Controllable synthesis, characterization, and magnetic properties of nanoscale zerovalent iron with specific high Brunauer–Emmett–Teller surface area

This article reports a novel approach for the controllable synthesis of nanoscale zerovalent iron (NZVI) particles with specific high Brunauer–Emmett–Teller (BET) surface areas. Borohydride reduction is a primary and effective liquid phase reduction method for the synthesis of zerovalent iron nanoparticles. However, previous methods for synthesizing NZVI did not suggest a standard technique for controlling the size of particles during the synthesis process; in addition, previous literature generally reported that NZVI had a BET surface area of <37 m²/g. In this communication, a novel approach for the controllable synthesis of NZVI particles with specific high BET surface areas is presented. As a result, the BET surface areas of the NZVI particles synthesized increased to 47.49 and 62.48 m²/g, and the particle sizes decreased to 5–40 and 3–30 nm. Additionally, the physical and chemical properties of the synthesized NZVI particles were investigated by a series of characterizations, and magnetic analysis indicated that the synthesized NZVI particles had super-paramagnetic properties.     

Encapsulation of iron nanoparticles in alginate biopolymer for trichloroethylene remediation

Nanoscale zero-valent iron (NZVI) particles (10–90 nm) were encapsulated in biodegradable calcium-alginate capsules for the first time for application in environmental remediation. Encapsulation is expected to offers distinct advances over entrapment. Trichloroethylene (TCE) degradation was 89–91% in 2 h, and the reaction followed pseudo first order kinetics for encapsulated NZVI systems with an observed reaction rate constant (k _obs) of 1.92–3.23 × 10⁻² min⁻¹ and a surface normalized reaction rate constant (k _sa) of 1.02–1.72 × 10⁻³ L m⁻² min⁻¹. TCE degradation reaction rates for encapsulated and bare NZVI were similar indicating no adverse affects of encapsulation on degradation kinetics. The shelf-life of encapsulated NZVI was found to be four months with little decrease in TCE removal efficiency.     

Low temperature CO induced growth of Pd supported on a monolayer silica film

Nucleation, growth and sintering of Pd deposited on an ultra-thin silica film were studied by scanning tunneling microscopy and infrared reflection absorption spectroscopy. No preferential nucleation of Pd on the silica surface was observed both at 90 and 300 K deposition. When adsorbed on Pd clusters formed at 90 K, CO causes a strong sintering effect even at this temperature. The results are rationalized on the basis of a high mobility of Pd carbonyl-like species on the silica film. At a given Pd coverage, the extent of CO induced sintering cannot be achieved by annealing in vacuum. In addition, vacuum sintering, which commences above 700 K, goes simultaneously with interdiffusion of Pd and support.     

Fullerenes in molecular liquids. Solutions in “good” solvents: Another view

Brief review and update information concerning the state of “bare” (unmodified) fullerenes in different solvents, including organosols and hydrosols, is given. The hydrophobic nature of fullerene dispersions in aqueous media is discussed. The possibility of the existence of thermodynamic equilibrium in (fullerene + non-polar solvent) system is questioned. The modern data allow returning to the consideration of C₆₀ (C₇₀, etc.) molecules as colloidal (or sub-colloidal) species, inclined to aggregation. Recent publications support the idea of the solvophobic solvation of fullerene molecules even in “good” solvents. Hence, the solvophobic effect, in concert with the van-der-Waals attraction, seems to be driving forces of permanent (though sometimes very slow) aggregate formation, analogous to coagulation of nano-sized particles of common solvophobic colloidal systems.     

Impact of potassium on the heats of adsorption of adsorbed CO species on supported Pt particles by using the AEIR method

The heats of adsorption at several coverages of the linear and bridged CO species (denoted L and B, respectively) adsorbed on the Pt⁰ sites of the 2.9 wt% Pt/10% K/Al₂O₃ catalyst are determined using the Adsorption Equilibrium Infrared spectroscopy method. The addition of K on 2.9% Pt/Al₂O₃ modifies significantly the adsorption of CO on the Pt particles: (a) the ratio L/B is decreased from 8.4 to 1, (b) a new adsorbed CO species is detected with an IR band at 1763 cm⁻¹, (c) the heats of adsorption of L and B CO species are significantly altered and the positions of their IR bands are shifted. The heats of adsorption of L CO species are decreased: i.e. 206 and 105 kJ/mol at low coverages on Pt/Al₂O₃ and Pt/K/Al₂O₃ respectively. Two B CO species denoted B1 and B2, with different heats of adsorption are observed on Pt/K/Al₂O₃. The heats of adsorption of B2 CO species (major B CO species) are significantly larger than those measured in the absence of K: i.e. 94 and 160 kJ/mol at low coverages on Pt/Al₂O₃ and Pt/K/Al₂O₃ respectively, whereas those of B1 CO species (minor species) are similar: 90 kJ/mol at low coverages. These values are consistent with the qualitative High Resolution Electron Energy Loss Spectrometry literature data on Pt(1 1 1) modified by potassium.     

A novel ultrasound assisted method in synthesis of NZVI particles

This research is about a novel ultrasound assisted method for synthesis of nano zero valent iron particles (NZVI). The materials were characterized using TEM, FESEM, XRD, BET and acoustic PSA. The effect of ultrasonic power, precursor/reductant concentration (NaBH₄, FeSO₄·7H₂O) and delivery rate of NaBH₄ on NZVI characteristics were investigated. Under high ultrasonic power the morphology of nano particles changed from spherical type to plate and needle type. Also, when high precursor/reductant and high ultrasonic power was used the particle size of NZVI decreased. The surface area of NZVI particles synthesized by ultrasonic method was increased when compared by the other method. From the XRD patterns it was found also the crystallinity of particles was poor.     

The effect of preadsorbed K on the size distribution of Au nanoparticles on TiO2(1 1 0) surface

The effect of K on the morphology of Au nanoparticles deposited on TiO₂(1 1 0) surface is investigated by STM-STS and AES methods. For comparison, the enhanced concentration of oxygen defect sites generated by Ar⁺ bombardment was also studied. It was found that both the K additive and the oxygen defect sites induce a pronounced decrease in the average size of the Au nanoparticles evolved at 320 K. On the clean TiO₂(1 1 0) the average size of Au particles is 4.3 nm at approximately monolayer coverage of gold, while in the presence of K or oxygen vacancies this value decreased to 2.5 nm. In spite of the reduced average diameter detected at room temperature, the mean size of the Au nanoparticles increased significantly from 2.5 nm up to 7 nm on the effect of annealing at 500-700 K for K precoverages of 0.3-1 ML. For the clean and the Ar⁺ pretreated TiO₂(1 1 0) surfaces the mean size of the Au particles changed only slightly on the effect of the same thermal treatments.     

Fabrication of magnetic nickel–tungsten–phosphorus particles by electroless deposition

Nickel–tungsten–phosphorus (NiWP) particles with diameters ranging from 100 to 300 nm were fabricated by electroless deposition on silica particles and Au seeds. TEM, SEM equipped with EDX, and SQUID were employed to characterize these particles. It is found that 70 °C is sufficient to deposit NiWP particles, in contrast to 90 °C required for NiP or NiWP deposited on planar substrates. Magnetic properties of these particles are profoundly influenced by P-contents, whereas replacement of P with W changes the particles from paramagnetic to soft-ferromagnetic nature. Curie temperatures and saturation magnetization of these particles are around 300 K and from 0.1 to 20 emu/g, respectively.     

稳态荧光探针法研究槐糖脂生物表面活性剂的胶束化行为

应用稳态荧光探针法测定了非离子生物表面活性剂槐糖内脂临界胶束浓度(CMC)和胶束聚集数(N_agg),并考察了添加无机电解质和短链脂肪醇对槐糖内酯CMC的影响。结果表明,槐糖内酯的CMC为1.3×10-4 mol·L-1,并随加入电解质浓度的升高而略有降低,外加短链脂肪则使其CMC值升高;在4~8倍的CMC浓度范围内,槐糖内酯溶液N_agg随其浓度增大而增大,但胶束聚集数较小,为4~8个;激光纳米粒径结果显示槐糖内酯胶束动态直径较大且分布较为集中,平均约为90 nm。槐糖内酯胶束具有聚集数小而直径大的特点,表明该生物表面活性剂所形成的胶束排列较为松弛。     

Formation and characterization of Rh-Mo bimetallic layers on the TiO2(1 1 0) surface

The investigation of Rh, Mo and Rh-Mo nanosized clusters formed by physical vapor deposition on TiO₂(1 1 0) single crystal was performed by X-ray Photoelectron Spectroscopy (XPS), Low Energy Ion Scattering (LEIS) and Auger Electron Spectroscopy (AES). There was no sign for site-exchange between Mo and Rh atoms during deposition of Mo onto Rh particles at 330 K. Mixing between Ti and Mo ions was facilitated at the Mo particle-titania interface due to reaction at 550-700 K. The redox process between titania and Mo deposit was hindered at 330 K by forming predeposited rhodium layer (Θ_Rh = 2.0 ML), but reached nearly the same extent as without Rh after moderate heating to 600 K. The encapsulation of Rh by titania was complete by about 700 K in the presence of 1.2 ML Mo, in case of Mo-predeposition and Mo-postdeposition as well. Elevating the temperature of TiO₂/Rh-Mo layers above 700 K, these metals form alloy at the Mo-Rh interface irrespective of deposition sequences.     

Adsorption of CO and C2H4 on Rh-loaded thin-film dysprosium oxide

A dysprosium oxide thin film was deposited on Ru(0 0 0 1) by vapor depositing Dy in 2 × 10⁻⁷ torr O₂ while the Ru was at 700 K. The film was ca. 5 nm thick and produced a p(1.4 × 1.4) LEED pattern relative to the Ru(0 0 0 1) substrate. The adsorption and reaction of CO and C₂H₄ adsorbed on Rh supported on the Dy₂O₃ film were studied by TPD and SXPS. The CO initially reacted with loosely bound oxygen in the substrate to produce CO₂. After the loosely bound oxygen was removed, the CO adsorbed non-dissociatively in a manner similar to what is seen on Rh(1 1 1). C₂H₄ adsorbed on the Rh particles and underwent progressive dehydrogenation to produce H₂ during TPD. The C from the C₂H₄ reacted with the O in Dy₂O₃ to produce CO. CO dissociation on the Rh particles could be promoted by treating the Dy₂O₃ with C₂H₄ before CO exposure.     

Molecular and atomic oxygen adsorption on the kinked Pt(321) surface

Oxygen adsorption and desorption were characterized on the kinked Pt(321) surface using high resolution electron energy loss spectroscopy, thermal desorption spectroscopy and Auger electron spectroscopy. Some dissociation of molecular oxygen occurs even at 100 K on the (321) surface indicating that the activation barrier for dissociation is smaller on the Pt(321) surface than on the Pt(111) surface. Molecular oxygen can be adsorbed at 100 K but only in the presence of some adsorbed atomic oxygen. The dominance of the v(OO) molecular oxygen stretching mode in the 810 to 880 cm^?1 range indicates that the molecular oxygen adsorbs as a peroxo-like species with the OO axis parallel or nearly parallel to the surface, as observed previously on the Pt(111) surface [Gland et al., Surface Sci. 95 (1980) 587]. The existence of at least two types of peroxo-like molecular oxygen is suggested by both the unusual breadth of the v(OO) stretching mode and breadth of the molecular oxygen desorption peak. Atomic oxygen is adsorbed more strongly on the rough step sites than on the smooth (111) terraces, as indicated by the increased thermal stability of atomic oxygen adsorbed along the rough step sites. The two forms of adsorbed atomic oxygen can be easily distinguished by vibrational spectroscopy since oxygen adsorbed along the rough step sites causes a v(PtO) stretching mode at 560 cm^?1, while the v(PtO) stretching mode for atomic oxygen adsorbed on the (111) terraces appears at 490 cm^?1, a value typical of the (111) surface. Two desorption peaks are observed during atomic oxygen recombination and desorption from the Pt(321) surface. These desorption peaks do not correlate with the presence of the two types of adsorbed atomic oxygen. Rather, the first order low temperature peak is a result of the fact that about three times more atomic oxygen can be adsorbed on the Pt(321) surface than on the Pt(111) surface (where only a second order peak is observed). The heat of desorption for atomic oxygen decreases from about 290kJ/mol (70 kcal/mol) to about 196 kJ/mol (47 kcal/mol) with increasing coverage. Preliminary results concerning adsorption of molecular oxygen from the gas phase in an excited state are also briefly discussed.     

Colloidal behavior of goethite nanoparticles modified with humic acid and implications for aquifer reclamation

Nanosized colloids of iron oxide adsorb heavy metals, enhance the biodegradation of contaminants, and represent a promising technology to clean up contaminated aquifers. Goethite particles for aquifer reclamation were recently synthesized with a coating of humic acids to reduce aggregation. This study investigates the stability and the mobility in porous media of this material as a function of aqueous chemistry, and it identifies the best practices to maximize the efficacy of the related remediation. Humic acid-coated nanogoethite (hydrodynamic diameter ～90 nm) displays high stability in solutions of NaCl, consistent with effective electrosteric stabilization. However, particle aggregation is fast when calcium is present and, to a lesser extent, also in the presence of magnesium. This result is rationalized with complexation phenomena related to the interaction of divalent cations with humic acid, inducing rapid flocculation and sedimentation of the suspensions. The calcium dose, i.e., the amount of calcium ions with respect to solids in the dispersion, is the parameter governing stability. Therefore, more concentrated slurries may be more stable and mobile in the subsurface than dispersions of low particle concentration. Particle concentration during field injection should be thus chosen based on concentration and proportion of divalent cations in groundwater.

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Graphical abstract Goethite nanoparticles are used in contaminated site remediation. The particles are stable in monovalent ion solutions due to an adsorbed layer of humic acids. Above a threshold dose of divalent cations, particles aggregate and sediment. High particle/calcium ratios increase colloidal stability. Stability in suspension and transport in porous media correlate well. Delivery into subsurface can be improved by either increasing particle concentration or reducing divalent cation content in the carrier fluid.

     

Molecular statistical model for adsorbed membrane particles

Indirect membrane-mediated forces influence aggregation, segregation and freezing processes of large particles inserted into a membrane or adsorbed to its surface. Colloidal particles, polymers, peptides and proteins are the source of deformations of the lipid double layer. These perturbations cause membrane-mediated attractive or repulsive forces between the particles. A molecular statistical treatment is useful for investigating the lateral organization of peripheral and trans-membrane peptides. To describe aggregation and freezing phenomena a density functional, which includes conventional short-range forces and membrane-mediated effects, is proposed. The method is applied to an ensemble of adsorbed peptides. It is investigated how the elastic splay-distortion modulus, the surface tension, the compression-expansion modulus of the bilayer and the cross-section of adsorbed particles influence aggregation and freezing. Assuming conventional values for the material parameters, membrane-mediated attractive forces are found to be sufficiently strong to enforce aggregation.     

Magnetization scaling in the ruthenate-cuprate RuSr2Eu1.4Ce 0.6Cu2O10-δ (Ru-1222)

The magnetic properties of the superconducting ruthenate-cuprate RuSr₂Eu _1.4Ce_0.6Cu₂O_10-δ (Ru-1222) have been studied by a scaling analysis of the dc magnetization and ac susceptibility measurements. Non-linear M(H) curves reveal the presence of nano-size clusters with a net magnetic moment of ∼10² μ_B at 180 K, near the deviation from a Curie-Weiss behavior. On cooling, no scaling was observed down to 90 K, discarding the possibility of magnetic phase separation of collinear ferromagnetic particles. We explain this result in terms of a variable number of contributing particles, with a temperature dependent net magnetic moment. For 70 K ≤T≤ 90 K the scaling plots evidence the emergence of a system of non-interacting particles, which couple on further cooling. The observed cluster-glass features are preserved down to the lowest measured temperature (10 K); no signature of long-range order was detected. The frequency shift of the peak in the real part of the ac susceptibility does not follow the Vogel-Fulcher type dependence, as previously reported. The puzzling temperature dependence of the coercive field, H_C(T), is correlated with the changes in the scaling factors.     

Polarization and asymmetry of protons in an annihilation process e− + e+ → p + ¯p in the presence of weak neutral currents

The differential and total cross sections for annihilation of longitudinally polarized and transversely polarized electrons and positrons into pairs of longitudinally polarized protons and antiprotons are calculated in the center-of-mass system. The expressions obtained for the cross sections have electromagnetic, weak, and interference terms. It is shown that the existence of a weak current-current interaction (e) (¯pp) must lead for protons and antiprotons, emitted at an angle ®=90° to a nonzero degree of longitudinal polarization P(E) =1.3 and 36% for E=2.5 and 10 GeV and G=G_F=10^–5 M^–2,to the presence of forward-backward asymmetry in the angular distribution of the protons A(E)=1 and 12% for E=2.5 and 10 GeV (the asymmetry exists even when all the particles are unpolarized), and to other effects which are absent in the case of a pure electromagnetic interaction. It is shown that in experiments with polarized particles the contributions of different form factors can be distinguished and studied separately.Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 1, pp. 93–100, January, 1974.We thank the participants in the seminars of Professor A. A. Sokolov and Professor Ya. P. Terletskii for discussions of the work.     

Roughness influence on the sheet resistance of the PEDOT:PSS printed on paper

The use of paper as a platform to manufacture organic electronic devices, electronic paper, has expanding potential for many applications because of several properties offered. In this work, we show a study of PEDOT:PSS printed by inkjet on bond paper, vegetal paper and sheets of PET. The relation between the surface density of the deposited material, morphology and resistivity was investigated for samples printed with a commercial Hewlett-Packard(HP)^® printer and Microsoft Word^® software. The amount of material deposited, i.e. surface density, was controlled using the print number in the same position and changing the gray scale used in the image formation. Changing the surface density of printed PEDOT:PSS, it is possible to produce a continuous film permeating the papers fibers. Sheet resistances obtained, when 7.0 mg cm⁻² of PEDOT:PSS were deposited on the surfaces, were: (a) 413.2 kΩ/Sq for bond paper, (b) 5.6 kΩ/Sq for vegetable paper and (c) 2.3 kΩ/Sq for PET. The exponential dependence of sheet resistance with the surface density of printed material allows us to evaluate the strong influence of substrate roughness on PEDOT:PSS conductivity and to predict, for each one, conditions to minimize it.     

γ irradiation effect on the polarization and resistance of Li-Co-Yb-ferrite

The effect of γ irradiation on some physical properties of rare earth ferrite of the general formula Li_0.5+zCo_z Yb_xFe_2.5−2z−xO₄, (z=0.1, x=0.00, 0.025, 0.050, … , 0.200) is discussed. The temperature dependence of the polarization and resistance is studied in the range (300 K≤T≤700 K) at different frequencies (10 kHz≤f≤1 MHz). The relaxation time and the activation energy have been calculated before and after irradiation with γ rays doses of 1 and 3 Mrad. A comparison was made between the ac resistance before and after irradiation for the samples with (0.0≤x≤0.2). The results after irradiation with 1 Mrad γ rays showed that the resistance at the critical concentration decreases from 800 to 25 kΩ at room temperature. Furthermore, with increasing temperature the resistance ranged from R≈130 kΩ at T≈310 K to R≈0.13 kΩ at T≈640 K. Thus, it is possible to improve the conductivity of this type of rare earth ferrite materials to be used in technological applications at room as well as at high temperature.     

Aggregation modeling of calcium carbonate particles by Monte Carlo simulation

The mechanism on aggregation of spindle granular particles of calcite was investigated for the carbonation of calcium hydroxide in aqueous suspension for the purpose of controlling morphology of CaCO₃. The experimental carbonation process was carried out in a semi-batch bubble column reactor under different conditions. Although, fine rhombic nano-particles diameter ranged from 100 to 200 nm were obtained at 291 K, a higher temperature of 300 K provided spindle granular particles with a length of 1.0–1.5 μm and a width of 0.3–0.5 μm. The average crystallite size was 28 nm for the fine rhombic nano-particles and 43 nm for the spindle granules. Zeta potential measurement for the spindle granules indicated that the suspension tended to be aggregated during the carbonation process. The effect of the degree of particle aggregation on the shape of the obtained calcite particles was studied by Monte Carlo simulations. Our simulation results elucidated the dependence of aggregation on unit particles, i.e., primary particles, on the experiment carbonation condition where the spindle granules were formed out of the unit particles under the same condition as the experiments. In addition, the formation mechanism of the granules was investigated by applying classical nucleation theory to the present simulations.     

Studies on the Preparation of Magnetic Photocatalysts

A crystalline titanium dioxide coating was deposited onto silica insulated magnetite particles to prepare a stable magnetic photocatalyst. The direct deposition of crystalline titanium dioxide was conducted by aging dispersions of insulated magnetite particles in a titanium sol–gel precursor mixture at 60–90°C. The coating process was found to be influenced by pH, alkoxide precursor concentration, aging time and reaction temperature. A mechanism for the formation of the titanium dioxide coating has been proposed. The photocatalytic performance of the prepared particles was found to be related to the preparation conditions.