A Metatitanic Acid Particulate Xerogel: Green Synthesis, Structure Determination, and Detailed Characterization.

The manuscript focuses on an original method of preparation of metatitanic acid when only environmentally safe base substances are used in the synthesis process. The synthesis is based on the reaction of solid titanyl sulfate in an aqueous solution of sodium hydroxide. This method allows for (i) a full preservation of the morphology of the starting titanyl sulfate and (ii) a preparation of metatitanic acid substances with specific parameters. This can be achieved via a precise control of the alkali metal/titanyl sulfate ratio resulting in substances with varying contents of alkali metals or even sulfate anions. The prepared metatitanic acid then also contains very small weakly crystalline particles (2-3 nm) and forms pseudomorphic aggregates whose shape and dimensions correspond to those of the starting titanyl sulfate. These aggregates exhibit regular nanoporosity with a high surface area of up to 500 m2·g-1, have no tendency to form colloids, and are mechanically highly resistant even by high-energy ultrasound. The characterization of the resulting products is done via their chemical composition and methods of structural analysis, as well as by electron microscopy and local analysis. The mechanism of product formation is discussed based on the structure of the precursor, including the so far unknown structure of metatitanic acid.

Highly efficient eco-friendly sodium titanate sorbents of Cs(i), Sr(ii), Co(ii) and Eu(iii): synthesis, characterization and detailed adsorption study.

Development of useful all-around materials which can quickly and efficiently adsorb radionuclides in response to environmental radioactive contamination is an urgent research objective. In response to this need, our team developed a simple preparation method for stable sodium titanates which can serve as efficient agents for removal of radionuclides from water. With an emphasis on an environmentally friendly synthesis, the resulting materials were defined by a range of means and methods measuring e.g. pH, ionic strength, contact time or metal ion concentration in order to assess their potential for use and applications as sorbents. The data obtained from measurements revealed rapid removal kinetics (up to 10 minutes), wide range of pH use and high equilibrium capacity. The maximum amount of adsorbed ions as calculated from the Langmuir isotherm was equal to 206.3 mg g-1 for Cs(i), 60.0 mg g-1 for Sr(ii), 50.2 mg g-1 for Co(ii) and 103.4 mg g-1 for Eu(iii), significantly exceeding published data obtained with related materials. The removal mechanism is most likely ion exchange followed by complexation reactions, as indicated by TEM/EDS analyses. Given their extraordinary sorption capacity and facile synthesis under mild conditions, these materials are promising candidates for the efficient removal of radionuclides from aqueous solutions during the clean-up of radioactive pollution in the environment.

Removal of manganese by adsorption onto newly synthesized TiO2-based adsorbent during drinking water treatment.

Manganese is naturally present in water, but its increased concentration in potable water is undesirable for multiple reasons. This study investigates an alternative method of demanganization by a newly synthesized TiO2-based adsorbent prepared through the transformation of titanyl sulphate monohydrate to amorphous sodium titanate. Its adsorption capacity for Mn2+ was determined, while a range of influential factors, such as the effect of contact time, adsorbent dosage, pH value, and added ions was evaluated. The adsorbent appeared highly effective for Mn2+ removal owing to its unique characteristics. Besides adsorption via electrostatic interactions, ion-exchange was also involved in the Mn2+ removal. Although the Mn2+ removal occurred within the whole investigated pH range of 4-8, the maximum was achieved at pH 7, with qe = 73.83 mg g-1. Equilibrium data revealed a good correlation with Langmuir isotherm in the absence of any ions or in the presence of monovalent co-existing ions, while the results in the presence of divalent co-existing ions showed a better fit to Freundlich isotherm. Additionally, the presence of monovalent cations (Na+, K+) only slightly decreased the Mn2+ removal efficiency as compared to divalent cations (Ca2+, Mg2+) that caused a greater decrease; however, the effect of anions (Cl-, SO42-) was insignificant. To provide insight into the adsorbent safety, the toxicity assessment was performed and showed no harmful effect on cell activity. Furthermore, the residual concentration of titanium after adsorption was always below the detection limit. The results imply that the synthesized TiO2-based adsorbent is a safe promising alternative method for demanganization.Highlights The synthesis of amorphous TiO2-based adsorbent was presented.The TiO2-based adsorbent was found to be efficient for Mn2+ removal.The Mn2+ removal mechanisms were adsorption and ion-exchange.Increasing pH enhanced the efficiency of Mn2+ removal.Divalent cations decreased the Mn2+ removal efficiency more than monovalent cations.

Highly-efficient removal of Pb(ii), Cu(ii) and Cd(ii) from water by novel lithium, sodium and potassium titanate reusable microrods.

In this work, we report on the efficient removal of heavy metal ions with nanostructured lithium, sodium and potassium titanates from simulated wastewater. The titanates were obtained via a fast, easy and cost effective process based on extraction of sulfate ions from the crystals of titanyl sulfate and their replacement with hydroxyl groups of NaOH, LiOH and KOH solutions leaving the Ti-O framework intact. The as-prepared titanates were carefully examined by scanning and transmission electron microscopy. Furthermore, the effect of contact time, pH, annealing temperature, together with adsorption in real conditions including competitive adsorption and reusability were studied. It was found that the maximum adsorption capacity, as calculated from the Langmuir adsorption model, is up to 3.8 mmol Pb(ii) per g, 3.6 mmol Cu(ii) per g and 2.3 mmol Cd(ii) per g. Based on the characterization results, a possible mechanism for heavy metal removal was proposed. This work provides a very efficient, fast and convenient approach for exploring promising materials for water treatment.

High-aspect-ratio and high-flatness Cu3(SiGe) nanoplatelets prepared by chemical vapor deposition.

Cu3(SiGe) nanoplatelets were synthesized by low-pressure chemical vapor deposition of a SiH3C2H5/Ge2(CH3)6 mixture on a Cu-substrate at 500 degrees C, total pressure of 110-115 Pa, and Ge/Si molar ratio of 22. The nanoplatelets with composition Cu76Si15Ge12 are formed by the 4'-phase, and they are flattened perpendicular to the [001] direction. Their lateral dimensions reach several tens of micrometers in size, but they are only about 50 nm thick. Their surface is extremely flat, with measured root mean square roughness R(q) below 0.2 nm. The nanoplatelets grow via the non-catalytic vapor-solid mechanism and surface growth. In addition, nanowires and nanorods of various Cu-Si-Ge alloys were also obtained depending on the experimental conditions. Morphology of the resulting Cu-Si-Ge nanoobjects is very sensitive to the experimental parameters. The formation of nanoplatelets is associated with increased amount of Ge in the alloy.

From shelled Ge nanowires to SiC nanotubes.

Shelled germanium nanowires up to 100 nm in diameter and several micrometers in length were prepared by low pressure chemical vapor deposition (LPCVD) of tris(trimethylsilyl)germane (SiMe(3))(3)GeH. Vapors of the precursor were deposited on tantalum substrates in an oven at 365 degrees C. Subsequently, the products were annealed at 700 degrees C in vacuum. The wires consist of a crystalline Ge core surrounded by a two-layer jacket. The presence of hexagonal Ge in the core was documented in some of the nanowires. The inner jacket is formed by amorphous germanium, the outer part by an Si/C material. By annealing at 900 degrees C, germanium in the core is expelled and nanotubes formed by the Si/C material remain. The samples were studied by SEM, HRTEM, EDX, FTIR and Raman spectroscopy, and the XRD technique.

Magnetic susceptibility measurement of single iron/cobalt carbonyl microcrystal by atmospheric magnetophoresis.

In this study, the use of an innovative atmospheric magnetophoresis, which enables us to measure the mass magnetic susceptibility and mass of a microparticle simultaneously, was demonstrated. Using this technique, we determined the magnetic susceptibility of a crystalline deposit of iron/cobalt carbonyl, mainly composed of Fe2(CO)9, which was prepared photochemically from a gaseous mixture of iron pentacarbonyl (Fe(CO)5) and cobalt tricarbonyl nitrosyl (Co(CO)3NO). The mass magnetic susceptibility and the characteristic relaxation time of the microcrystal were (7.0±1.9)×10-9 m3 kg-1 and (5.6±2.2)×10-4 s, respectively. The observed magnetic susceptibility shows that the microparticle was paramagnetic. Assuming that the density was equal to that of Fe2(CO)9 (2.1×103 kg m-3) and that the shape of the particle was spherical, a hydrodynamic radius of 4.7 µm and a mass of 0.91 ng were observed. It was suggested that Co was incorporated in Fe2(CO)9.

Carboranethiol-modified gold surfaces. A study and comparison of modified cluster and flat surfaces.

Four different carboranethiol derivatives were used to modify the surfaces of gold nanoparticles and flat gold films. The novel materials engendered from these modifications are extraordinarily stable species with surfaces that support self-assembled monolayers of 1-(HS)-1,2-C2B10H11, 1,2-(HS)2-1,2-C2B10H10, 1,12-(HS)2-1,12-C2B10H10, and 9,12-(HS)2-1,2-C2B10H10, respectively. Surprisingly, characterization of these materials revealed that a number of molecules of the carboranethiol derivatives are incorporated inside the nanoparticles. This structural feature was studied using a number of techniques, including X-ray photoelectron spectroscopy (XPS), UV-vis, and IR spectroscopies. Thermal desorption experiments show that carborane molecules detach and leave the nanoparticle surface mostly as 1,2-C2B10H10 isotopic clusters, leaving sulfur atoms bound to the gold surface. The surfaces of both the gold nanoparticles and the flat gold films are densely packed with carboranethiolate units. One carborane cluster molecule occupies an area of six to seven surface gold atoms of the nanoparticle and eight surface gold atoms of the flat film. XPS data showed that molecules of 1,12-(HS)2-1,12-C2B10H10 bind to the flat gold surface with only half of the thiol groups due to the steric demands of the icosahedral carborane skeleton. Electrochemical measurements indicate complete coverage of the modified gold surfaces with the carboranethiol molecules.