Spectroscopy and Diffraction

Molecular level solid-, liquid- and gas-interactions can be investigated through structural, chemical and compositional analysis with remarkable atomic scale spatial and high-energy resolution spectrometers and diffractometers for novel fundamental research.

Resources and Techniques

  • Electron spectroscopy
  • Electron backscatter diffraction
  • Atom probe tomography
  • Ion/molecular beam spectroscopy
  • 57Fe-Mössbauer spectroscopy
  • Optical spectroscopy
  • X-ray tomography and diffractometers

Additional Information

Capability Details

  • Electron spectrometers with high spatial and energy resolution in-situ and ex-situ x-ray photoelectron spectroscopy
  • Secondary ion mass spectrometers with single and cluster ion sources, and time-of-flight and magnetic mass analyzers
  • Electron microscopes with energy dispersive X-ray spectroscopy, electron energy loss spectroscopy and electron backscatter diffraction
  • Local Electrode Atom Probe tomography system with 355 nm UV laser and reflectron flight path for high mass resolution
  • Fourier transform infrared spectrometers with vacuum bench and variable temperature capability
  • Confocal-Raman, cryogenic time-resolved fluorescence, circular dichroism, stopped-flow absorbance, laser-induced breakdown and sum frequency generation optical tools
  • Variable temperature Mössbauer spectroscopy systems for bulk (transmission mode) and surface (emission) measures
  • X-ray diffraction instruments with sealed tube or rotating anode for analysis of powder, thin film and single crystal samples; point, CCD and image plate detection. X-ray computed tomography with 225- and 320-kV fixed, and 225-kV rotating target options using a 2000x2000 pixel area detector and state-of-the-art processing and visualization software

Electron spectroscopy – Achieving nanoscale spatial resolution, users can study elemental composition, structural properties, and chemical states of materials with applications to thin films, nanomaterials, catalysis, biological and environmental sciences, corrosion, and atmospheric aerosols.

Electron backscatter diffraction – Samples of microstructures in environmental and material science can be examined with three dimensional reconstruction and characterization using focused ion beam-electron backscatter diffraction analysis.

Atom probe tomography – Atom Probe Tomography (APT) provides comprehensive and accurate three dimensional chemical imaging for characterization of both metallic materials and low electrical conductivity materials, such as semiconductors, oxides, carbides, nitrides and composites.

Ion/molecular beam spectroscopy – Secondary ions and scattered ions from various materials are analyzed in straight, magnetic or time-of-flight mass spectrometers to investigate elemental, isotopic and molecular compositions through surface spectra, one dimensional depth profiling and two dimensional and three dimensional chemical imaging.

57Fe-Mössbauer spectroscopy – Using 57Fe (a versatile, highly sensitive, and stable isotope with natural abundance of 2.2%), users can obtain information about the valence state, coordination number and magnetic ordering temperatures for a wide range of Fe-containing samples; (e.g., Fe-organic matter complexes, sediments, catalysts, glass materials).

Optical spectroscopy – Fluorimetry, stopped-flow absorbance, FTIR and confocal-Raman tools enable analysis for biology, radiochemistry, and catalysis. Sum frequency generation-vibrational spectroscopy and second harmonic generation are available to study liquid, liquid and solid, and liquid interfaces.

X-ray tomography and diffractometers – X-ray computed tomography delivers images of microstructures (components, pore structure and connectivity) in biological and geological samples at tens of microns spatial resolution. General purpose and specialized x-ray diffraction systems, including single-crystal, microbeam and variable temperature powder capabilities, empower phase analysis of polycrystalline, epitaxial thin films, protein structure determination, and studies of problematic small inorganic molecules.

The atmospheric pressure reactor system is designed for testing the efficiency of various catalysts for the treatment of gas-phase pollutants. EMSL...
Custodian(s): Russell Tonkyn
The LEAP® 4000 XHR local electrode atom probe tomography instrument enabled the first-ever comprehensive and accurate 3-D chemical imaging studies...
The Bio-Logic® SFM-400/S is a 4-syringe stopped-flow system that offers the capability to carry out complex, multi-mixing experiments with the...
Custodian(s): Zheming Wang
EMSL's non-thermal interfacial reactions instrumentation is available for use in research directed toward understanding non-thermal interfacial...
Custodian(s): Greg Kimmel
EMSL's ultrahigh vacuum (UHV) surface chemistry-high-resolution electron energy loss spectroscopy (HREELS) system is designed to study the molecular...
Custodian(s): Mike Henderson
Commonly, SOFCs are operated at high temperatures (above 800°C). At these temperatures expensive housing is needed to contain an operating...
We modified our multi-channel, steady-state flow-through (SSFT), soil-CO2 flux monitoring system to include an array of inexpensive pyroelectric non-...
We fabricated large area (>1 × 1 cm2), epitaxial Fe nanowire arrays on MgO(001) substrates by nanoimprint...
We report the XPS characterization of a thermally evaporated iron thin film (6 nm) deposited on an Si/SiO_2/Al_2O_3 substrate using Al Ka X-rays. An...
Application of inorganic nanoparticles in diagnosis and therapy has become a critical component in targeted treatment of diseases. The surface...
Posted: September 12, 2014
Green fluorescent proteins, or GFPs, are found in jellyfish and other marine animals and glow green when exposed to light. Scientists use GFPs use...
Posted: June 17, 2014
The Science Hexavalent chromium is a major environmental contaminant at several Department of Energy (DOE) sites as well as other sites around the...
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The Science Uranium poses a serious risk of groundwater contamination at the Hanford Site. But most previous experimental studies addressing this...
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The Science Lithium-sulfur batteries are promising options for electric vehicles and for storing renewable energy because they can store a lot of...
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The Science Biological material derived from plants represents a promising source for renewable and sustainable biofuel production, but there is a...

Molecular level solid-, liquid- and gas-interactions can be investigated through structural, chemical and compositional analysis with remarkable atomic scale spatial and high-energy resolution spectrometers and diffractometers for novel fundamental research.

Resources and Techniques

  • Electron spectroscopy
  • Electron backscatter diffraction
  • Atom probe tomography
  • Ion/molecular beam spectroscopy
  • 57Fe-Mössbauer spectroscopy
  • Optical spectroscopy
  • X-ray tomography and diffractometers

Additional Information

Attachments: 

Effects of Oxygen-Containing Functional Groups on Supercapacitor Performance.

Abstract: 

Molecular dynamics (MD) simulations of the interface between graphene and the ionic liquid 1-butyl-3-methylimidazolium trifluoromethanesulfonate (BMIM OTf) were carried out to gain molecular-level insights into the performance of graphene-based supercapacitors and, in particular, determine the effects of the presence of oxygen-containing defects at the graphene surface on their integral capacitance. The MD simulations predict that increasing the surface coverage of hydroxyl groups negatively affects the integral capacitance, whereas the effect of the presence of epoxy groups is much less significant. The calculated variations in capacitance are found to be directly correlated to the interfacial structure. Indeed, hydrogen bonding between hydroxyl groups and SO3 anion moieties prevents BMIM+ and OTf- molecules from interacting favorably in the dense interfacial layer and restrains the orientation and mobility of OTf- ions, thereby reducing the permittivity of the ionic liquid at the interface. The results of the molecular simulations can facilitate the rational design of electrode materials for supercapacitors.

Citation: 
Kerisit SN, B Schwenzer, and M Vijayakumar.2014."Effects of Oxygen-Containing Functional Groups on Supercapacitor Performance."Journal of Physical Chemistry Letters 5(13):2330-2334. doi:10.1021/jz500900t
Authors: 
SN Kerisit
B Schwenzer
M Vijayakumar
Volume: 
5
Issue: 
13
Pages: 
2330-2334
Publication year: 
2014

Preface: Challenges for Catalytic Exhaust Aftertreatment.

Abstract: 

This special issue of Catalysis Today continues the tradition established since the 18th NAM in Cancun, 2003, of publishing the highlights coming from these catalytic after-treatment technologies sessions, where this volume contains 18 papers based on oral and poster presentations of the 23rd NAM, 2013. The guest editors would like to thank all of the catalyst scientists and engineers who presented in the "Emission control" sessions, and especially the authors who contributed to this special issue of Catalysis Today.

Citation: 
Nova I, B Epling, and CHF Peden.2014."Preface: Challenges for Catalytic Exhaust Aftertreatment."Catalysis Today 231(1):1-2. doi:10.1016/j.cattod.2014.02.017
Authors: 
I Nova
B Epling
CHF Peden
Instruments: 
Volume: 
231
Issue: 
1
Pages: 
1-2
Publication year: 
2014

Effects of Potassium loading and thermal aging on K/Pt/Al2O3 high-temperature lean NOx trap catalysts.

Abstract: 

The effects of K loading and thermal aging on the structural properties and high temperature performance of Pt/K/Al2O3 lean NOx trap (LNT) catalysts were investigated using in situ X-ray diffraction (XRD), temperature-programmed decomposition/desorption of NOx (NOx-TPD), transmission electron microscopy (TEM), NO oxidation and NOx storage tests. In situ XRD results demonstrate that KNO3 becomes extremely mobile on the Al2O3 surface, and experiences complex transformations between orthorhombic and rhombohedral structures, accompanied by sintering, melting and thermal decomposition upon heating. NOx storage results show an optimum K loading around 10% for the best performance at high temperatures. At lower K loadings where the majority of KNO3 stays as a surface layer, the strong interaction between KNO3 and Al2O3 promotes KNO3 decomposition and deteriorates high-temperature performance. At K loadings higher than 10%, the performance drop is not caused by NOx diffusion limitations as for the case of barium-based LNTs, but rather from the blocking of Pt sites by K species, which adversely affects NO oxidation. Thermal aging at 800 ºC severely deactivates the Pt/K/Al2O3 catalysts due to Pt sintering. However, in the presence of potassium, some Pt remains in a dispersed and oxidized form. These Pt species interact strongly with K and, therefore, do not sinter. After a reduction treatment, these Pt species remain finely dispersed, contributing to a partial recovery of NOx storage performance.

Citation: 
Luo J, F Gao, DH Kim, and CHF Peden.2014."Effects of Potassium loading and thermal aging on K/Pt/Al2O3 high-temperature lean NOx trap catalysts."Catalysis Today 231:164–172. doi:10.1016/j.cattod.2013.12.020
Authors: 
J Luo
F Gao
DH Kim
CHF Peden
Instruments: 
Publication year: 
2014

Following the movement of Cu ions in a SSZ-13 zeolite during dehydration, reduction and adsorption: a combined in situ TP-XRD,

Abstract: 

Cu-SSZ-13 has been shown to possess high activity and superior N2 formation selectivity in the selective catalytic reduction of NOx under oxygen rich conditions. Here, a combination of synchrotron-based (XRD and XANES) and vibrational (DRIFTS) spectroscopy tools have been used to follow the changes in the location and coordination environment of copper ions in a Cu-SSZ-13 zeolite during calcinations, reduction with CO, and adsorption of CO and H2O. XANES spectra collected during these procedures provides critical information not only on the variation in the oxidation state of the copper species in the zeolite structure, but also on the changes in the coordination environment around these ions as they interact with the framework, and with different adsorbates (H2O and CO). Time-resolved XRD data indicate the movement of copper ions and the consequent variation of the unit cell parameters during dehydration. DRIFT spectra provide information about the adsorbed species present in the zeolite, as well as the oxidation states of and coordination environment around the copper ions. A careful analysis of the asymmetric T-O-T vibrations of the CHA framework perturbed by copper ions in different coordination environments proved to be especially informative. The results of this study will aid the identification of the location, coordination and oxidation states of copper ions obtained during in operando catalytic studies. Financial support was provided by the US Department of Energy (DOE), Office of Energy Efficiency and Renewable Energy, Vehicle Technologies Program. Part of this work (sample preparation) was performed in the Environmental Molecular Sciences Laboratory (EMSL) at Pacific Northwest National Laboratory (PNNL). The EMSL is a national scientific user facility supported by the US DOE, Office of Biological and Environmental Research. PNNL is a multi-program national laboratory operated for the US DOE by Battelle. All of the spectroscopy work reported here was carried out at the National Synchrotron Light Source (NSLS) at Brookhaven National Laboratory (BNL). NSLS is a national scientific user facility supported by the US DOE.

Citation: 
Kwak JH, T Varga, CHF Peden, F Gao, JC Hanson, and J Szanyi.2014."Following the movement of Cu ions in a SSZ-13 zeolite during dehydration, reduction and adsorption: a combined in situ TP-XRD, XANES/DRIFTS study."Journal of Catalysis 314(1):83-93. doi:10.1016/j.jcat.2014.03.003
Authors: 
JH Kwak
T Varga
CHF Peden
F Gao
JC Hanson
J Szanyi
Instruments: 
Volume: 
314
Issue: 
1
Pages: 
83-93
Publication year: 
2014

Mesoscale Origin of the Enhanced Cycling-Stability of the Si-Conductive Polymer Anode for Li-ion Batteries.

Abstract: 

Electrode used in lithium-ion battery is invariably a composite of multifunctional components. The performance of the electrode is controlled by the interactive function of all components at mesoscale. Fundamental understanding of mesoscale phenomenon sets the basis for innovative designing of new materials. Here we report the achievement and origin of a significant performance enhancement of electrode for lithium ion batteries based on Si nanoparticles wrapped with conductive polymer. This new material is in marked contrast with conventional material, which exhibit fast capacity fade. In-situ TEM unveils that the enhanced cycling stability of the conductive polymer-Si composite is associated with mesoscale concordant function of Si nanoparticles and the conductive polymer. Reversible accommodation of the volume changes of Si by the conductive polymer allows good electrical contact between all the particles during the cycling process. In contrast, the failure of the conventional Si-electrode is probed to be the inadequate electrical contact.

Citation: 
Gu M, X Xiao, G Liu, S Thevuthasan, DR Baer, J Zhang, J Liu, ND Browning, and CM Wang.2014."Mesoscale Origin of the Enhanced Cycling-Stability of the Si-Conductive Polymer Anode for Li-ion Batteries."Scientific Reports 4:Article No. 3684. doi:10.1038/srep03684
Authors: 
Gu M
X Xiao
G Liu
S Thevuthasan
DR Baer
J Zhang
J Liu
ND Browning
CM Wang
Facility: 
Instruments: 
Publication year: 
2014

Demonstration of an Electrochemical Liquid Cell for Operando Transmission Electron Microscopy Observation of the Lithiation

Abstract: 

Over the last few years, in-situ transmission electron microscopy (TEM) studies of lithium ion batteries using an open-cell configuration have helped us to gain fundamental insights into the structural and chemical evolution of the electrode materials in real time. In the standard open-cell configuration, the electrolyte is either solid lithium oxide or an ionic liquid, which is point-contacted with the electrode. This cell design is inherently different from a real battery, where liquid electrolyte forms conformal contact with electrode materials. The knowledge learnt from open cells can deviate significantly from the real battery, calling for operando TEM technique with conformal liquid electrolyte contact. In this paper, we developed an operando TEM electrochemical liquid cell to meet this need, providing the configuration of a real battery and in a relevant liquid electrolyte. To demonstrate this novel technique, we studied the lithiation/delithiation behavior of single Si nanowires. Some of lithiation/delithation behaviors of Si obtained using the liquid-cell are consistent with the results from the open-cell studies. However, we also discovered new insights different from the open cell configuration - the dynamics of the electrolyte and, potentially, a future quantitative characterization of the SEI layer formation and structural and chemical evolution.

Citation: 
Gu M, LR Parent, BL Mehdi, RR Unocic, MT Mcdowell, RL Sacci, W Xu, JG Connell, P Xu, P Abellan Baeza, X Chen, Y Zhang, DE Perea, JE Evans, L Lauhon, J Zhang, J Liu, ND Browning, Y Cui, I Arslan, and CM Wang.2013."Demonstration of an Electrochemical Liquid Cell for Operando Transmission Electron Microscopy Observation of the Lithiation/Delithiation Behavior of Si Nanowire Battery Anodes."Nano Letters 13(12):6106-6112. doi:10.1021/nl403402q
Authors: 
Gu M
LR Parent
BL Mehdi
RR Unocic
MT Mcdowell
RL Sacci
W Xu
JG Connell
P Xu
P Abellan Baeza
X Chen
Y Zhang
DE Perea
JE Evans
L Lauhon
J Zhang
J Liu
ND Browning
Y Cui
I Arslan
CM Wang
Volume: 
13
Issue: 
12
Pages: 
6106-6112
Publication year: 
2013

Effect of H2O on the morphological changes of KNO3 formed on K2O/Al2O3 NOx storage materials: Fourier transform infra-red (FTIR)

Abstract: 

Based on combined FTIR and XRD studies, we report here that H2O induces a morphological change of KNO3 species formed on model K2O/Al2O3 NOx storage-reduction catalysts. Specifically as evidenced by FTIR, the contact of H2O with NO2 pre-adsorbed on K2O/Al2O3 promotes the transformation from bidentate (surface-like) KNO3 species to ionic (bulk-like) ones irrespective of K loadings. Once H2O is removed from the sample, a reversible transformation into bidentate KNO3 is observed, demonstrating a significant dependence of H2O on such morphological changes. TR-XRD results show the formation of two different types of bulk KNO3 phases (orthorhomobic and rhombohedral) in an as-impregnated sample. Once H2O begins to desorb above 400 K, the former is transformed into the latter, resulting in the existence of only the rhombohedral KNO3 phase. On the basis of consistent FTIR and TR-XRD results, we propose a model for the morphological changes of KNO3 species with respect to NO2 adsorption/desorption, H2O and/or heat treatments. Compared with the BaO/Al2O3 system, K2O/Al2O3 shows some similarities with respect to the formation of bulk nitrates upon H2O contact. However, there are significant differences that originate from the lower melting temperature of KNO3 relative to Ba(NO3)2.

Citation: 
Kim DH, KK Mudiyanselage, J Szanyi, JC Hanson, and CHF Peden.2014."Effect of H2O on the morphological changes of KNO3 formed on K2O/Al2O3 NOx storage materials: Fourier transform infra-red (FTIR) and time-resolved x-ray diffraction (TR-XRD) studies."Journal of Physical Chemistry C 118(8):4189–4197. doi:10.1021/jp410816r
Authors: 
DH Kim
KK Mudiyanselage
J Szanyi
JC Hanson
CHF Peden
Publication year: 
2014

Current Understanding and Remaining Challenges in Modeling Long-Term Degradation of Borosilicate Nuclear Waste Glasses.

Abstract: 

Chemical durability is not a single material property that can be uniquely measured. Instead it is the response to a host of coupled material and environmental processes whose rates are estimated by a combination of theory, experiment, and modeling. High-level nuclear waste (HLW) glass is perhaps the most studied of any material yet there remain significant technical gaps regarding their chemical durability. The phenomena affecting the long-term performance of HLW glasses in their disposal environment include surface reactions, transport properties to and from the reacting glass surface, and ion exchange between the solid glass and the surrounding solution and alteration products. The rates of these processes are strongly influenced and are coupled through the solution chemistry, which is in turn influenced by the reacting glass and also by reaction with the near-field materials and precipitation of alteration products. Therefore, those processes must be understood sufficiently well to estimate or bound the performance of HLW glass in its disposal environment over geologic time-scales. This article summarizes the current state of understanding of surface reactions, transport properties, and ion exchange along with the near-field materials and alteration products influences on solution chemistry and glass reaction rates. Also summarized are the remaining technical gaps along with recommended approaches to fill those technical gaps.

Citation: 
Vienna JD, JV Ryan, S Gin, and Y Inagaki.2013."Current Understanding and Remaining Challenges in Modeling Long-Term Degradation of Borosilicate Nuclear Waste Glasses."International Journal of Applied Glass Science 4(4):283-294. doi:10.1111/ijag.12050
Authors: 
JD Vienna
JV Ryan
S Gin
Y Inagaki
Instruments: 
Volume: 
4
Issue: 
4
Pages: 
283-294
Publication year: 
2013

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