Ammonia adsorption and decomposition on silica supported Rh nanoparticles observed by in situ attenuated total reflection infrared spectroscopy

Attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR) is applied to study NH₃, adsorbed from the gas phase, and its decomposition products, i.e. NH_x species, on Rh nanoparticles, produced by spincoating from a RhCl₃ solution in water followed by reduction. A silicon ATR crystal with a hydroxilated SiO₂ layer acts as the support for the nanoparticles. Upon exposure to NH₃ in the vacuum chamber, NH₃ adsorbed to both silica and Rh is detected (sensitivity ∼5 × 10⁻⁵ absorbance units). Interaction of the NH₃ with the silica OH groups is observed around ∼2840 cm⁻¹ in combination with peaks showing the disappearance of unperturbed OH vibrations between 3500 and 3700 cm⁻¹. In addition, NH bend vibrations at 1634 cm⁻¹ and NH stretch vibrations at 3065 and 3197 cm⁻¹ are observed for substrate temperatures between 20 and 100 °C. The latter two correspond to NH on Rh, as verified with a sample without Rh, and probably correspond to undecomposed NH₃. Moreover, they remain after evacuation, suggesting strongly bound species. For a substrate temperature of 75 and 100 °C, additional NH stretch peaks at 3354 and 3283 cm⁻¹ are observed, possibly due to NH₂ intermediates, indicating NH₃ decomposition. It is shown that ATR-FTIR can contribute to the sensitive detection of adsorption and decomposition of gaseous species on realistic planar model catalysts.     

Textural and electronic characteristics of mechanochemically activated composites with nanosilica and activated carbon

Nanosilicas (A-50, A-300, A-500)/activated carbon (AC, S_BET = 1520 m²/g) composites were prepared using short-term (5 min) mechanochemical activation (MCA) of powder mixtures in a microbreaker. Smaller silica nanoparticles of A-500 (average diameter d_av = 5.5 nm) can more easily penetrate into broad mesopores and macropores of AC microparticles than larger nanoparticles of A-50 (d_av = 52.4 nm) or A-300 (d_av = 8.1 nm). After MCA of silica/AC, nanopores of non-broken AC nanoparticles remained accessible for adsorbed N₂ molecules. According to ultra-soft X-ray emission spectra (USXES), MCA of silica/AC caused formation of chemical bonds Si-O-C; however, Si-C and Si-Si bonds were practically not formed. A decrease in intensity of OK_α band in respect to CK_α band of silica/AC composites with diminishing sizes of silica nanoparticles is due to both changes in the surface structure of particles and penetration of a greater number of silica nanoparticles into broad pores of AC microparticles and restriction of penetration depth of exciting electron beam into the AC particles.     

Characterization of Cr/SiO2 catalysts and ethylene polymerization by XPS

Cr/SiO₂ catalysts with 1 or 3 wt.% Cr loadings and different chromium precursors were characterized by X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD). A method to determine chromium species in the sample was developed through the decomposition of the Cr 2p XPS spectrum in Cr⁶⁺ and Cr³⁺ standard spectra. The results of the binding energy from the Cr 2p region and of the distribution of chromium species allowed to evaluate the dynamic photo-reduction of the surface chromium species during XPS analysis. Photo-reduction of surface Cr⁶⁺ to Cr³⁺ species was verified for all samples supported in silica, depending on the precursor and chromium content. Bulk CrO₃ and Cr₂O₃ standards did not reveal variation in the binding energy of Cr 2p_3/2, but a physical mixture of CrO₃ with SiO₂ presented photo-reduction. The behavior of this mixture resembled to the catalysts and suggests the participation of the surface hydroxyls of silica in the photo-reduction process. XPS intensity measurements for assessing dispersion of chromium oxide were used to compare the calcined and reduced catalysts to different chromium precursors. Polyethylene chains were detected by in situ XPS, while oligomerization products were not observed.     

Adsorption performance and mechanism of 2,4,6-trinitrotoluene on a novel adsorption material polyvinylbenzyl acid/SiO2

Polyvinylbenzene (PVB, namely polystyrene, PSt) was grafted on the surface of silica gel particles by “grafting from” in solution polymerization system, and grafting particles PVB/SiO₂ were obtained. The chloromethylation reaction of the grafted polyvinylbenzene was performed using a novel chloromethylation reagent, 1,4-bis (chloromethyoxy) butane that is un-carcinogenic, and grafting particles CMPVB/SiO₂ were obtained. Subsequently, chloromethyl groups on grafting particles CMPVB/SiO₂ were hydrolyzed and oxidized, and finally adsorption material polyvinylbenzyl acid/SiO₂ (PVBA/SiO₂) was prepared. The adsorption performances and mechanism of 2,4,6-trinitrotoluene (TNT) on PVBA/SiO₂ were investigated through static methods. The experimental results showed that PVBA/SiO₂ possessed strong adsorption ability for TNT with adsorption amount of 26.84 mg g⁻¹. The empirical Freundlich isotherm was also found to agree well with the equilibrium adsorption data. In addition, pH was found to have great influence on the adsorption amount. Finally, PVBA/SiO₂ was observed to possess excellent reusability as well.     

Fine structure on the excitonic emission in AgI nanoparticles embedded in silica glass

Stable photoluminescence (PL) from AgI nanoparticles embedded in silica glass was investigated at room temperature. The Z_1,2 excitonic emission of AgI exhibits fine structure with spacing of ∼0.20 eV (1610 cm⁻¹), which is assigned to the frequency of vibration in interfacial water species. The PL excitation spectrum displays two newly observed bands at 3.45 and 4.35 eV associated with AgI-silica interaction. We suggest that the excitons in AgI are localized in the AgI/SiO₂ interface region before radiative recombination.     

Synthesis of magnetic hollow silica using polystyrene bead as a template

In this paper, we report a new route to synthesize novel magnetic hollow silica nanospheres (MHSNs) using polystyrene particles as sacrificial templates, and TEOS and Fe₃O₄ as precursors. TEM, EDS, XRD, and SQUID were applied to characterize MHSNs. TEM and EDS results show that the MHSNs consist of about 200 nm of hollow cores and ∼35 nm shells with ∼10 nm of Fe₃O₄ nanoparticles embedded. The polystyrene beads were successfully removed by immersing the as-prepared silica nanocomposite in a toluene solution. XRD results demonstrate that the Fe₃O₄ magnetic nanoparticles still keep spinel structure even heated at low temperature. The surface status of the polystyrene beads and Fe₃O₄ nanoparticles has an important effect on the formation of the MHSNs. The MHSNs present a superparamagnetism at room temperature by SQUID measurement. The MHSNs have potential applications in biosystem and nanomedicine.     

Effect of charged deep states in hydrogenated amorphous silicon on the behavior of iron oxides nanoparticles deposited on its surface

Langmuir-Blodgett technique has been used for the deposition of ordered two-dimensional arrays of iron oxides (Fe₃O₄/Fe₂O₃) nanoparticles onto the photovoltaic hydrogenated amorphous silicon (a-Si:H) thin film. Electric field at the a-Si:H/iron oxides nanoparticles interface was directly in the electrochemical cell modified by light soaking and bias voltage (negative or positive) pretreatment resulting in the change of the dominant type of charged deep states in the a-Si:H layer. Induced reversible changes in the nanoparticle redox behavior have been observed. We suggest two possible explanations of the data obtained, both of them are needed to describe measured electrochemical signals. The first one consists in the electrocatalytical effect caused by the defect states (negatively or positively charged) in the a-Si:H layer. The second one consists in the possibility to manipulate the nanoparticle cores in the prepared structure immersed in aqueous solution via the laser irradiation under specific bias voltage. In this case, the nanoparticle cores are assumed to be covered with surface clusters of heterovalent complexes created onto the surface regions with prevailing ferrous or ferric valency. Immersed in the high viscosity surrounding composed of the wet organic nanoparticle envelope these cores are able to perform a field-assisted pivotal motion. The local electric field induced by the deep states in the a-Si:H layer stabilizes their “orientation ordering” in an energetically favourable position.     

The roles of the exchange and dipole couplings on the magnetoresistance for the nanoparticle arrays

Based on Monte Carlo simulations and resistor network model, the tunneling magnetoresistance (TMR) for the square anisotropic magnetic nanoparticle arrays with the exchange coupling J and dipolar coupling D has been studied. The simulated results reveal that, the coercivity H_c increases with decreasing value of D and increasing magnitude of J; the value of TMR_max decreases with enhancing value of J; for D<0.1, the value of TMR_max decreases with increasing value of D, while in contrast for D>0.1, it increases with increasing value of D. Those behaviours have been interpreted with the competition of the different energies, including the random anisotropy, exchange and dipolar energies.     

Luminescent characteristics of CaTiO3:Pr thin films prepared by pulsed laser deposition method with various substrates

CaTiO₃:Pr³⁺ films were deposited on different substrates such as Al₂O₃ (0 0 0 1), Si (1 0 0), MgO (1 0 0), and fused silica using pulsed laser deposition method. The crystallinity and surface morphology of these films were investigated by XRD and SEM measurements. The films grown on the different substrates have different crystallinity and morphology. The FWHM of (2 0 0) peak are 0.18, 0.25, 0.28, and 0.30 for Al₂O₃ (0 0 0 1), Si (1 0 0), MgO (1 0 0), and fused silica, respectively. The grain sizes of phosphors grown on different substrates were estimated by using Scherrer's formula and the maximum crystallite size observed for the thin film grown on Al₂O₃ (0 0 0 1). The room temperature PL spectra exhibit only the red emission peak at 613 nm radiated from the transition of (¹D₂ → ³H₄) and the maximum PL intensity for the films grown on the Al₂O₃ (0 0 0 1) is 1.1, 1.4, and 3.7 times higher than that of the CaTiO₃:Pr³⁺ films grown on MgO (1 0 0), Si (1 0 0), and fused Sillica substrates, respectively. The crystallinity, surface morphology and luminescence spectra of thin-film phosphors were highly dependent on substrates.     

Eu luminescence in tellurite glasses with gold nanostructures

Luminescence properties of Eu³⁺ doped TeO₂-PbO-GeO₂ glasses containing gold nanoparticles (NPs) were investigated. The emission spectra of the samples exhibited enhancement of Eu³⁺ luminescence due to the presence of gold NPs. The emission at 614 nm, due to the Eu³⁺ hypersensitive transition ⁵D₀-⁷F₂, is much influenced by the gold NPs and increases by ≈100% for samples heat-treated at 350 °C during 41 h.     

Silicon-rich/silica multilayers: A means to provide a link between the excitonic 1D quantum confinement and the photoluminescence parameters

The photoluminescence properties—intensity I_PL, emission energy E_PL and decay lifetime τ_PL—of silicon-rich silicon oxide (SRSO)/silica (SO) multilayers are investigated as a function of the optical pump flux (φ) of an argon laser and the measurement temperature in four kinds of samples corresponding to different SRSO sublayer thicknesses (namely 0.7, 1.4, 3.3 and 4.5 nm). The excitons created by the incident laser light mainly within the SRSO layers or at the SRSO/silica interface are confined in the multilayer growth direction (normal to the layers). This so-called 1D exciton quantum confinement effect has been independently described by two models (the state filling, the electron-hole exchange interaction). It is shown in this paper that both models are complementary since we have been able to reproduce, on the one hand, flux dependence of main PL features (energy, intensity and lifetime) of all fabricated samples and on the other hand, the evolution of the singlet-triplet energy splitting as a function of the SRSO sublayer thickness.     

Finite size effect on critical transition temperature of superconductive nanosolids

A simple and unified model is developed for finite size effect on the critical transition temperature of superconductive nanosolids, which is based on the size-dependent Debye temperature of crystals within the McMillan expression. In the model, two material and structure dependent parameters of D₀ and α are used, which, respectively, are the critical size at which all atoms of a low-dimensional material are located on its surface, and the ratio of the mean square vibrational amplitude between surface atoms and interior atoms, In light of this model, the critical transition temperatures of superconductive nanosolids can decrease or increase with the dropping size of nanosolids depending on the bond strength changes of interfacial atoms. The predicated results are consistent with the available experimental results for superconductors MgB₂ and Nb thin films, Bi and Pb granular thin films and nanoparticles, Al thin films and nanoparticles.     

D3→FJ emission in terbium-doped sol-gel glasses

In silicate sol-gel glass doped with trivalent terbium, the intensity of violet and blue fluorescence from the ⁵D₃ level is highly dependent on terbium concentration, on the presence of Al³⁺ co-dopant, and on annealing conditions. Evidence is presented that aluminum co-doping prevents rare earth clusters from forming, and also modifies the coupling of rare earth ions to the local environment. ⁵D₃ emission is observed in glasses annealed at 750 °C, and increases in intensity with increasing annealing time and with higher temperature. This behavior is shown to be due to the removal of residual hydroxyl ions.     

Interaction of PH3 coadsorbed with H2, D2, O2 and H2O on Rh(100)

The coadsorption of PH₃ with H₂, D₂, O₂ and H₂O on Rh(100) has been studied using temperature programmed desorption (TPD), Auger electron spectroscopy (AES) and low energy electron diffraction (LEED). The adsorption and molecular desorption of PH₃ is not affected by preadsorbed H₂, D₂ and O₂. Preadsorbed PH₃ blocks H₂ desorption sites while postdosed PH₃ displaces H₂ (D₂₁) from the Rh(100). When D₂ and PH₃ are coadsorbed, no D appears in desorbed phosphine. Preadsorbed O₂ reduces the amount of H₂ desorption (from PH₃ decomposition) and increases the H₂ desorption temperature. There is also some reaction between O(a) and H(a) to form water. Preexposure to H₂O decreases the extent of PH₃ adsorption and of PH₃ decomposition.     

The effects of hydrogen plasma pretreatment on the formation of vertically aligned carbon nanotubes

The effects of H₂ plasma pretreatment on the growth of vertically aligned carbon nanotubes (CNTs) by varying the flow rate of the precursor gas mixture during microwave plasma chemical vapor deposition (MPCVD) have been investigated in this study. Gas mixture of H₂ and CH₄ with a ratio of 9:1 was used as the precursor for synthesizing CNTs on Ni-coated TiN/Si(1 0 0) substrates. The structure and composition of Ni catalyst nanoparticles were investigated by using scanning electron microscopy (SEM) and cross-sectional transmission electron microscopy (XTEM). Results indicated that, by manipulating the morphology and density of the Ni catalyst nanoparticles via changing the flow rate of the precursor gas mixture, the vertically aligned CNTs could be effectively controlled. The Raman results also indicated that the intensity ratio of the G and D bands (I_D/I_G) is decreased with increasing gas flow rate. TEM results suggest H₂ plasma pretreatment can effectively reduce the amorphous carbon and carbonaceous particles and, thus, is playing a crucial role in modifying the obtained CNTs structures.     

Giant injection magnetoresistance in the heterostructure gallium arsenide/granular film with cobalt nanoparticles

We have studied the electron transport and have observed new phenomenon—the positive injection magnetoresistance on heterostructures gallium arsenide/granular film SiO₂ with Co nanoparticles and gallium arsenide/granular film TiO₂ with Co island layers.     

Ablation process of silica glass induced by laser plasma soft X-ray irradiation

Silica glass can be machined by irradiation with laser plasma soft X-rays on nano- and micrometer scale. We have investigated the ablation process of silica glass induced by laser plasma soft X-ray irradiation. We observed ionic and neutral species emitted from silica surfaces after irradiation. Dominant ions and neutrals are O⁺ and Si⁺ ions and Si, O, SiO and Si₂ neutrals, respectively. The ions have kinetic energies of 13 and 25 eV, which are much higher than those of particles emitted by evaporation. The energy of laser plasma soft X-rays absorbed to silica glass at a fluence of 1.4 J/cm² is estimated to be 380 kJ/cm³, which is higher than the binding energy of SiO₂ of 76 kJ/cm³. These results suggest that the most of the bonds in silica glass are broken by absorption of laser plasma soft X-rays, that several percent of the atoms are ionized, and that neutral atoms are emitted together with repulsive ions. The process possibly enables us to fabricate nano structures.     

Optical absorption and emission properties of Gd in silica host

We present a study of the optical properties of Gd-doped sol-gel silica glasses densified at different temperatures (from 450 up to 1050 °C) by means of optical absorption (OA) and radio luminescence (RL). The effect of a post-densification rapid thermal treatment (RTT) at approximately 1800 °C is also considered. Room temperature OA and RL measurements have revealed a slight low-energy shift of Gd³⁺ absorption/emission lines by densification temperature increasing accompanied by a parallel increase of Gd³⁺ RL intensities, especially strong after RTT. These effects are interpreted on the basis of structural modifications of the silica matrix and of the removal of non-radiative channels competing with Gd³⁺ emission. Moreover, RL spectra of fully densified samples display high-energy shoulders on the ⁶P_7/2-⁸S Gd³⁺ emission possibly related to crystal field splitting of the ⁶P_7/2 state. This interpretation is supported by the temperature dependence of RL spectra, investigated in the 10-320 K temperature interval: an increase of the intensity of high-energy components vs. temperature has been observed, which can be interpreted as due to thermally assisted excitation of electrons belonging to the lower ⁶P_7/2 state to higher crystal field states and their subsequent radiative recombination.     

Preparation and characterization of silica-coated Fe3O4 nanoparticles used as precursor of ferrofluids

Fe₃O₄ magnetic nanoparticles (MNPs) were synthesized by the co-precipitation of Fe³⁺ and Fe²⁺ with ammonium hydroxide. The sodium citrate-modified Fe₃O₄ MNPs were prepared under Ar protection and were characterized by Fourier transform infrared spectroscopy (FT-IR), transmission electron microscopy (TEM), X-ray powder diffraction (XRD) and vibrating sample magnetometer (VSM). To improve the oxidation resistance of Fe₃O₄ MNPs, a silica layer was coated onto the modified and unmodified MNPs by the hydrolysis of tetraethoxysilane (TEOS) at 50 °C and pH 9. Afterwards, the silica-coated Fe₃O₄ core/shell MNPs were modified by oleic acid (OA) and were tested by IR and VSM. IR results revealed that the OA was successfully grafted onto the silica shell. The Fe₃O₄/SiO₂ core/shell MNPs modified by OA were used to prepare water-based ferrofluids (FFs) using PEG as the second layer of surfactants. The properties of FFs were characterized using a UV-vis spectrophotometer, a Gouy magnetic balance, a laser particle size analyzer and a Brookfield LVDV-III+ rheometer.     

Probing the interactions of charmed mesons with nuclei in ¯p-induced reactions

We study the perspectives of resonant and nonresonant charmed-meson production in ˉp + A reactions within the Multiple Scattering Monte Carlo (MSMC) approach. We calculate the production of the resonances Ψ(3770),Ψ(4040) and Ψ(4160) on various nuclei, their propagation and decay to D,ˉD, D ^*,ˉD^*, D _s,ˉD_s in the medium and vacuum, respectively. The modifications of the open charm vector mesons in the nuclear medium are found to be rather moderate or even small such that dilepton spectroscopy will require an invariant mass resolution of a few MeV. Furthermore, the elastic and inelastic interactions of the open charm mesons in the medium are taken into account, which can be related to (u, d )-, s- or c-quark exchange with nucleons. It is found that by studying the D/ˉD ratio for low momenta in the laboratory ( ? 2 - 2.2 GeV/c) as a function of the target mass A stringent constraints on the c-quark exchange cross-section can be obtained. On the other hand, the ratios D ^- _s/D ⁺ _s as well as D/D ^- _s and D/D ⁺ _s at low momenta as a function of A will permit to fix independently the strength of the s-quark exchange reaction in D ^- _s N scattering. Received: 1 March 2002 / Accepted: 21 March 2002