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1.
In this work, surface modification at atomic level was applied to study the reactivity of step sites on platinum single crystal surfaces. Stepped platinum single crystal electrodes with (1 1 1) terraces separated by monoatomic step sites with different symmetry were decorated with irreversibly adsorbed adatoms, without blocking the terrace sites, and characterized in 0.1 M HClO4 solution. The kinetics of CO oxidation on the different platinum single crystal planes as well as on the step decorated surfaces has been studied using chronoamperometry. The apparent rate constants, which were determined by fitting the experimental data to a mean-field model, decrease after the steps of platinum single crystal electrodes have been blocked by the adatoms. This behavior indicates that steps are active sites for CO oxidation. Tafel slopes measured from the potential dependence of the apparent rate constants of CO oxidation were similar in all cases. This result demonstrates that the electrochemical oxidation of the CO adlayer on all the surfaces follows the same Langmuir–Hinshelwood model, irrespectively of step modification.  相似文献   

2.
The catalytic activity of the Pt(110) surface for the reaction of NO + H2 was much less than that of the Pt(100) surface. However, the catalytic activity of the Rh deposited Pt(1l0) surface was almost equal to that of the Rh deposited Pt(100) surface. That is, the catalytic reaction of NO + H2 on Pt(110) and Pt(100) surfaces is highly structure sensitive, but it changes to structure insensitive by the deposition of Rh atoms. These results are rationalized by formation of an active overlayer on the Pt(110) and Pt(100) surfaces, which is very analogous to the Rh-O/Pt-layer formed on Rh/Pt(100), Pt/Rh(100) and Pt-Rh(100) alloy surfaces during catalysis. The formation of the common overlayer of Rh-O/Pt-layer during catalysis is responsible for the structure insensitive catalysis of Rh deposited Pt-based catalysts, which is an important role of Rh in a three way catalyst.  相似文献   

3.
We studied the borohydride oxidation reaction (BOR) by voltammetry for BH4 concentrations between 10−3 M and 0.1 M NaBH4 in 0.1–1 M NaOH for bulk polycrystalline Pt, Ag and alloyed Pt–Ag electrocatalysts. In order to compare the different electrocatalysts, we measured the kinetic parameters and the number of electrons exchanged (faradic efficiency). BOR on bulk Pt is more efficient when the concentration of NaBH4 increases (3e in 1 mM and 6e in 10 mM BH4/0.1 M NaOH). BOR on Pt can occur both in a direct pathway and in an indirect pathway including hydrogen generation via heterogeneous hydrolysis of BH4 and subsequent oxidation of its by-products (e.g. BH3OH and H2). BOR on Ag strongly depends on the pH: improved faradic efficiency is monitored for high pH (2e at pH 12.6 and 6e at pH 13.9 at 25 °C). The BOR kinetics is faster for Pt than for Ag (iPt=0.02 A cm−2, iAg=1.4 10−7 A cm−2 at E=−0.65 V vs. NHE in 1 mM NaBH4/0.1 M NaOH, 25 °C) both as a result from Pt high activity regarding the BH4 heterogeneous hydrolysis and subsequent HOR, above −0.83 V vs. NHE and following direct oxidation of BH4 or BH3OH below −0.83 V vs. NHE. Both Pt–Ag bulk alloys show unique behaviour: the number of electrons exchanged is rather high whatever the BH4 concentration and pH, while the kinetic parameters are quite similar to that of platinum, showing possible synergistic alloying effect.  相似文献   

4.
Formic acid oxidation on palladium submonolayers on well-defined Pt(100) and Pt(111) electrodes has been studied using voltammetry and Differential Electrochemical Mass Spectrometry (DEMS). A combination of the two techniques allows a better understanding of the reaction taking place on the electrode surface. Thus, an exact correlation between the CO2 mass signal and the current density in the voltammogram corresponding to the formic acid oxidation has been obtained. On palladium modified Pt(100) electrodes and in the potential region below 0.3 V, the currents in the positive scan are higher than those recorded in the negative scan. This diminution on the signal in the negative scan has been associated with CO2 reduction to CO on the palladium adlayer. In addition, the CO2 reduction reaction seems to take place on the border of the palladium islands. Finally, the adsorption of (bi)sulfate anions has an inhibiting behavior on the formic acid oxidation reaction.  相似文献   

5.
Rhodium adlayers on Pt(1 1 1) substrates have been prepared by electrodeposition from dilute Rh3+ acidic solutions. Resulting deposition rates are lower than 0.03 ML min−1. Pseudomorphic growth of the first monolayer has been confirmed by scanning tunneling microscopy (STM) as well as the formation of small compact islands in the submonolayer range. Carbon monoxide oxidation and nitrous oxide reduction have been studied on Rh/Pt(1 1 1) electrodes. The oxidation of carbon monoxide is catalyzed by the presence of very low coverages of rhodium as demonstrated by the negative shift of the CO oxidation profile. Results are compatible with a bifunctional mechanism for catalysis including CO diffusion in the Pt domains toward the edges of the islands (splitting of the voltammetric oxidation profile). The reduction of nitrous oxide occurs at different potential and with different rates on Pt domains, at the center of the Rh islands and at their edges, being the latter sites especially active. In any case, the adsorptive and catalytic activity of the adlayers differ from those of the bulk Pt(1 1 1) and Rh(1 1 1) electrodes. The existence of strain in the film together with a diminution in the coordination number for adatoms at the edges of the islands are considered to be at the origin of the observed behavior.  相似文献   

6.
任宇  宋卫余  刘坚  赵震 《工业催化》2018,26(11):46-49
使用密度泛函理论对甲醛分子在Pd(111)晶面与Pd(100)晶面的氧化反应机理进行研究,结果表明,Pd(100)晶面相比于Pd(111)晶面更有利于甲醛分子的氧化,为进一步合理设计甲醛氧化贵金属催化剂提供了理论依据。  相似文献   

7.
The adsorption/desorption kinetics of adenine on Au(1 1 1) electrodes is studied by Electrochemical Impedance Spectroscopy (EIS) in 0.5 M NaF solutions at four adenine concentrations. The experimental procedure is designed in order to obtain impedance data unaffected by surface reconstruction on the entire potential region of adsorption. The frequency dispersion of the impedance at potentials of the adsorption region has been analysed according to the Frumkin-Melik-Gaykazyan adsorption theory without any “a priori” assumption about the potential dependence of the adsorption rate constant. The analysis provides the values of the adsorption capacitance, Cad, adsorption resistance, Rad and the Warburg coefficient, σad, at every potential, and from them the relaxations times τH and τD. A mixed adsorption-diffusion control has been detected and the specific rate constant of adsorption has been obtained in a wide potential region.  相似文献   

8.
The electrochemical reduction of nitrate ion was studied by cyclic voltammetry on Pt(1 1 1) and [n(1 1 1) × (1 1 1)] stepped Pt surfaces, where n (=14, 10, 7, 6, 5, 4, 3, 2) is the number of terrace atoms, in 0.1 M HClO4 + 10 mM KNO3. The electrocatalytic nitrate reduction was found to hardly proceed on Pt(1 1 1) in the hydrogen adsorption region, while the electrocatalytic activity was improved with the increase in the step density. Inactivation was observed in the presence of adsorbed hydrogen or nitrate-derived reduced adsorbate, i.e. adsorbed NO, on (1 1 1) step sites. It was, therefore, concluded that the electrocatalytically active NO3 species does not adsorb on the (1 1 1) terraces but on the (1 1 1) monoatomic steps. The nitrate reduction current increased with the step density in a non-linear relationship. The overall current density at 0.21 V (RHE) corresponding to the peak potential of the main electrocatalytic nitrate reduction wave which was maximum at n = 2, abruptly increased with short terraces, i.e. n < 5, where the current wave of adsorbed hydrogen on the Pt stepped surface with comparatively narrow (1 1 1) terraces, denoted as Hnt, also appeared unmodified for n < 5 on voltammograms recorded in 0.1 M HClO4 in the absence of nitrate.  相似文献   

9.
The coverage of Sn on Pt(1 1 1) which is obtained by electrochemical deposition from 5×10−5 M Sn2+ in 0.5 M H2SO4 has been determined by XPS for different deposition times. Complete suppression of hydrogen adsorption corresponds to a coverage of ?max=0.35 (Sn to surface Pt atoms).Co-adsorption of CO with Sn on Pt(1 1 1) has been studied by FTIR spectroscopy. The IR spectra of the stretching vibration of CO can be interpreted in terms of the vibrational signature of the Pt(1 1 1)/CO system and no vibrational bands associated with CO on Sn are detected. At high Sn coverages, the 1840 cm−1 band associated with bridge-bonded CO and the 2070 cm−1 band assigned to on-top CO are present, however, no hollow site adsorption which is characterized by the 1780 cm−1 band is revealed within the resolution of the experiment. This vibrational signature corresponds to a less compressed adlayer compared to the (2×2)-3CO saturation structure on Pt(1 1 1). At lower Sn coverages, signatures from both the compressed and the less compressed CO adlayer structures are seen in the spectra. From earlier structural and electrochemical studies it is known that Sn is adsorbed in 2D islands and influences CO molecules in its neighbourhood electronically. This leads to a disappearance of the IR band from CO adsorbed in the hollow site at high Sn coverages and to higher population of the weakly adsorbed state of CO for all Sn-modified surfaces, i.e. a relative increase of the amount of CO oxidised at low potentials. In addition to this electronic effect, Sn also exerts a co-catalytic effect at low Sn coverages on that part of CO which is adsorbed at a larger distance from Sn due to a bi-functional mechanism. The IR spectra shows for the Sn-modified Pt(1 1 1) surface that the transition from the compressed CO adlayer which is characterized by the hollow site adsorption of CO to the less compressed one which exhibits a characteristic band associated with bridge-bonded CO occurs already at 250 mV instead of 400 mV.  相似文献   

10.
Gold colloid solutions were prepared by reduction of Au(III) with Sn(II) in both acidic (HCl) and alkaline (carbonate) media, and characterized by electron microscopy, X-ray diffraction and light absorption spectra. Depending on the colloid preparation conditions, metal particles of 5-30 nm in size were obtained. Light absorption spectra of the Au colloid solutions contain an absorption band at 500-600 nm, typical of small gold particles. According to XRD data, colloid particles contain the metallic Au and SnO2 phases. The colloid formation rate and colloid solution stability depend on solution pH; the alkaline colloid solutions are formed more slowly and are more stable. The gold nanoparticles adsorbed on the dielectrics surface were found to initiate the electroless copper deposition process. The glassy carbon (GC) electrode modified by Au nanoparticles (200-900 ng cm−2 Au) was found to be an electrocatalyst for dimethylamine borane, borohydride, hydrazine, and formaldehyde oxidation in alkaline solutions. The activity of the reducers can be arranged as follows: DMAB > NaBH4 > N2H4 > CH2O.  相似文献   

11.
The oxidation and reforming kinetics of methane by O2, CO2 and H2O were studied on a stepped Pt(5 5 7) single crystal from 623 to 1050 K under methane rich conditions. The rate of carbon deposition was followed by ex-situ Auger electron spectroscopy under non-oxidative conditions. The apparent activation energy for methane decomposition was significantly lower than the apparent barriers measured for both total oxidation, CO2 and H2O reforming. Total oxidation of methane to CO2 and H2O followed by combined dry and steam reforming (combined combustion-reforming) led to CO production rates which were higher than direct CO2 or H2O reforming rates. The enhanced rates are most likely due to the ability of adsorbed oxygen to prevent carbon nucleation and/or scavenge carbon enabling the reforming reaction to turnover on a larger fraction of sites. Comparable amounts of carbon were found by Auger electron spectroscopy measurements after both direct dry or steam reforming, while combined oxidation-reforming had considerable less carbon. During direct dry or steam reforming, CO2 and H2O serve only to scavenge adsorbed atomic carbon, while in the presence of oxygen, carbon is removed by both combustion and reforming routes.  相似文献   

12.
The adsorption of phosphate anions from phosphate solutions at poly-oriented and single-crystal platinum electrodes, primarily Pt(1 1 1), was studied over a wide range of pH by cyclic voltammetry. The features observed at the poly-oriented Pt electrode in phosphate solution may be related to the different crystalline facets, the (1 1 1) orientation presenting the most significant behavior in terms of phosphate adsorption. On the reversible hydrogen electrode (RHE) scale, the phosphate adsorption strength decreases with increasing alkalinity of the solution. Qualitatively, three different pH regions can be distinguished. At pH < 6 only a broad reversible peak is observed, corresponding to the adsorption of H2PO4 and further deprotonation to adsorbed HPO4. For 6 < pH < 11 a butterfly feature followed by one or two anodic peaks (depending on scan rate) is observed, ascribed to the adsorption of HPO4 followed by its subsequent deprotonation to adsorbed PO43−. The splitting into two or three voltammetric features, and the irreversibility of the two features at more positive potential, is ascribed to the deprotonation reaction leading to a surface species (i.e. phosphate) which needs to change its surface coordination. At pH > 11 a reversible pre-wave and a sharp spike are observed, ascribed to the co-adsorption of phosphate and hydroxide.  相似文献   

13.
Hybrid films composed of poly(luminol) and nanometer-sized clusters of polyoxometalate, SiMo12O404− and PMo12O403− have been prepared in acidic aqueous solutions. These films are stable and electrochemically active, and produced on glassy carbon, platinum, gold and transparent semiconductor tin oxide electrodes. The electrochemical quartz crystal microbalance and cyclic voltammetry were used to study in situ growth of the hybrid poly(luminol)/SiMo12O404− and poly(luminol)/PMo12O403−. Both the poly(luminol)/SiMo12O404− and poly(luminol)/PMo12O403− hybrid films showed four redox couples and the electrochemical properties were compared to SiMo12O404− and PMo12O403−. When transferred to various acidity aqueous solutions, the four redox couples and the formal potentials of two hybride film were observed to be pH-dependent. The electrocatalytic reduction of ClO3, BrO3, IO3, S2O82− and NO2 by a poly(luminol)/PMo12O403− hybrid film in an acidic aqueous solution showed an electrocatalytic reduction activity of IO3 > BrO3 and ClO3. The electrocatalytic oxidation of dopamine and epinephrine by a poly(luminol)/PMo12O403− hybrid film was also investigated.  相似文献   

14.
Studies of the electrochemical oxidation of a series of straight-chain terminal alkenoic acids adsorbed at a Pt(111) electrode surface are reported. Compounds adsorbed were: propenoic acid (acrylic acid, PPA); 3-butenoic acid (vinylacetic acid, 3BTA); 4-pentenoic acid (allylacetic acid, 4PTA); 6-heptenoic acid (6HPA); and 10-undecenoic acid (10UDA). Vibrational spectra of adsorbed layers were obtained by use of electron energy-loss spectroscopy (EELS). Molecular packing densities were measured by use of Auger spectroscopy. Electrochemical oxidation of each adsorbed layer was explored by means of cyclic voltammetry in aqueous inert electrolyte (KF/HF). As the analogous aliphatic acids are not chemisorbed at Pt under the same conditions, the alkenoic acids evidently adsorb at Pt(111) predominantly through the C=C double bond. Molecular packing densities indicate that the carboxylic acid moiety is in contact with the Pt surface only in the case of PPA. EELS spectra also indicate that the carboxylate groups (other than in PPA) are present as pendants. The carboxylic acid O-H stretching bands of most of the adsorbed acids are red-shifted and broadened, evidently due to extensive intermolecular hydrogen bonding; the exceptions are PPA, for which the interaction is primarily with the Pt surface, and 3BTA, for which intermolecular interaction between the carboxylic acid pendants is apparently prevented by steric considerations. The surface-attached carboxylic acid moieties react with KOH solution, leading to retention of K+ ions, detected by Auger spectroscopy, and to changes in the vibrational spectra indicative of carboxylate anions; reactivity toward KOH decreases with chain length. Adsorbed alkenoic acids at Pt(111) surfaces are stable in water and in vacuum. Oxidation of the adsorbed short-chain acids PPA and 3BTA proceeds to completion, forming CO2 as the principal product. Oxidation of the adsorbed long-chain acids converts the C=C moiety to 2CO2, and transforms the remainder of the molecule to an unadsorbed diacid (likely possibilities are malonic acid from 4PTA; glutaric acid from 6HPA; and heptane-1,7-dioic acid from 10UDA).  相似文献   

15.
Glassy carbon electrodes coated with adsorbed single layers of the cationic polyelectrolyte poly(allylamine hydrochloride), PAH, were produced by solvent evaporation for subsequent development of PAH modified thin mercury film electrodes (PAH/TMFE). The present work describes the preparation, incorporation features towards lead(II) species, as well as the morphological characterization of PAH coatings of different molar loadings, prepared from polyelectrolyte solutions of different composition. The present PAH films revealed interesting morphologic features, related to the process of solvent evaporation and to the specific structural properties of the PAH polyelectrolyte in the assembling medium.The novel PAH-thin mercury film electrodes, developed for the determination of trace lead(II) as its anionic forms in chloride medium, were found to be stable, sensitive and reproducible. Concentrations in the ppb concentration region could be easily assessed using 20 s accumulation time (detection limit 1.2 ppb, i.e. 6 nM, 3σ) with low relative standard deviations (<2.5%). The sensitivity of the SWASV determination of lead(II) increased 20% compared to the uncoated TMFE. The linearity range reached at least two orders of magnitude. Additionally, the PAH-coated mercury film electrodes presented an improved resistance to fouling by common surfactants.  相似文献   

16.
The reduction of CO2 on bismuth modified Pt(1 1 0) single crystal surfaces has been studied voltammetrically. The effect of bismuth and the amount of formed CO species on the rate of hydrogen evolution has also been investigated. A decrease in the rate of CO2 reduction is observed due to the modification of the surface with bismuth adsorption. This decrease goes beyond the simple third body effect expected from the blockage of active sites on the platinum surface after bismuth adsorption. However, the hydrogen evolution reaction is relatively insensitive to the presence of adsorbed species, in contrast with previous result reported for Pt(1 1 1) and Pt(1 0 0) surfaces.  相似文献   

17.
A new chemically modified chitosan hydrogel with 2,5‐dimercapto‐1,3,4‐thiodiazole (CTS‐DMTD) has been synthesized. The structure of CTS‐DMTD was confirmed by elemental analysis and FTIR. It was found that adsorption capacities were significantly affected by the pH of solution, with optimum pH values of 3.0 for Au(III), 2.0 for Pd(II) and Pt(IV). The saturated adsorption capacities were 198.5 mg/g for Au(III), 16.2 and 13.8 mg/g for Pd(II) and Pt(IV), respectively. Langmuir and Freundlich isotherm adsorption models were applied to analyze the experimental data. The results showed that adsorption isotherms of Pd(II) and Pt(IV) could be well described by the Langmuir equation. The adsorption kinetic investigations indicated that the kinetic data correlated well with the pseudo‐second‐order model. The recovery experimental data showed that CTS‐DMTD had a higher affinity toward Au(III), Pd(II), and Pt(IV) in the coexistence system containing Cu(II), Fe(III), Cd(II), Ni(II), Mg(II), and Zn(II). The studies of desorption were carried out using various reagents and the optimum effect was obtained using thiourea. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009  相似文献   

18.
The present paper reviews our investigations concerning the mechanism of H2 + O2 reaction on the metal surfaces (Pt, Pd) at different structures: single crystals (Pt(1 1 1), Pt(1 0 0), Pd(1 1 0)); microcrystals (Pt tips); and nanoparticles (Pd–Ti3+/TiO2). Field electron microscopy (FEM), field ion microscopy (FIM), high-resolution electron energy loss spectroscopy (HREELS), XPS, UPS, work function (WF), TDS and temperature-programmed reaction (TPR) methods have been applied to study the kinetics of H2 oxidation on a nanolevel. The adsorption of both O2 and H2 and several dissociative products (Hads, Oads, OHads) was studied by HREELS. Using the DFT technique the equilibrium states and stretching vibrations of H, O, OH, H2O, adsorbed on the Pt(1 1 1) surface, have been calculated depending on the surrounding of the metal atoms. Sharp tips of Pt, several hundreds angstroms in radius, were used to perform in situ investigations of the dynamic surface processes. The FEM and FIM studies on the Pt-tip surface demonstrate that the self-oscillations and waves propagations are connected with periodic changes in the surface structure of nanoplane (1 0 0)-(hex) ↔ (1 × 1), varying the catalytic property of metal. The role of defects (Ti3+-□O) in the adsorption centers formation, their stabilization by the palladium nanoparticles, and then the defects participation in H2 + O2 steady-state reaction over Pd–Ti3+/TiO2 surface have been studied by XPS, UPS and photodesorption techniques (PhDS). This reaction seems to involve the “protonate” hydrogen atoms (H+/TiOx) as a result of spillover effect: diffusion of Hads atoms from Pd particles on a TiOx surface. The comprehensive study of H2, O2 adsorption and H2 + O2 reaction in a row: single crystals → tips → nanoparticles has shown the same nature of active centers over these metal surfaces.  相似文献   

19.
Three complexes [K(DC18C6-A)]2[M(mnt)2] (DC18C6-A=cis-syn-cis-dicyclohexyl-18-crown-6, isomer A; M=Ni, 1; Pd, 2; Pt, 3; mnt = 1,2-dicyanoethene-1,2-dithiolate, maleonitriledithiolate, [C2S2(CN)2]2−) have been synthesized and characterized by elementary analysis, UV–vis, FT-IR spectroscopy and X-ray single crystal diffraction. They are isomorphous and all display infinite one-dimensional chain-like structure formed by [K(DC18C6-A)]+ complex cations and [M(mnt)2]2− (M=Ni, Pd, Pt) complex anions through K–N interactions. Thermal analysis indicates that three complexes are all thermal stable under 260 °C and experience the same decomposition process of dissociation and evaporation of crown ether molecules. Their electrochemical behaviors have been studied by cyclic voltammetry.  相似文献   

20.
Henequen fibers were grafted with a double impregnating monomer 2‐hydroxyethylacrylate (HEA) and ethylacrylate (EA) to improve the physicomechanical properties. The fibers soaked in different concentration (1–10%) of monomer + MeOH solution along with photoinitiator Irgacure 907 [2%] were cured under ultraviolet (UV) lamp at different UV radiation intensities (2–14 passes). Concentration of monomer at different radiation intensities was optimized with extent of mechanical properties such as polymer loading, tensile strength, and elongation at break. Enhanced tensile strength (268%) and elongation at break (110%) were achieved by the polymer treated fibers than untreated virgin fibers. We observed that, henequen fibers treated by 3% EA showed better physico‐mechanical properties than those treated by 5% HEA. The tensile properties of henequen fibers treated by 3% EA can be enhanced by adding aloxysilane; 3‐(trimethoxysilyl) propylmethacrylate additives with bulk monomer EA (3%). The degradability of the treated and untreated fibers due to accelerated weathering were also studied and it has been found that surface modified henequen fibers produced more resistivity towards different weathering conditions than untreated fibers. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 4000–4006, 2006  相似文献   

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