Experimental and density functional theory studies on PtPb/C bimetallic electrocatalysts for methanol electrooxidation reaction in alkaline media

Carbon-supported bimetallic Pt_mPb₁ (m = 1, 2, 3) electrocatalysts with different Pt/Pb atomic ratios were synthesized by a polyol method. The X-ray diffraction results reveal that a PtPb alloy formed in the Pt_mPb₁/C electrocatalysts. TEM images show that the PtPb nanoparticles distribute uniformly on the carbon support, and are about 4–5 nm in size. The Pt_mPb₁/C bimetallic catalysts show superior activities toward methanol electrooxidation reaction (MOR) than the Pt/C in alkaline media. Both CO stripping measurements and density functional theory studies reveal that CO adsorption decreased significantly on the Pt_mPb₁/C bimetallic catalysts compared with on pure Pt, which may offer an explanation for the enhanced MOR activity of the Pt_mPb₁/C bimetallic catalysts.     

Electrocatalytic oxidation of methanol on Cu modified polyaniline electrode in alkaline medium

Electrolytically deposited Cu on polyaniline film covered Pt substrate (Cu/PANI/Pt) is used as anode for the electrooxidation of methanol in alkaline medium. The electrochemical behavior and electrocatalytic activity of the electrode were characterized using cyclic voltammetry, impedance spectroscopy, chronomethods, rotating disc voltammetry and polarization studies. The morphology and composition of the modified film were obtained using SEM and EDAX techniques. The electrooxidation of methanol in NaOH is found to be more efficient on Cu/PANI/Pt than on bare Cu (Cu), electrodeposited Cu on Cu (Cu/Cu) and electrodeposited Cu on Pt (Cu/Pt) substrates. Partial chemical displacement of dispersed Cu on PANI with Pt or Pd further improved its performance towards methanol oxidation.     

Electroreduction of dioxygen (ORR) in alkaline medium on Ag/C and Pt/C nanostructured catalysts—effect of the presence of methanol

Ag/C catalysts with different loading were prepared using a colloidal route to obtain well dispersed catalysts on carbon, with a particle size close to 15 nm. An amount of 20 wt.% Ag on carbon was found to be the best loading in terms of current density and mass activity. The 20 wt.% Ag/C catalyst was then studied and the kinetics towards ORR was determined and compared with that of a 20 wt.% Pt/C catalyst. The number of exchanged electrons for the ORR was found to be close to four with the rotating disk electrode (RDE) as well as with the rotating ring disc electrode (RRDE) techniques. From the RDE results, the Tafel slopes b, the diffusion limiting current density inside the catalytic film (j_l^film) and the exchange current density (j₀) were evaluated. The Tafel slopes b and diffusion limiting current densities inside the catalytic film (j_l^film) were found to be in the same order for both catalysts, whereas the exchange current density (j₀), which is a suitable estimation of the activity of the catalyst, was at least 10 times higher at the Pt/C catalyst than at the Ag/C catalyst. The behavior of both catalysts in methanol containing electrolyte was investigated and it was found that at a low methanol concentration, the Pt/C catalyst was quasi-tolerant to methanol. But, at a high methanol concentration, the ORR at a Pt/C was affected. However, the Pt/C catalyst showed in each case better activity towards ORR than the Ag/C catalyst, even if the latter one was less affected by the presence of methanol than the former one.     

Oxide (CeO2, NiO, Co3O4 and Mn3O4)-promoted Pd/C electrocatalysts for alcohol electrooxidation in alkaline media

This study investigated Pt/C, Pd/C and oxide (CeO₂, NiO, Co₃O₄ and Mn₃O₄)-promoted Pd/C for electrooxidation reactions of methanol, ethanol, ethylene glycol and glycerol in alkaline media. The results show that Pd/C electrocatalysts alone have low activity and very poor stability for the alcohol electrooxidation. However, addition of oxides like CeO₂, NiO, Co₃O₄ and Mn₃O₄ significantly promotes catalytic activity and stability of the Pd/C electrocatalysts for the alcohol electrooxidation. The Pd-Co₃O₄ (2:1, w:w)/C shows the highest activity for the electrooxidation of methanol, EG and glycerol while the most active catalyst for the ethanol electrooxidation is Pd-NiO (6:1, w:w)/C. On the other hand, Pd-Mn₃O₄/C shows significantly better performance stability than other oxide-promoted Pd/C for the alcohol electrooxidation. The poor stability of the Pd-Co₃O₄/C electrocatalysts is most likely related to the limited solubility of cobalt oxides in alkaline solutions.     

The role of DNA membrane in the electro-oxidation methanol by nickel ions modified electrode in alkaline medium

A DNA-Ni²⁺ complex film was prepared by using direct electrodeposited method. The nickel ions immobilized in the DNA membrane exhibited an excellent and stable catalytic activity to the electro-oxidation of methanol. It was indicated that the DNA membrane would not block the methanol molecules diffuse into the catalytic active site in the membrane. Furthermore, it could make oxidation intermediate products which may poison the active site react sufficiently. As a result, the DNA membrane was an ideal carrier for the Ni ion immobilizing, and the utilization efficiency of catalysts Ni²⁺ could get higher.     

Anodic growth of passive layers on steel rebars in an alkaline medium simulating the concrete pores

Electrochemical impedance spectroscopy (EIS) and cyclic voltammetry (CV) techniques have been used to study passive layers anodically grown on steel rebars in an aqueous alkaline solution simulating the electrolyte of the concrete pores. Nyquist diagrams recorded by EIS at the different stabilization potentials show a diffusional tail at low frequencies. The analysis of the impedance measurements has been made by means of an equivalent circuit with a Warburg component and within the framework of the point defect model (PDM) theory. It is observed that the calculated concentration of vacancies is a function of the potential in accordance with the theoretical prediction of the PDM.     

Synergistic effect of halide ions and polyethylene glycol on the corrosion inhibition of aluminium in alkaline medium

The corrosion inhibition of aluminium in alkaline medium was studied at 30 and 40°C in the presence of polyethylene glycol (PEG) using gravimetric (weight loss) and thermometric techniques. The effect of halides (KCl, KBr, and KI) on the inhibitory action of PEG was also studied. It was found that PEG acted as inhibitor for aluminium corrosion in the alkaline medium. Inhibition efficiency increased with increasing inhibitor concentration. An increase in temperature led to increase in both the corrosion rate and inhibition efficiency in the absence and presence of inhibitor and halides. Phenomenon of chemical adsorption mechanism is proposed from the values of E_a, Q_ads, and ΔG obtained. The adsorption of PEG on the surface of aluminium was found to obey Flory–Huggins and Temkin adsorption isotherms. The synergism parameter, S₁ evaluated was found to be greater than unity indicating that the enhanced inhibition efficiency caused by the addition of halides is synergistic in nature. The inhibition efficiency, surface coverage and synergism parameter increased in the order; I^?> Br^?> Cl^? showing that a joint adsorption of PEG and halide ions on aluminium plays a significant role in the adsorption process. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Investigation of chemical bonds in the ordered Ba3Zn(Nb2-xMox)O9+x/2 ceramics and its effects on the microwave performance

1:2 ordered Ba₃Zn(Nb_2-xMo_x)O_9+x/2(BZNM) ceramics with space group $\text{P}\overline{3}\text{ml}$ were prepared by solid-state method. The nature of chemical bonds in Ba₃Zn(Nb_2-xMo_x)O_9+x/2(BZNM) ceramics was investigated for the first time. Firstly, the bond energy was closely related to the lattice vibration. High bond energy would lead to weak non-harmonic interactions, which were the main factors of improving Qf. Secondly, polarization of the chemical bond was the principal contributor to the relative permittivity of microwave ceramics. Compared with the traditional method, the calculated result based on the P-V theory reduced the error from 81% to 4.4%. Through the discussion, it was confirmed that the analysis method based on chemical bond was highly feasible and scientific in the microwave ceramics. At last, the system of Ba₃Zn(Nb_1.992Mo_0.008)O_9.004 sintered at 1435?°C for 6?h and annealed at 1300?°C for 10?h had excellent microwave dielectric properties: ε_r?=?38.9, Qf?=?102,931?GHz, τ_f?=?19.2?ppm/°C, which, to our best knowledge, provided a alternative for the application of millimeter-wave communications.     

Comparison of the degradation of polycaprolactone and polycaprolactone–(β‐tricalcium phosphate) scaffolds in alkaline medium

The design and fabrication of scaffolds and biodegradable devices using slow‐degrading polymers and composites (degradation/resorption > 2 years) involve the necessity for long‐term in vitro and in vivo studies. If multiple designs and materials need to be tested, then this would use much time and financial resources. Accelerated degradation systems aim to achieve comparable degradation profiles within a shorter period of time. This investigation considers the hydrolytic degradation of polycaprolactone (PCL) and PCL–calcium phosphate (CaP) scaffolds in 5 mol L^?1 NaOH at 37 °C. The scaffolds degrade via surface erosion, which proceeds in a consistent and predictable manner. The hydrolytic degradation of PCL‐based scaffolds alone is slow, governed by their high molecular weights, crystallinity, hydrophobicity, surface‐to‐volume ratio and porosity. The incorporation of CaP significantly increases the degradation rate. Copyright © 2007 Society of Chemical Industry     

Influence of anionic stabilization of alumina particles in 2-propanol medium on the electrophoretic deposition and mechanical properties of deposits

The ceramic dispersions were prepared using 0.85, 1.70, 4.25, 12.75 or 21.25 wt.% of monochloroacetic, dichloroacetic or trichoroacetic acid, 15 wt.% alumina and 2-propanol. The mechanism of anionic stabilization in 2-propanolic media was described. Alumina green bodies were prepared from the stable dispersion via electrophoretic deposition (EPD). It was found that increasing dispersion conductivity significantly influenced the EPD yields. The most effective electrophoretic depositions were performed from dispersions with conductivity in range 4.0–5.3 × 10⁻⁴ S m⁻¹. Deposits with the highest green density were prepared from the dispersion stabilized by trichloroacetic acid. This behavior was explained by low voltage drop during deposition. The surface roughness was high at low dispersion conductivity and with increasing acid concentration in dispersion the surface of deposits was smoother. The mechanism of particle arrangement in deposit was discussed. Influence of stabilizer amount in the dispersion on the hardness and fracture toughness was described.     

1／2中黏煤在炼焦配煤中的应用研究

分析了1／2中黏煤的煤质与结焦性能，并进行40kg小焦炉试验和工业炼焦试验，研究表明，1／2中黏煤在配比逐步提高到15％的过程中，随着肥煤配比的提高，焦炭质量能达到高炉要求，炼焦成本显著降低。     

Effect of alkaline earth promoters (MgO,CaO, and BaO) on the activity and coke formation of Ni catalysts supported on nanocrystalline Al2O3 in dry reforming of methane

Ni/Al₂O₃ promoted catalysts with alkaline earth metal oxides (MgO, CaO, and BaO) were prepared and employed in dry reforming of methane (DRM). The catalysts were prepared by impregnation method and characterized by XRD, BET, TPR, TPO, and SEM techniques. The obtained results showed that the addition of MgO, CaO, and BaO as promoter decreased the surface area of catalysts (S_BET). The catalysis results exhibited that adding alkaline earth promoters (MgO, CaO, and BaO) enhanced the catalytic activity and the highest activity was observed for the MgO promoted catalyst. TPR analysis showed that addition of MgO increased the reducibility of nickel catalyst and decreased the reduction temperature of NiO species. The TPO analysis revealed that addition of promoters decreased the amount of deposited coke; and among the studied promoters, MgO has the most promotional effect for suppressing the carbon formation. SEM analysis confirmed the formation of whisker type carbon over the spent catalysts.     

A comparative study of the electrocatalytic oxidation of ethylene glycol on PtAu nanocomposite catalysts in alkaline, neutral and acidic media

Electrocatalytic oxidation of ethylene glycol on platinum-gold nanocomposite catalysts is investigated by cyclic voltammetry. Platinum-gold nanoparticles are prepared by chemical reduction, and cyclic voltammograms of carbon-supported platinum-gold nanocomposite catalysts show significant differences in alkaline, neutral and acidic solutions. The catalysts exhibit high electrocatalytic activity and stability in alkaline solution, showing oxidation peaks at low potentials with high current densities. Oxidation peaks at higher potentials with significant current declines are observed in neutral solution, and further positive shifts in peak potential are observed in acidic solution. The concentrations of ethylene glycol and the supporting electrolytes also affect the reaction. A higher alkaline concentration is favorable for oxidation at low potential with high current density. Increased phosphate concentration in neutral buffer solution yields a negative shift in peak potential and minor enhancement in peak current density. Changes in the sulfuric acid concentration mainly affect peak current density. Factors such as the synergic catalysis effect and increased active surface area are thought to be responsible for the reactivity of the platinum-gold nanocomposite catalysts.     

Characterization of surface species on V/SiO2 and V,Na/SiO2 and their role in the partial oxidation of methane to formaldehyde

Silica-supported vanadium (1–8 wt%) and vanadium (5 wt%)-sodium (0.4 wt%) catalysts have been characterized by laser Raman spectroscopy, temperature-programmed reduction, X-ray photoelectron spectroscopy, NO + NH₃ rectangular pulses and oxygen chemisorption. The presence of different vanadium species was correlated with activity and selectivity during the methane partial oxidation reaction. The pre-impregnation of the silica support with sodium favors vanadium dispersion, but strongly diminishes V=O concentration due to the formation of orthovanadate-like compounds. As a result of these modifications, methane conversion is strongly inhibited while formaldehyde decomposition is favored.     

金川龙首矿中深孔破坏规律及护孔措施

金川龙首矿西二采区拟采用无底柱分段崩落法代替胶结充填法开采低品位矿石,从而寻求降低采矿成本的新途径.该矿地质条件复杂,中深孔能否成孔以及是否具有较好的保持率,是无底柱分段崩落法能否顺利实施的关键.采用不连续变形分析方法对西二采区地质条件下的中深孔破坏形式及规律进行了分析,得出中深孔最易发生破坏的部位主要集中在巷道周边破...     

Effect of Ni Substitution on the Structural,Magnetic, and Electronic Structure Properties of Gd0.4Tb0.6(Co1−xNix)2 Compounds

The comprehensive research of magnetic and electronic structure properties of the new class of Gd_0.4Tb_0.6(Co_1−xNi_x)₂ compounds, crystallizing in the cubic Laves phase (C15), is reported. The magnetic study was completed with electrical resistivity and electronic structure investigations. The analysis of Arrott plots supplemented by a study of temperature dependency of Landau coefficients revealed that all compounds undergo a magnetic phase transition of the second type. Based on magnetic isotherms, magnetic entropy change (ΔS_M) was determined for many values of the magnetic field change (μ₀H), which varied from 0.1 to 7 T. For each compound, the ΔS_M had a maximum around the Curie temperature. Both values of the |ΔS_M^max| and relative cooling power RCP parameters increased with increasing nickel content. It is shown that structural disorder upon Co/Ni substitution influences some magnetic parameters. The magnetic moment values of Co atoms determined from different methods are quantitatively consistent. From the M(T) dependency, the exchange integrals J_RR, J_RT, and J_TT between rare-earths (R) and transition metal (T) moments were evaluated within the mean-field theory (MFT) approach. The experimental study of the electronic structure performed with the use of the X-ray photoelectron spectroscopy (XPS) was completed by calculations using the full-potential linearized augmented plane waves (FP-LAPW) method based on the density functional theory (DFT). The calculations explained experimentally observed changes in the XPS valence band spectra upon the Ni/Co substitution.     

Combined effects of internal heat generation and higher order chemical reaction on the non‐darcian forced convective flow of a viscous incompressible fluid with variable viscosity and thermal conductivity over a stretching surface embedded in a porous medium

In this paper, we study the combined effects of internal heat generation and higher order chemical reaction on a steady two‐dimensional non‐Darcian forced convective flow of a viscous incompressible fluid with variable dynamic viscosity and thermal conductivity in a fluid saturated porous medium passing over a linear stretching sheet. Using similarity transformations, the governing nonlinear‐coupled partial differential equations are made dimensionless and solved numerically for similarity solutions using very robust computer algebra software Maple 8. The non‐dimensional velocity, temperature and concentration distributions are presented graphically for various pertinent parameters such as relative temperature difference parameter, Darcy number, porosity parameter, reaction rate parameter and the order of the chemical reaction. The variations of Prandtl number and Schmidt number within the boundary layer are also displayed graphically when the fluid dynamic viscosity and thermal conductivity are temperature dependent. From the present numerical computations it is found that Prandtl number as well as Schmidt number must be taken as variables within the flow domain when the fluid's dynamic viscosity and thermal conductivity are variable. In the presence of internal heat generation, dynamic viscosity and thermal conductivity of the fluid are found to be higher than when it is absent. Increasing Darcy number reduces dynamic viscosity as well as thermal conductivity whereas increasing pore size reduces the Schmidt number and increases the Prandtl number within the boundary layer. For higher order reaction the rate of increase in mass transfer function is less compared to the rate of increase for the lower order reaction. © 2011 Canadian Society for Chemical Engineering     

Surface, kinetics and electrocatalytic properties of the Ti/(Ti + Ru + Ce)O2-system for the oxygen evolution reaction in alkaline medium

Ti-supported (Ti + Ru + Ce)O₂ electrodes, prepared at 450 °C, were characterised by XRD, open-circuit potential (E_oc), capacity data (C) and morphology factor (φ) determinations. XRD measurements showed mixed oxides present a low degree of crystallinity. E_oc-data and CV-spectra support surface electrochemistry of mixed oxides is governed by the Ru(III)/Ru(IV) redox couple. In situ surface characterisation revealed the active surface area increases on increasing nominal CeO₂-content. φ-Values remained in the 0.18-0.3 interval supporting the coatings have a low electrochemical porosity. Kinetics was studied recording polarisation and chronopotentiometric curves, which permitted to determine the Tafel slope and reaction order (with respect to OH⁻), in the low and high overpotential domains. Tafel slope data, b, presented a dependence on overpotential and oxide composition indicating the OER electrode mechanism depends on these variables. A unit reaction order with respect to OH⁻ was found for all electrode compositions investigated. The theoretical analysis of the electrode mechanism permitted to analyse the changes in the experimental Tafel slopes taking into account modifications in the apparent electronic transfer coefficient, α_ap. Analysis of the true and apparent electrocatalytic activities revealed the O₂-evolution reaction rate is affected by oxide composition due to morphologic effects.     

A comparative study on the thermal stability,textural, and structural properties of mesostructured γ-Al2O3 granules in the presence of La,Sn, and B additives

Mesoporous γ-alumina is widely used as catalyst support in various catalytic reactions of industrial interest. However, due to the instability of γ-alumina at elevated temperatures, many efforts have been reported to inhibit the α-alumina phase transition through doping with suitable metalloids, as well as transition, post-transition, or rare-earth elements. In the present study, undoped and La-, Sn-, and B-doped alumina granules were synthesized via sol-gel/oil drop method with the aim to clarify the role of the additives and their content on the porous structure as well as on the chemical, structural, and microstructural behavior of γ-alumina. XRD and DTA/TG results demonstrated that thermal stability of transition aluminas increases more than 100 °C by 3 wt% lanthanum and tin doping; however, boron doping seems to have only negligible effect on the thermal stability. On the other hand, based on nitrogen adsorption-desorption analysis, tin and boron-doped aluminas showed a higher surface area at 750 °C (between 214.74 m²/g to 245.97 m²/g) but higher loss in the surface area after calcination at 1200 °C (between 25.45 m²/g to 8.57 m²/g). On the contrary, the 3 wt% La-doped alumina sample, with a relatively high surface area at 750 °C (227.17 m²/g), exhibited the highest surface area after calcination at 1200 °C (53.07 m²/g). ²⁷Al MAS NMR and HRTEM studies indicated that the presence of 3 wt% La in alumina structure leads to thermal and mesoporous structure stability up to 1200 °C by inhibiting oxygen lattice restructuring. These results provide a comparative perspective of La, B, and Sn additives' behavior in γ-alumina.     

A comparative study of the thermal stability and reactions of CH2, CH3 and C2H5 species on the Pd(100) surface

Adsorbed CH₂, CH₂ and C₂H₅ moieties were produced on Pd(100) at 90 K by photoinduced dissociation of the corresponding iodo compounds, and their thermal reactions were established.This laboratory is a part of the Center of Catalysis, Surface and Material Science at the University of Szeged.