Ponnusamy Nachimuthu

Application of Surface Chemical Analysis Tools for Characterization of Nanoparticles

AbstractThe important role that surface chemical analysis methods can and should play in the characterization of nanoparticles is described. The types of information that can be obtained from analysis of nanoparticles using Auger electron spectroscopy (AES), X-ray photoelectron spectroscopy (XPS), time-of-flight secondary-ion mass spectrometry (TOF-SIMS), low-energy ion scattering (LEIS), and scanning-probe microscopy (SPM), including scanning tunneling microscopy (STM) and atomic force microscopy (AFM), are briefly summarized. Examples describing the characterization of engineered nanoparticles are provided. Specific analysis considerations and issues associated with using surface-analysis methods for the characterization of nanoparticles are discussed and summarized, with the impact that shape instability, environmentally induced changes, deliberate and accidental coating, etc., have on nanoparticle properties. FigureAtomic force microscopy image of Cu2O nanodots formed on a SrTiO3 substrate.

The structure of Na2O–Al2O3–SiO2 glass: impact on sodium ion exchange in H2O and D2O

Abstract The kinetics of matrix dissolution and alkali-exchange for a series of sodium aluminosilicate glass compositions was determined at constant temperature and solution pH(D) under conditions of silica-saturation. Steady state release rate for sodium was 10–50 times faster than the rate of matrix dissolution, demonstrating that alkali exchange is an important long-term reaction mechanism that must be considered when modeling systems near saturation with respect to dissolved glass components. Sodium release rates were 30% slower in D 2 O compared to rates in H 2 O; but matrix dissolution rates were unaffected. These results are consistent with rupture of the OH bond as the rate-limiting reaction in Na + –H + exchange whereas matrix dissolution is controlled by OH − or H 2 O catalyzed hydrolysis of SiOSi and SiOAl bonds. Changes in Na exchange rate with increasing Al 2 O 3 content could not be reconciled with changes in the number of non-bridging oxygen (NBO) sites in the glass alone. A simple model was used to estimate a structural energy barrier for alkali ion exchange using NaO bond length and co-ordination as measured by Na K-edge X-ray absorption spectroscopy, and binding energy shifts for SiONa sites measured by X-ray photoelectron spectroscopy (XPS). The energy barrier was calculated to increase from 34 kJ mol −1 for Na 2 O·2SiO 2 glass to 49 kJ mol −1 for a glass containing 15 mol% Al 2 O 3 , consistent with stronger bonding of Na on NBO sites and increasing mechanical stiffness of the glass network with increasing Al content. The calculated ion-exchange enthalpies were then used to calculate Na ion-exchange rates as a function of glass composition. Agreement between the calculated and measured Na ion exchange rates was excellent.

Lack of ferromagnetism in n-type cobalt-doped ZnO epitaxial thin films

Epitaxial thin films of cobalt-doped ZnO (Co : ZnO) were deposited by pulsed laser deposition (PLD) on both c-plane and r-plane sapphire (Al2 O3). The films exhibited high structural quality with narrow x-ray diffraction (XRD) rocking curve peak widths. X-ray absorption spectroscopy (XANES and EXAFS) confirmed well-ordered Co substitution for Zn in ZnO without the formation of secondary phases. A wide range of n-type conductivities (10−4–105 Ω cm) was achieved by controlling the deposition conditions, post-annealing in vacuum, and/or addition of Al during deposition. Despite the high structural quality of the Co : ZnO thin films, no significant room temperature ferromagnetism was observed under any processing or treatment conditions. The lack of ferromagnetism indicates that itinerant conduction band electrons alone are not sufficient to induce ferromagnetism in Co : ZnO, even when the carrier concentration is a significant fraction of the magnetic dopant concentration. The implications of this observation are discussed.

Comparison of the sputter rates of oxide films relative to the sputter rate of SiO2

There is a growing interest in knowing the sputter rates for a wide variety of oxides because of their increasing technological importance in many different applications. To support the needs of users of the Environmental Molecular Sciences Laboratory, a national scientific user facility, as well as our research programs, the authors made a series of measurements of the sputter rates from oxide films that have been grown by oxygen plasma-assisted molecular beam epitaxy, pulsed laser deposition, atomic layer deposition, electrochemical oxidation, or sputter deposition. The sputter rates for these oxide films were determined in comparison with those from thermally grown SiO2, a common reference material for sputter rate determination. The film thicknesses and densities for most of these oxide films were measured using x-ray reflectivity. These oxide films were mounted in an x-ray photoelectron or Auger electron spectrometer for sputter rate measurements using argon ion sputtering. Although the primary objec...

Role of outer‐membrane cytochromes MtrC and OmcA in the biomineralization of ferrihydrite by Shewanella oneidensis MR‐1

In an effort to improve the understanding of electron transfer mechanisms at the microbe-mineral interface, Shewanella oneidensis MR-1 mutants with in-frame deletions of outer-membrane cytochromes (OMCs), MtrC and OmcA, were characterized for the ability to reduce ferrihydrite (FH) using a suite of microscopic, spectroscopic, and biochemical techniques. Analysis of purified recombinant proteins demonstrated that both cytochromes undergo rapid electron exchange with FH in vitro with MtrC displaying faster transfer rates than OmcA. Immunomicroscopy with cytochrome-specific antibodies revealed that MtrC co-localizes with iron solids on the cell surface while OmcA exhibits a more diffuse distribution over the cell surface. After 3-day incubation of MR-1 with FH, pronounced reductive transformation mineral products were visible by electron microscopy. Upon further incubation, the predominant phases identified were ferrous phosphates including vivianite [Fe(3)(PO(4))(2)x8H(2)O] and a switzerite-like phase [Mn(3),Fe(3)(PO(4))(2)x7H(2)O] that were heavily colonized by MR-1 cells with surface-exposed outer-membrane cytochromes. In the absence of both MtrC and OmcA, the cells ability to reduce FH was significantly hindered and no mineral transformation products were detected. Collectively, these results highlight the importance of the outer-membrane cytochromes in the reductive transformation of FH and support a role for direct electron transfer from the OMCs at the cell surface to the mineral.

Competitive reduction of pertechnetate (99TcO4-) by dissimilatory metal reducing bacteria and biogenic Fe(II).

The fate of pertechnetate ((99)Tc(VII)O(4)(-)) during bioreduction was investigated in the presence of 2-line ferrihydrite (Fh) and various dissimilatory metal reducing bacteria (DMRB) (Geobacter, Anaeromyxobacter, Shewanella) in comparison with TcO(4)(-) bioreduction in the absence of Fh. In the presence of Fh, Tc was present primarily as a fine-grained Tc(IV)/Fe precipitate that was distinct from the Tc(IV)O(2)·nH(2)O solids produced by direct biological Tc(VII) reduction. Aqueous Tc concentrations (<0.2 μm) in the bioreduced Fh suspensions (1.7 to 3.2 × 10(-9) mol L(-1)) were over 1 order of magnitude lower than when TcO(4)(-) was biologically reduced in the absence of Fh (4.0 × 10(-8) to 1.0 × 10(-7) mol L(-1)). EXAFS analyses of the bioreduced Fh-Tc products were consistent with variable chain length Tc-O octahedra bonded to Fe-O octahedra associated with the surface of the residual or secondary Fe(III) oxide. In contrast, biogenic TcO(2)·nH(2)O had significantly more Tc-Tc second neighbors and a distinct long-range order consistent with small particle polymers of TcO(2). In Fe-rich subsurface sediments, the reduction of Tc(VII) by Fe(II) may predominate over direct microbial pathways, potentially leading to lower concentrations of aqueous (99)Tc(IV).

Room-temperature ferromagnetism in ion-implanted Co-doped TiO2(110) rutile

Ferromagnetic Co-doped rutile TiO2 single crystals were synthesized by high-temperature ion implantation and characterized by a variety of techniques. Co is uniformly distributed to a depth of ∼300 nm with an average concentration of ∼2 at. %, except in the near-surface region, where the concentration is ∼3 at. %. Ferromagnetic behavior is exhibited at room temperature with an effective saturation magnetization of ∼0.6 μB/Co atom. The Co is in a formal oxidation state of +2 throughout the implanted region, and no Co(O) is detected.

Epitaxial growth and microstructure of Cu2O nanoparticle/thin films on SrTiO3(100)

Cuprous oxide (Cu2O) was grown on SrTiO3 (STO)(100) by oxygen plasma-assisted molecular-beam epitaxy. The microstructure of the grown layer and the Cu valence state were analysed using x-ray diffraction (XRD), x-ray photo-electron spectroscopy (XPS), atomic force microscopy (AFM) and cross-sectional transmission electron microscopy (TEM) as well as electron diffraction. The grown layer was dominated by the Cu2O phase, possessing an epitaxial orientation of and with respect to the substrate. The morphology of the Cu2O film shows a dependence on the growth rate. Typically, fast growth will lead to the formation of a thin film with a relatively smooth surface. Slow growth will lead to the development of nanoparticles, featuring the formation of Cu2O pyramids. The pyramids are invariantly defined by the Cu2O{111} planes. Given the fact that the {111} planes correspond to the lowest surface energy of Cu2O, slow growth will give the system enough time to allow it to adopt the pyramid configuration by which the overall energy of the system is minimized.

Oxygen transport studies in nanocrystalline ceria films

Oxygen uptake and conductivity were measured by nuclear reaction analysis and ac impedance technique at the intermediate temperature range on sol-gel grown nanocrystalline ceria films with average grain-sizes 7 nm and 38 nm synthesized at 723 K and 1173 K, respectively. Higher oxygen uptake and lower ionic conductivity are observed in ceria films with {approx}7 nm grain-size. High permeation-assisted oxygen diffusion in nanocrystallites combined with oxygen trapping in the disordered region contributes in higher oxygen uptake. However the lower ionic conductivity in the film results from absence of long-range lattice ordering. Relationship between oxygen uptake and conductivity in ceria is discussed in details by considering grain-size dependent defect density, related surface area and enhanced oxygen mobility.

X-Ray absorption spectroscopy of transition metal–magnesium hydride thin films

Mixed metal thin films containing magnesium and a first-row transition element exhibit very large changes in both reflectance and transmittance on exposure to hydrogen gas. Changes in electronic structure and coordination of the magnesium and transition metal atoms during hydrogen absorption were studied using dynamic in situ transmission mode X-ray absorption spectroscopy. Mg K-edge and Ni, Co, and Ti L-edge spectra reflect both reversible and irreversible changes in the metal environments. A significant shift in the nickel L absorption edge shows it to be an active participant in hydride formation. The effect on cobalt and titanium is much less dramatic, suggesting that these metals act primarily as catalysts for formation of magnesium hydride.