Engineering Disorder at a Nanoscale: A Combined TEM and XAS Investigation of Amorphous versus Nanocrystalline Sodium Birnessite

2015 ◽  
Vol 68 (11) ◽  
pp. 1715 ◽  
Author(s):  
Rosalie K. Hocking ◽  
Hannah J. King ◽  
Aimee Hesson ◽  
Shannon A. Bonke ◽  
Bernt Johannessen ◽  
...  
Keyword(s):  
Water Oxidation ◽  
Nanocrystalline Material ◽  
Oxidation Catalysis ◽  
X Ray Diffraction ◽  
X Ray ◽  
Transmission Electron ◽  
Water Oxidation Catalysis ◽  
Catalytically Active ◽  
Amorphous Metal Oxide ◽  
X Ray Absorption

The term amorphous metal oxide is becoming widely used in the catalysis community. The term is generally used when there are no apparent peaks in an X-ray diffraction pattern. However, the absence of such features in X-ray diffraction can mean that the material is either truly amorphous or that it is better described as nanocrystalline. By coprecipitating a sodium birnessite-like phase with and without phosphate (1.5 %), we are able to engineer two very similar but distinct materials – one that is nanocrystalline and the other that is amorphous. The two closely related phases were characterized with both Mn K-edge X-ray absorption spectroscopy and high-resolution transmission electron microscopy. These structural results were then correlated with catalytic and electrocatalytic activities for water oxidation catalysis. In this case, the amorphous phosphate-doped material was less catalytically active than the nanocrystalline material.

scholarly journals Structural Evolution in Wet Mechanically Alloyed Co-Fe-(Ta,W)-B Alloys

Metals ◽  
2021 ◽  
Vol 11 (5) ◽  
pp. 800
Author(s):  
Vladimír Girman ◽  
Maksym Lisnichuk ◽  
Daria Yudina ◽  
Miloš Matvija ◽  
Pavol Sovák ◽  
...  
Keyword(s):  
Structural Changes ◽  
Magnetic Measurements ◽  
Structural Evolution ◽  
High Energy ◽  
Control Agent ◽  
X Ray Diffraction ◽  
Mechanically Alloyed ◽  
X Ray ◽  
Transmission Electron ◽  
X Ray Absorption

In the present study, the effect of wet mechanical alloying (MA) on the glass-forming ability (GFA) of Co43Fe20X5.5B31.5 (X = Ta, W) alloys was studied. The structural evolution during MA was investigated using high-energy X-ray diffraction, X-ray absorption spectroscopy, high-resolution transmission electron microscopy and magnetic measurements. Pair distribution function and extended X-ray absorption fine structure spectroscopy were used to characterize local atomic structure at various stages of MA. Besides structural changes, the magnetic properties of both compositions were investigated employing a vibrating sample magnetometer and thermomagnetic measurements. It was shown that using hexane as a process control agent during wet MA resulted in the formation of fully amorphous Co-Fe-Ta-B powder material at a shorter milling time (100 h) as compared to dry MA. It has also been shown that substituting Ta with W effectively suppresses GFA. After 100 h of MA of Co-Fe-W-B mixture, a nanocomposite material consisting of amorphous and nanocrystalline bcc-W phase was synthesized.

Size dependent behavior of Fe3O4crystals during electrochemical (de)lithiation: an in situ X-ray diffraction, ex situ X-ray absorption spectroscopy, transmission electron microscopy and theoretical investigation

2017 ◽  
Vol 19 (31) ◽  
pp. 20867-20880 ◽  
Author(s):  
David C. Bock ◽  
Christopher J. Pelliccione ◽  
Wei Zhang ◽  
Janis Timoshenko ◽  
K. W. Knehr ◽  
...  
Keyword(s):  
Electron Microscopy ◽  
Structural Changes ◽  
Ex Situ ◽  
X Ray Diffraction ◽  
X Ray ◽  
Size Dependent ◽  
Transmission Electron ◽  
Dependent Behavior ◽  
X Ray Absorption

Crystal and atomic structural changes of Fe3O4upon electrochemical (de)lithiation were determined.

scholarly journals Effects of pH and Ca exchange on the structure and redox state of synthetic Na-birnessite

2021 ◽  
Vol 106 (1) ◽  
pp. 15-27
Author(s):  
Chiara Elmi ◽  
Jeffrey E. Post ◽  
Peter J. Heaney ◽  
Eugene S. Ilton
Keyword(s):  
Photoelectron Spectroscopy ◽  
Water Oxidation ◽  
Structure Refinement ◽  
Oxidation Catalysis ◽  
X Ray ◽  
Cell Parameters ◽  
Ph Values ◽  
Water Oxidation Catalysis ◽  
Effects Of Ph ◽  
End Members

Abstract Birnessite-like minerals are among the most common Mn oxides in surficial soils and sediments, and they mediate important environmental processes (e.g., biogeochemical cycles, heavy metal confinement) and have novel technological applications (e.g., water oxidation catalysis). Ca is the dominant interlayer cation in both biotic and abiotic birnessites, especially when they form in association with carbonates. The current study investigated the structures of a series of synthetic Ca-birnessite analogs prepared by cation-exchange with synthetic Na-birnessite at pH values from 2 to 7.5. The resulting Ca-exchanged birnessite phases were characterized using powder X-ray diffraction and Rietveld refinement, Fourier transform infrared spectroscopy, Raman spectroscopy, X-ray photoelectron spectroscopy, and scanning and transmission electron microscopy. All samples synthesized at pH values greater than 3 exhibited a similar triclinic structure with nearly identical unit-cell parameters. The samples exchanged at pH 2 and 3 yielded hexagonal structures, or mixtures of hexagonal and triclinic phases. Rietveld structure refinement and X-ray photoelectron spectroscopy showed that exchange of Na by Ca triggered reduction of some Mn3+, generating interlayer Mn2+ and vacancies in the octahedral layers. The triclinic and hexagonal Ca-birnessite structures described in this study were distinct from Na- and H-birnessite, respectively. Therefore, modeling X-ray absorption spectra of natural Ca-rich birnessites through mixing of Na- and H-birnessite end-members will not yield an accurate representation of the true structure.

scholarly journals Observation and Characterization of Fragile Organometallic Molecules Encapsulated in Single-Wall Carbon Nanotubes

2014 ◽  
Vol 2014 ◽  
pp. 1-5
Author(s):  
Daisuke Ogawa ◽  
Ryo Kitaura ◽  
Takeshi Saito ◽  
Shinobu Aoyagi ◽  
Eiji Nishibori ◽  
...  
Keyword(s):  
Carbon Nanotubes ◽  
High Yield ◽  
Single Wall Carbon Nanotubes ◽  
X Ray Diffraction ◽  
Single Wall Carbon ◽  
X Ray ◽  
Transmission Electron ◽  
Organometallic Molecules ◽  
X Ray Absorption

Thermally fragile tris(η5-cyclopentadienyl)erbium (ErCp3) molecules are encapsulated in single-wall carbon nanotubes (SWCNTs) with high yield. We realized the encapsulation of ErCp3with high filling ratio by using high quality SWCNTs at an optimized temperature under higher vacuum. Structure determination based on high-resolution transmission electron microscope observations together with the image simulations reveals the presence of almost free rotation of each ErCp3molecule in SWCNTs. The encapsulation is also confirmed by X-ray diffraction. Trivalent character of Er ions (i.e., Er3+) is confirmed by X-ray absorption spectrum.

Thiol-Capped CdSe and CdTe Nanoclusters: Synthesis by a Wet Chemical Route, Structural and Optical Properties

1998 ◽  
Vol 536 ◽  
Author(s):  
A. L. Rogach ◽  
A Eychmüller ◽  
J. Rockenberger ◽  
A. Kornowski ◽  
H. Weller ◽  
...  
Keyword(s):  
Particle Size ◽  
X Ray Diffraction ◽  
Structural And Optical Properties ◽  
Chemical Route ◽  
X Ray ◽  
Stabilizing Agents ◽  
Transmission Electron ◽  
Wet Chemical ◽  
Wet Chemical Route ◽  
X Ray Absorption

AbstractCdSe and CdTe nanoclusters were formed in aqueous solutions at moderate temperatures by a wet chemical route in the presence of thiols as effective stabilizing agents. The nature of the stabilizing agent (thioalcohols or thioacids) had an important influence on the particle size and largely determined the photoluminescence properties. The nanoclusters were characterized by means of UV-vis absorption and photoluminescence spectroscopy, powder X-ray diffraction, high resolution transmission electron microscopy, and extended X-ray absorption fine structure measurements. CdSe and CdTe nanoclusters were crystalline, in the cubic zincblende phase, with mean sizes in the range of 2 to 5 nm depending on the preparative conditions and the postpreparative size-selective fractionation, and showed pronounced electronic transitions in the absorption spectra. Thioglycerol-stabilized CdTe nanoclusters possessed sharp band-egde photoluminescence being tunable with particle size.

Structural, morphological, and magnetic study of nanocrystalline cobalt-copper powders synthesized by the polyol process

1995 ◽  
Vol 10 (6) ◽  
pp. 1546-1554 ◽  
Author(s):  
G.M. Chow ◽  
L.K. Kurihara ◽  
K.M. Kemner ◽  
P.E. Schoen ◽  
W.T. Elam ◽  
...  
Keyword(s):  
Electron Microscopy ◽  
Transmission Electron Microscopy ◽  
Face Centered Cubic ◽  
X Ray Diffraction ◽  
X Ray ◽  
Transmission Electron ◽  
Copper Powders ◽  
Face Centered ◽  
Increasing Temperature ◽  
X Ray Absorption

Nanocrystalline CoxCu100−x (4 ⋚ x ⋚ 49 at. %) powders were prepared by the reduction of metal acetates in a polyol. The structure of powders was characterized by x-ray diffraction (XRD), transmission electron microscopy (TEM), high resolution transmission electron microscopy (HRTEM), extended x-ray absorption fine structure (EXAFS) spectroscopy, solid-state nuclear magnetic resonance (NMR) spectroscopy, and vibrating sample magnetometry (VSM). As-synthesized powders were composites consisting of nanoscale crystallites of face-centered cubic (fcc) Cu and metastable face-centered cubic (fcc) Co. Complementary results of XRD, HRTEM, EXAFS, NMR, and VSM confirmed that there was no metastable alloying between Co and Cu. The NMR data also revealed that there was some hexagonal-closed-packed (hcp) Co in the samples. The powders were agglomerated, and consisted of aggregates of nanoscale crystallites of Co and Cu. Upon annealing, the powders with low Co contents showed an increase in both saturation magnetization and coercivity with increasing temperature. The results suggested that during preparation the nucleation of Cu occurred first, and the Cu crystallites served as nuclei for the formation of Co.

Doping and Characterisation of Nanocrystalline Materials

2007 ◽  
Vol 128 ◽  
pp. 61-72
Author(s):  
Th. Wichert ◽  
Z. Guan
Keyword(s):  
Nanocrystalline Materials ◽  
Local Information ◽  
Atomic Scale ◽  
Radioactive Isotopes ◽  
Correlation Technique ◽  
X Ray Diffraction ◽  
X Ray ◽  
Transmission Electron ◽  
Significant Process ◽  
X Ray Absorption

The synthesis behaviour and characterisation of nanocrystalline materials is presented. The materials synthesised are ZnO and InP doped with shallow donors and acceptors, respectively. Characterisation was performed with radioactive isotopes using the perturbed γγ angular correlation technique (PAC), thereby yielding local information on an atomic scale. The characterisation was supplemented by X-ray diffraction, transmission electron microscopy, UV/VIS absorption spectroscopy, photoluminescence spectroscopy, and extended X-ray absorption fine structure spectroscopy. It was shown that the successful incorporation of dopants in nanocrystalline ZnO and InP requires annealing at temperatures at which the growth of the nanocrystals in the sample becomes a significant process.

Compositional and structural studies of amorphous GaN grown by ion-assisted deposition

2001 ◽  
Vol 693 ◽  
Author(s):  
U. D. Lanke ◽  
A. Koo ◽  
B. J. Ruck ◽  
H. K. Lee ◽  
A. Markwitz ◽  
...  
Keyword(s):  
Atomic Ratio ◽  
Nuclear Reaction Analysis ◽  
X Ray Diffraction ◽  
X Ray ◽  
Transmission Electron ◽  
Local Bonding ◽  
Ion Energies ◽  
Nitrogen Ion ◽  
Tetrahedral Bonding ◽  
X Ray Absorption

AbstractAmorphous GaN films have been deposited onto various substrates by ion-assisted deposition. The films were deposited at room temperature using nitrogen ion energies in the range 40-900 eV. Rutherford backscattering spectroscopy and nuclear reaction analysis show that the Ga:N atomic ratio is approximately one for films grown with ion energy near 500 eV; these films have the highest transparency. Films grown with ion energies below 300 eV are Ga rich, and show reduced transparency across the visible. Raman spectroscopy, x-ray diffraction, and transmission electron microscopy confirm the amorphous nature of the films. Annealing studies on a-GaN establish that the films begin to crystallise at a temperature of about 700 C. To investigate the local bonding environment of the Ga or N atoms, we have measured the extended x-ray absorption fine structure (EXAFS) of the transparent GaN films. The EXAFS results indicate that the films are dominated by heteropolar tetrahedral bonding, with a low density of homopolar bonds.

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