde has been investigated on a Ti/SnO₂ + Sb₂O₄/PbO₂ electrode by cyclic voltammetry (CV) and stable polarization curves in sulfuric acid. The results showed that it was an irreversible reaction controlled by diffusion. The formation mechanism of 2,2-dimethylolpropionic acid in the sulfuric acid was then proposed and the transfer coefficients of the reaction were calculated. It was concluded that RCHO+ỌH_ads→RCHOỌH_ads was the rate-determining step in the electrolysis process. The rate of this step obtained from the assumed process agrees well with experiment.     

The Study of Nitric Oxide Adsorption and the Mechanism of Surface “Explosions” in the Reaction of CO + NO on Pt(100) and Pd(110) Single Crystal Surfaces

High resolution electron energy loss spectroscopy (HREELS), temperature-programmed desorption (TPD) and temperature-programmed reaction (TPR) were used to study NO adsorption and the reactivity of CO_ads and NO_ads molecules on Pd(110) and Pt(100) single crystal surfaces. Compared to the Pt(100)-(1 × 1) surface, the unreconstructed Pt(100)-hex surface is chemically inert toward NO dissociation into N_ads and O_ads atoms. When a mixed adsorbed CO_ads + NO_ads layer is heated, a so-called surface explosion is observed when the reaction products (N₂, CO₂, and N₂O) synchronously desorb in the form of sharp peaks with a half-width of 7-20 K. The shape specificity of TPR spectra suggests that the vacancy mechanism consists of the autocatalytic character of the reaction initiated by the formation an initial concentration of active sites due to partial desorption of molecules from the CO_ads + NO_ads layer upon heating to high temperatures. Kinetic experiments carried out on the Pd(110) surface at a constant reaction pressure and a linear increase in the temperature confirm the explosive mechanism of the reaction NO + CO.     

Infrared studies of the effect of acetylene, hydrogen, and oxygen on CO adsorption on platinum hydrosols

Infrared spectra of CO-treated platinum hydrosols subsequently treated with acetylene, hydrogen, and oxygen reveal that v(CO)_ads decreases from 2070 cm⁻¹ with increasing gas-treatment time. This has been attributed to a reduction in the coverage of adsorbed CO. In Pt sol/CO/C₂H₂ systems, v(CO)_ads decreases to a limiting value of ca. 2060 cm⁻¹ after exposure to acetylene. In the Pt sol/CO/H₂ systems, v(CO)_ads decreases to ca. 2050 cm⁻¹ after exposure to hydrogen gas. The lower frequency in the Pt sol/CO/H₂ system has been attributed to CO adsorption on more active metal sites formed from the reduction of surface platinum oxides. Exposure of the CO-treated platinum hydrosols to O₂ gas was found to cause the eventual disappearance of the v(CO)_ads band in infrared spectra, which was attributed to oxidation of adsorbed CO to CO₂ by weakly bound surface layers of platinum oxides formed by the oxygen treatment.     

Exploration of electrodeposited platinum alloy catalysts for methanol electro-oxidation in 0.5 M H<Subscript>2</Subscript>SO<Subscript>4</Subscript>: Pt-Ni system

In this work, we examine the electrocatalytic activity of electrodeposited Platinum (Pt)-Nickel (Ni) alloy layers on an inert substrate electrode for methanol oxidation reaction. Analyses using energy-dispersive fluorescent X-ray analysis and powder X-ray diffractometry confirm alloying of Pt with Ni in a range of compositions. Steady-state polarisation measurements in 0.5 M methanol+0.5 M H₂SO₄ solutions clearly show that the onset of electro-oxidation shifts to less anodic potential values (approximately 160 mV), while also exhibiting current enhancements up to ~15 times the currents obtained for the pure Pt electrodeposit. A linear relationship between the cyclic voltammetric peak (oxidation) current and [MeOH] is observed at a scan rate of 50 mVs^–1, thus indicating reduced influence of adsorbed CO (CO_ads) surface poison. A critical composition, Pt (92%)/Ni (8%) [denoted Pt-Ni(3) alloy] is found to exhibit maximum electrocatalytic activity, beyond which the activity drops, whereas pure Ni does not catalyse the reaction. While the promotion of electro-oxidation is understood to be largely due to the alloy catalyst, surface redox species of Ni oxide formed during the electro-oxidation process may also contribute to the oxygenation of CO_ads, thereby enhancing the oxidation current. Plausible mechanisms of methanol oxidation on Pt/ transition metal alloy electrocatalysts are discussed in terms of electron transfer (in the alloy) and the role of Ni oxide species.     

Single-Cu-atoms anchored on 3D macro-porous carbon matrix as efficient catalyst for oxygen reduction and Pt co-catalyst for methanol oxidation

Single metal atoms immobilized on a carbon substrate are of great potential for enhancing the catalytic activities for oxygen reduction and methanol oxidation reactions（ORR/MOR） owing to the maximized atom utilization. Herein, single copper atoms（SCAs） are loaded on macro-porous nitrogen-doped carbon（Cu-NC） derived from zeolitic imidazolate framework-8（ZIF-8）, which are used as catalysts for ORR and Pt-supports for MOR. For ORR, the catalyst marked as Cu-NC-3 exhibits a higher peak potential of ...     

Simultaneous Detection of Peracetic Acid and Hydrogen Peroxide by Amperometry at Pt and Au Electrodes

Based on preliminary voltammetric investigations at both Pt and Au electrodes in aqueous solutions buffered at different pH values in the range 0–10, two possible profitable triple‐pulse amperometric approaches were developed for determining simultaneously peroxyacetic acid (PAA) and hydrogen peroxide present in the same samples. At both surfaces a pulsed waveform applied at rotating‐disc electrodes was adopted to take advantage on one hand of the optimized signal reproducibility achieved by this potential multistep antifouling approach and on the other hand of the constant thickness of the diffusion layer, which is necessary when the recording of time‐independent currents is desired. At a rotating‐disc Pt electrode an anodic selective signal was indeed recorded for H₂O₂ alone, while PAA contents could be inferred only from the difference of convenient signals, since at all pHs explored its sole cathodic reaction could be observed at potentials coincident with those proper for the reduction of H₂O₂ too. The same pulse approach at Au electrodes instead provided totally independent signals for the two analytes considered, thus proving to be suitable for their independent detection. In fact, H₂O₂ alone undergoes anodic oxidation also at this surface, while the reduction of PAA occurs at potentials less cathodic than those required for H₂O₂. At both electrodes, the best results turned out to be achieved at pH 0 in terms of both precision (±2–4%) and detection limits (0.2–0.3 mM), as well as of linear range which extended for about three orders of magnitude. The kinetics of the equilibrium involving the generation of H₂O₂ from the reaction of PAA with water was also evaluated, since it was suspected of making unreliable the proposed amperometric approaches.