Anomalous IR optical properties of aggregates of Pd nanoparticles induced through electrochemical cyclic voltammetry

IR optical properties of Pd nanoparticles with different size and aggregation state were studied in the current paper. The dispersed Pd nanoparticles () stabilized with poly(N-vinylpyrrolidone) (PVP) were synthesized by the seeding growth method, in which the seeds were formed step by step through reducing H₂PdCl₄ with ethanol. The dispersed Pd nanoparticles of much large size () were grown from the by keeping the colloid of undisturbed for 150 days at room temperature around 20 °C. The aggregates of () were prepared through an agglomeration process induced during a potential cyclic scanning between −0.25 V and 1.25 V for 20 min at a scan rate of 50 mV s⁻¹. Scanning electron microscope (SEM) patterns confirmed such aggregation of . Fourier transform infrared (FTIR) spectroscopy together with CO adsorption as probe reaction was employed in studies of IR optical properties of the prepared Pd nanoparticles. The results demonstrated that CO adsorbed on films substrated on CaF₂ IR window or glassy carbon (GC) electrode yielded two strong IR absorption bands around 1970 cm⁻¹ and 1910 cm⁻¹, which were assigned to IR absorption of CO bonded on asymmetric and symmetric bridge sites, respectively. Similar IR bands were observed in spectra of CO adsorbed on films, except the IR bands were much weak, whereas CO adsorbed on film produced an IR absorption band near 1906 cm⁻¹, and an anomalous IR absorption band whose direction has been completely inverted around 1956 cm⁻¹. The direction inversion of the IR band of CO bonded to asymmetric bridge sites on was ascribed to the interaction between Pd nanoparticles inside the aggregates. Based on FTIR spectroscopic and cyclic voltammetric results, the aggregation mechanism of Pd nanoparticles from to has been suggested that the agglomeration of Pd nanoparticles was driven by the alteration of electric field across electrode-electrolyte interface, when the PVP stabilizer was stripped via oxidation during cyclic voltammetry.     

A new method to determine the microbial kinetic parameters in biological air filters

This paper presents a new method to determine kinetic parameters of the biodegradation of various pollutants in a biofilter. Toluene, a readily biodegradable volatile organic compound, and methane, a hydrocarbon and a greenhouse gas, have been chosen as the target pollutants. The new protocol utilized biomass immobilized on bed pellets; these directly sampled from a continuous steady-state biofilter. The comparison of this method with the conventional experimental protocol utilizing micro-organisms suspended in a liquid medium was made using the pollutant toluene. Indeed, with both methods, the kinetic parameters have been evaluated by following the microbial growth in batch, thermostated reactors, using determined amounts of pollutant substrate. This experiment has confirmed the pertinence of the new procedure. The interesting features of the new method are that: (1) it is easy to operate (no preliminary treatment of the bed samples) and (2) it provides reproducible parameters that represent the real biofilter case more adequately than liquid cultures. In addition, modeling of the experimental specific growth rates in the case of toluene has shown that the values obtained with the use of solid extracts can be correlated by a Haldane's formulation, where , , and . The maximum specific growth rate was reached for an initial concentration of toluene near . The determination of the experimental specific growth rates of micro-organisms in the methane biofilter has also been performed. This study allowed highlighting two methane concentrations’ ranges: from 1000 to 14 500 ppmv and from 14 500 to 27 000 ppmv. For the first range, the Monod model proves to be suitable with the kinetic parameters: and . For the second range, neither the Monod nor the Haldane's formulation could directly be used. However, a mathematical adjustment of the Monod model allows to find kinetic parameters and . The biomass yields for the tested methane concentrations have also been determined and showed two different tendencies, depending on the same two ranges. For the first range of methane concentrations, the biomass yield was quite constant with an average value around while for the second range, it could be approached by a polynomial second-order regression. The maximum value of the biomass yield obtained on the second range was at a methane initial concentration of 20 000 ppmv.     

Influence of carbon dioxide partial pressure and fluidization velocity on activated carbons prepared from scrap car tyre in a fluidized bed

The effect of carbon dioxide partial pressure and fluidization velocity on activated carbons produced by carbon dioxide activation of scrap car tyre rubber in a fluidized bed has been studied. The method consisted of carbonization at under nitrogen followed by activation at . Three types of activated carbons were produced using activated gas concentrations of 20, 60 and 100% carbon dioxide by volume, the rest nitrogen, at a constant fluidization velocity (0.0393 m/s) to investigate the influence of carbon dioxide partial pressure. Within the experimental setup and activation time of 4 h, it was observed that BET surface area and total pore volume increased with carbon dioxide partial pressure reaching and , respectively, for 100% activation with carbon dioxide. Three other types of activated carbons were produced using 100% carbon dioxide at two (0.0393 m/s), three (0.0589 m/s) and four (0.0786 m/s) times the minimum fluidization velocity (U_mf). The BET surface area and total pore volume were observed to increase with fluidization velocity (which can be viewed as an indicator of the intensity of mixing in the bed), reaching and , respectively, at four times the minimum fluidization velocity.     

Synthesis, characterization and thermodynamic properties of poly(3-mesityl-2-hydroxypropyl methacrylate-co-N-vinyl-2-pyrrolidone)

Poly(3-mesityl-2-hydroxypropyl methacrylate-co-N-vinyl-2-pyrrolidone) P(MHPMA-co-VP) was synthesized in 1, 4-dioxane solution using benzoyl peroxide (BPO) as initiator at 60 °C. The copolymer was characterized by ¹H ¹³C NMR, FT-IR, DSC, TGA, size exclusion chromatography analysis (SEC) and elemental analysis techniques. According to SEC, the number-average molecular weight (M_n), weight-average molecular weight (M_w) and polydispersity index (PDI) values of PMHPMA-co-VP were found to be 58,000, 481,000 g/mol and 8.26, respectively. According to TGA, carbonaceous residue value of PMHPMA-co-VP was found to be 6% at 500 °C. Also, some thermodynamic properties of PMHPMA-co-VP such as the adsorption enthalpy, ΔH_a, molar evaporation enthalpy, ΔH_v, the sorption enthalpy, , sorption free energy, , sorption entropy, , the partial molar free energy, , the partial molar heat of mixing, , at infinite dilution was determined for the interactions of PMHPMA-co-VP with selected alcohols and alkanes by inverse gas chromatography (IGC) method in the temperature range of 323-463 K. According to the specific retention volumes, , the weight fraction activity coefficients of solute probes at infinite dilution, , and Flory-Huggins interaction parameters, between PMHPMA-co-VP-solvents were determined in 413-453 K. According to and , selected alcohols and alkanes were found to be non-solvent for PMHPMA-co-VP at 413-453 K. The glass transition temperature, T_g, of the PMHPMA-co-VP found to be 370 and 363 K, respectively, by IGC and DSC techniques, respectively.     

Observation and modelling of capillary flow occlusion resulting from the capture of superparamagnetic nanoparticles in a magnetic field

The magnetic field mediated capture of 10 nm diameter superparamagnetic nanoparticles, in the form of agglomerates of mean diameter 330 and 580 nm, from microcapillary flows has been observed and modelled. The steady state thickness of the captured layer in microcapillaries of diameter 400- could be predicted for both the 330 and the 580 nm diameter agglomerates at flow rates of between 0.1 and . The model provides insight into blockage formation at a constant flow rate as a precursor to the prediction of thrombotic embolism in magnetic directed therapies. Capillary constriction was particularly acute for the 580 nm agglomerates in large microcapillaries with flow rates of . From this model, agglomerates of diameter 330 nm or less offer the potential for minimal microcapillary occlusion in a range of flow rates.     

Anodic behaviour of zinc in methanol solutions of lithium perchlorate

Anodic dissolution of poly- and single-crystals of zinc was performed in methanol solution of lithium perchlorate by means of cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). The mechanism of anodic dissolution of zinc in organic solvents occurs in two oxidation steps. It is the first step that surface anodic product is created. Stability of the surface product is much better in anhydrous organic environments than in aqueous media; because the product is stable, a barrier layer composed of is formed at low anodic overvoltage. The formation of the layer is much stronger on the low index than on the high-index plane (0 0 0 1), where the adsorption of anodic product is more difficult.     

Kinetics and equilibrium of dissolved oxygen adsorption on activated carbon

The macroscopic adsorption behavior of dissolved oxygen on a coconut shell-derived granular activated carbon has been studied in batch mode at 301 and 313 K for initial dissolved oxygen concentrations of 10-30 mg/l and oxygen/carbon ratios of 2-180 mg/g. BET (Brunauer, Emmett, and Teller) surface area, micropore volume, and pore size distribution were determined from N₂ isotherm data for fresh and used samples of carbon. The surface groups were characterized using Boehm titrations, potentiometric titrations, and FTIR study. The material is characterized by its high specific surface area , microporocity (micropore volume ), its basic character ( total basic groups) and its high iron content (15,480 ppm Fe). BET n-layer isotherm describes adsorption equilibrium suggesting cooperative adsorption and important adsorbate-adsorbate interactions. Kinetic data suggest a process dependent on surface coverage. At low coverage a Fickian, intraparticle diffusion rate model assuming a local equilibrium isotherm (oxygen dissociation reaction) adequately describes the process. The calculated diffusion coefficients (D) vary between and for initial oxygen concentration of 10 and 20 mg/l, respectively. Sensitivity analysis shows that the oxygen dissociation equilibrium constant determines the equilibrium concentration, whereas the diffusion coefficient controls the kinetic rate of the adsorption process having no effect at the final equilibrium concentration. A combined kinetic mass transfer model with concentration-dependent diffusion (parabolic form) has been developed and successfully applied on the dissolved oxygen adsorption system at high surface coverage. For equilibrium uptake of the estimated mean mass transfer coefficient and adsorption rate constant are and , respectively.     

Kinetic modelling of VOC catalytic steam pyrolysis for tar abatement phenomena in gasification/pyrolysis technologies

Tar elimination and hot-gas conditioning in thermochemical conversion processes, i.e. thermal gasification, pyrolysis of heterogeneous materials involved two main classes of catalysts and/or additives: metallic and mineral oxides. This communication focused on the experimental kinetic data on catalytic steam cracking of vaporized toluene ( space-time ) as a tar-derived species and/or Volatile Organic Compound (VOC). Toluene (C₇H₈) has been chosen as a model formula for reactive tar-derived one-ring species determined from tar constituents. Gaseous product distribution data were obtained at atmospheric pressure steam pyrolysis temperature range of 923-1223 K and GHSV 1200-2300 Nm³ (m³ h)⁻¹. The overall catalytic pyrolysis of toluene over a commercial available metal based catalyst NiMo/γ-Al₂O₃ was compared to the pyrolysis in presence of basic non-metallic mineral additives, i.e. Norwegian (Norsk Hydro) dolomitic magnesium oxide [MgO], Swedish low surface quicklime [CaO], and calcined dolomite [CaMg(O)₂]. The operational conditions were applied without internal or external mass-transfer limitations. Kinetics for the pyrolysis could be described by first-order reactions for all the studied additives. The influence of hydrogen gas (30 vol%, ) and water vapor () in vaporized toluene cracking runs over low surface quicklime [CaO] was determined. A mechanistic model of the Langmuir-Hinshelwood type describing toluene decomposition was also developed.     

Electrochemical performances of gel polymer electrolytes using tetra(ethylene glycol) diacrylate

A gel polymer electrolyte (GPE) was prepared using tetra(ethylene glycol) diacrylate monomer, benzoyl peroxide, and (). The LiCoO₂/GPE/graphite cells were prepared and their electrochemical properties were evaluated at various current densities and temperatures.The viscosity of the precursor containing the tetra(ethylene glycol) diacrylate monomer was around . The ionic conductivity of the gel polymer electrolyte at 20°C was around . The gel polymer electrolyte had good electrochemical stability up to vs. Li/Li⁺. The capacity of the LiCoO₂/GPE/graphite cell at rate was 63% of the discharge capacity at rate. The capacity of the cell at −10°C was 81% of the discharge capacity at 20°C. Discharge capacity of the cell with gel polymer electrolyte was stable with charge-discharge cycling.     

Characterization of anion diffusion in polymer hydrogels used for wastewater remediation

Ion exchange systems for the removal of nutrient pollutants, even at extremely low concentrations, from wastewater effluents are a major environmental need. This work reports on the features of batch sorption processes for the ultimate removal and recovery of reactive phosphorus, nitrogen, and sulfur anions from aquaculture production wastewater effluents. The sorbent used was a crosslinked polyamine (PAA·HCl) polymeric hydrogel. The PAA·HCl hydrogels were prepared by chemically crosslinking aqueous solutions of linear PAA·HCl chains with epichlorohydrin (EPI). The nutrient anion binding capacity of the gels was studied as a function of various processing parameters. Lab scale batch and experiments showed maximum anion removal, from aquaculture wastewater, with regard to by 99%, by 70%, and by 95%. diffusivities of 16, 10, and 8×10⁻⁶ cm²/s were measured at pH levels of 5.5, 7.0, and 8.5.     

Carbon dioxide absorption with aqueous potassium carbonate promoted by piperazine

Many commercial processes for the removal of carbon dioxide from high-pressure gases use aqueous potassium carbonate systems promoted by secondary amines. This paper presents thermodynamic and kinetic data for aqueous potassium carbonate promoted by piperazine. Research has been performed at typical absorber conditions for the removal of CO₂ from flue gas.Piperazine, used as an additive in 20- potassium carbonate, was investigated in a wetted-wall column using a concentration of at 40-80°C. The addition of piperazine to a potassium carbonate system decreases the CO₂ equilibrium partial pressure by approximately 85% at intermediate CO₂ loading. The distribution of piperazine species in the solution was determined by proton NMR. Using the speciation data and relevant equilibrium constants, a model was developed to predict system speciation and equilibrium.The addition of piperazine to potassium carbonate increases the rate of CO₂ absorption by an order of magnitude at 60°C. The rate of CO₂ absorption in the promoted solution compares favorably to that of MEA. The addition of piperazine to potassium carbonate increases the heat of absorption from 3.7 to . The capacity ranges from 0.4 to for PZ/K₂CO₃ solutions, comparing favorably with other amines.     

Influence of reaction parameters on the synthesis of hyperbranched polymers via reversible addition fragmentation chain transfer (RAFT) polymerization

The synthesis of hyperbranched poly(methyl methacrylate) (PMMA) via reversible addition fragmentation chain transfer (RAFT) polymerization was investigated by varying the ratio chain transfer agent (CTA): monomer (methyl methacrylate, MMA): brancher (ethylene glycol dimethyl methacrylate, EGDMA): free radical initiator (AIBN) at various temperatures (50, 55, 60, 65, 70 °C). The rate of polymerization was observed to increase with temperature and concentration in brancher, whilst it was lowered by an increase in chain transfer agent concentration. The molecular weight of the samples increased with the ratios brancher: CTA and monomer: CTA. The polydispersity of the samples increase with conversion, as the level of branching increases. At fixed concentration in brancher, an increase of CTA concentration led to polymers with lower PDI. The variation of enthalpy and entropy relative to the monomer reaction were calculated, and it was observed that an increase in the brancher concentration induced an increase in both and , whilst lower CTA concentrations led to an increase in . The variation in Gibbs energy for the monomer reaction was calculated at 60 °C, and results confirmed the presence of a retardation effect when increasing CTA concentration generally observed in RAFT polymerization.     

Inhibition of mild steel corrosion in hydrochloric acid solution by triazole derivatives: Part II: Time and temperature effects and thermodynamic treatments

The corrosion behaviour of mild steel in 0.1 M HCl solution without and with 5-amino-1,2,4-triazole (5-ATA), 5-amino-3-mercapto-1,2,4-triazole (5-AMT), 5-amino-3-methylthio-1,2,4-triazole (5-AMeTT) or 1-amino-3-methylthio-1,2,4-triazole (1-AMeTT) was studied as a function of the immersion time and the solution temperature. Potentiodynamic polarization and electrochemical impedance spectroscopy (EIS) techniques were used in this study. Results obtained showed that the inhibition efficiency (IE%) increases with increasing the immersion time reaching its maximum value after 1 h, IE% slightly decreased and subsisted at reasonable values at least during the studied 20 h. The adsorptive behaviour of the investigated inhibitors on the steel surface followed Langmiur-type isotherm. Increasing temperature was found to greatly enhance IE% till arriving plateau at about 80% for 5-ATA and more than 90% for the other compounds between 323 and 348 °K. The polarization and impedance measurements were in good agreement. These results indicate the suitability of the use of the investigated inhibitors in the cooling systems. The plots of lnK versus 1/T for the four studied inhibitors showed non-linear behaviour. The standard enthalpy, , entropy, and free energy changes of adsorption were evaluated using a proposed quadratic equation based on an inverse square dependence of the heat capacity on temperature. The calculated values of were negative while those for and were positive. The values of the three thermodynamic functions of adsorption for the four investigated inhibitors were decreased with increasing the solution temperature. All the above results are suggestive of chemisorption of inhibitor molecules on the steel surface.     

Study of limestone particle impact attrition

Impact attrition of limestone particles was investigated at temperatures from 25 to and 1 atm pressure. Impacts changed the particle size distribution and mean particle diameter significantly for conveying gas velocities of 20-100 m/s. With increasing temperature less attrition occurred due to a decrease in particle impact velocity and an increase in the threshold particle impact velocity. The activation energy for impact attrition was . The mean limestone particle diameter decreased with increasing number of impacts and increasing impact velocity. Two empirical equations give good agreement with the experiments. Based on the experimental observations and correlations, an impact mechanism is suggested, where the area of new surface generated is proportional to the total kinetic energy consumed, to the number of impact cycles and an exponential decrease with temperature. When particles break, each particle generally splits into 2-3 daughter particles. The threshold particle velocities for breaking limestone particles were found to be at , similar to the reported literature values.