Influence of initial oxygen on the formation of thiol layers

In this study, X-ray photoelectron spectroscopy (XPS) has been used to study thin organic films. For comparison, monolayers were formed on clean and air-exposed metal substrates. Obtained results show that thiols remove contamination oxygen from gold, silver, platinum and copper surfaces. The tightly packed thiolate layers can be formed. In addition, oxygen does not take part in the final bonding of molecules to the surfaces.     

Effect of illumination on magnetization and microwave absorption of La1−xCaxMnO3 (x<0.2) films

Light-induced changes of the hysteresis loops of magnetization and microwave absorption are investigated in low-doped La_1−xCa_xMnO₃ (x<0.2) thin films. The width of the hysteresis loops decreases clearly under illumination with visible or near-infrared light at temperatures below 50 K. The microwave conductivity has a minimum value at magnetic fields corresponding to the magnetization reversal and is shifted towards weaker fields under illumination. These effects show complex nonexponential time evolution and dependence on strength of the magnetic field. The results can be explained by assuming that small ferromagnetic metallic regions exist within the insulating ferromagnetic phase of the sample, and that these regions are expanded by optically induced charge transfer between Jahn–Teller split e_g states of neighboring Mn³⁺ ions. Decrease of the Mn³⁺ XPS core level spectrum is observed in the samples under illumination with a HeNe laser.     

Aqueous dispersion, surface thiolation, and direct self-assembly of carbon nanotubes on gold

We report the efficient aqueous dispersion of pristine HiPco single-walled carbon nanotubes (SWNTs) with ionic liquid (IL)-based surfactants 1-dodecyl-3-methylimidazolium bromide (1) and 1-(12-mercaptododecyl)-3-methylimidazolium bromide (2), the thiolation of nanotube sidewalls with 2, and the controlled self-assembly of positively charged SWNT-1,2 composites on gold. Optical absorption spectra and resonance Raman (RR) data of obtained aqueous SWNT-1,2 dispersions are consistent with debundled and noncovalently functionalized nanotubes whose electronic properties have not been disturbed. Additionally, the dispersion of pristine nanotube material with surfactants 1 and 2 leads to a high degree of purification from carbonaceous particles. The chiralities of the 14 smallest semiconducting HiPco SWNTs in resonance with Raman excitation at 1064 nm (1.165 eV) were determined in SWNT-2 aqueous dispersion using UV-vis-NIR and RR spectra. X-ray photoelectron spectroscopy (XPS) and surface-enhanced resonance Raman scattering (SERRS) spectroscopy of SWNT-2 submonolayers on gold verified the encapsulation of individualized SWNTs with IL surfactants, the cleavage of S-S disulfide bonds formed in aqueous SWNT-2 suspensions, and the direct chemisorption of the SWNT-2 composite on bare gold via the Au-S bond. Aqueous dispersions of SWNTs with IL-based surfactants add biofunctionality to carbon nanotubes by imparting the positive surface charge necessary for interactions with cell membranes. Our technique, which purifies pristine nanotube material and produces water-soluble, positively charged nanotubes with pendent surface-active thiol groups, may also be translated to other carbon nanotubes and carbon nanostructures. Self-assembled, positively charged submonolayers of SWNTs can be further used for applications in cell biology and sensor technology.     

Layer-by-layer electrostatic self-assembly of single-wall carbon nanotube polyelectrolytes

We have used anionic and cationic single-wall carbon nanotube polyelectrolytes (SWNT-PEs), prepared by the noncovalent adsorption of ionic naphthalene or pyrene derivatives on nanotube sidewalls, for the layer-by-layer self-assembly to prepare multilayers from carbon nanotubes with polycations, such as poly(diallyldimethylammonium) or poly(allylamine hydrochloride) (PDADMA or PAH, respectively), and polyanions (poly(styrenesulfonate), PSS). This is a general and powerful technique for the fabrication of thin carbon nanotube films of arbitrary composition and architecture and allows also an easy preparation of all-SWNT (SWNT/SWNT) multilayers. The multilayers were characterized with vis-near-IR spectroscopy, X-ray photoelectron spectroscopy (XPS), surface plasmon resonance (SPR) measurements, atomic force microscopy (AFM), and imaging ellipsometry. The charge compensation in multilayers is mainly intrinsic, which shows the electrostatic nature of the self-assembly process. The multilayer growth is linear after the initial layers, and in SWNT/polyelectrolyte films it can be greatly accelerated by increasing the ionic strength in the SWNT solution. However, SWNT/SWNT multilayers are much more inert to the effect of added electrolyte. In SWNT/SWNT multilayers, the adsorption results in the deposition of 1-3 theoretical nanotube monolayers per adsorbed layer, whereas the nominal SWNT layer thickness is 2-3 times higher in SWNT/polyelectrolyte films prepared with added electrolyte. AFM images show that the multilayers contain a random network of nanotube bundles lying on the surface. Flexible polyelectrolytes (e.g., PDADMA, PSS) probably surround the nanotubes and bind them together. On macroscopic scale, the surface roughness of the multilayers depends on the components and increases with the film thickness.     

XPS and SEM study of calcite bearing rock powders in the case of reactivity measurement with HCl solution

The dissolution of seven natural limestones and calcareous rocks in hydrochloric acid solution was examined to investigate their capability for wet flue gas desulphurisation. All samples were crushed, ground and sieved to a size‐fraction of 150–250 µm. Thereafter they were subjected to a dissolution experiment utilising stepwise titration with hydrochloric acid. The dissolution rates of three calcareous rocks were found to be controlled by reaction kinetics, while the limestones showed mass transfer control. The surface characterisation was implemented before and after dissolution experiments using X‐ray photoelectron spectroscopy and scanning electron microscopy. Additional characterisation was carried out with X‐ray diffraction, X‐ray fluorescence and polarizing microscope. Initial reactivities have been shown to decrease in the order limestone, calcareous rock with high calcium concentration, calcareous rock with low calcium concentration. Coarse grain structure is proposed to decrease the initial reactivity. Copyright © 2011 John Wiley & Sons, Ltd.     

Characterisation of dolomites before and after reactivity measurement with HCl solution

The aim of this study was to compare different types of dolomites through batch reactivity experiments between HCl and dolomite powders, and ex‐situ characterisation of the particles before and after dissolution. Sedimentary dolomites were observed to have higher initial reactivities than metamorphic ones with sufficiently low calcite concentrations (<6% according to our regression model). In addition, the initial reactivities of the metamorphic dolomites were dependent on calcite concentration and could exceed those of the sedimentary dolomites. A regression model is presented for the dependence of initial reactivity on mineral composition and type of origin (sedimentary/metamorphic). The samples with the highest initial reactivities had also the largest BET (Brunauer, Emmet, Teller) surface areas obtained with nitrogen physisorption. Yet our data indicates that mineral composition of the dolomite has a greater influence on the initial reactivity than the BET surface area. Furthermore, it was found that the surface of sedimentary dolomites, unlike the surface of metamorphic dolomites, becomes porous during dissolution. Copyright © 2014 John Wiley & Sons, Ltd.     

Low-cost reduced graphene oxide-based conductometric nitrogen dioxide-sensitive sensor on paper

The fabrication concept for a low-cost sensor device using reduced graphene oxide (rGO) as the sensing material on a porous paper substrate is presented. The sensors were characterized using conductivity and capacitance measurements, atomic force microscopy and X-ray photoelectron spectroscopy. The effects of different reducing agents, graphene oxide (GO) flake size and film thickness were studied. The sensor was sensitive to NO₂, and devices based on a thin (10-nm) hydrazine-reduced GO layer had the best sensitivity, reaching a 70 % reduction in resistance after 10 min of exposure to 10 ppm NO₂. The sensitivity was high enough for the detection of sub-parts per million levels of NO₂. Desorption of gas molecules, i.e. the recovery of the sensor, could be accelerated by UV irradiation. The structure and preparation of the sensor are simple and up-scalable, allowing their fabrication in bulk quantities, and the fabrication concept can be applied to other materials, too.

Core level spectroscopy of MoS2

X-ray photoelectron spectroscopy has been used to study mineral molybdenite, MoS₂. The fitted core level spectra of sulphur 2p and molybdenum 3d states reveal several photon energy sensitive components. The high binding energy component in both spectra is proposed to originate from the uppermost sulphur or molybdenum atoms of an S–Mo–S sandwich layer of the hexagonal structure, respectively. The other features are suggested to be caused by the edge structures formed during the sample cleavage. The edge facets have much stronger chemical properties than the basal planes and they are known as the active sites of MoS₂ when it is used as a catalyst. The spectral features and the effect of the structure of UHV cleaved MoS₂ on them are discussed.