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. See a complete list of Spectroscopy and Diffraction instruments.

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:

Description

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.

Instruments

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...
Custodian(s): Arun Devaraj, Daniel Perea
This unique instrument is capable of measuring gas/solid reaction rates under realistic, high-pressure (∼1 atm) conditions using model, low-surface...
Custodian(s): Janos Szanyi
EMSL's non-thermal interfacial reactions instrumentation is available for use in research directed toward understanding non-thermal interfacial...
Custodian(s): Greg Kimmel
The SMSAS is a multi-technique surface analysis instrument based on elemental mapping using either scanning small spot X-rays or the electronics in...
Custodian(s): Shuttha Shutthanandan

Publications

The ability to tune the atomic-scale structural and chemical ordering in nanoalloy catalysts is essential for achieving the ultimate goal of high...
Surface functionalized magnetic nanoparticles (MNPs) are appealing candidates for analytical separation of heavy metal ions from waste water and...
The interactions between proteins and surfaces are critical to a number of important processes including biomineralization, the biocompatibility of...
A series of cobalt nickel mixed oxide catalysts with the varying ratios of Co to Ni, prepared by co-precipitation method, were applied to methane...
Thisstudyemployed16SrRNAgeneampliconpyrosequencingtoexaminethehypothesisthatchemolithotrophicFe(II)-oxidizing bacteria(FeOB)would preferentially...

Science Highlights

Posted: January 13, 2016
The Science Technetium-99 (99Tc) is a long-lived radionuclide byproduct of the nuclear fuel cycle, making it a major radiological concern at nuclear...
Posted: December 08, 2015
Researchers at Pacific Northwest National Laboratory, EMSL and University of Wyoming found airborne dust particles, thought to be a perfect landing...
Posted: September 23, 2015
The Science Natural organic matter (NOM) is a mixture of organic molecules derived primarily from the natural decay of plant matter. Understanding...
Posted: September 22, 2015
The Science Uranium dioxide (UO2) contains the less soluble and immobile form of uranium in nature, so it is the desired end product of...
Posted: June 15, 2015
The Science The Chesapeake Bay is the largest and most productive estuary in the United States, containing more than 1,500 square miles of wetlands...

Instruments

The aim of this proposal is to build upon our initial success in the exploration of the 3-D location and distribution of the Al and Si atoms in...
A critical challenge for high temperature electrochemistry is metallic catalyst stability. Rapid migration of nickel features is a key limitation to...
This program is focused on obtaining a microscopic understanding of solution chemistry and solvation of negatively charged ions using cluster models...
Production of biofuels from lignocellulosic biomass, a renewable resource, can play a significant role in achieving goals of long term sustainability...
Since the sodium reserves are easily accessible, we decided to investigate sodium ion batteries (NaIBs), as new energy storage systems, for large-...

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. See a complete list of Spectroscopy and Diffraction instruments.

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: 

Design of Ternary Nanoalloy Catalysts: Effect of Nanoscale Alloying and Structural Perfection on Electrocatalytic Enhancement.

Abstract: 

The ability to tune the atomic-scale structural and chemical ordering in nanoalloy catalysts is essential for achieving the ultimate goal of high activity and stability of catalyst by design. This article demonstrates this ability with a ternary nanoalloy of platinum with vanadium and cobalt for oxygen reduction reaction in fuel cells. The strategy is to enable nanoscale alloying and structural perfection through oxidative–reductive thermochemical treatments. The structural manipulation is shown to produce a significant enhancement in the electrocatalytic activity of the ternary nanoalloy catalysts for oxygen reduction reaction. Mass activities as high as 1 A/mg of Pt have been achieved by this strategy based on direct measurements of the kinetic currents from rotating disk electrode data. Using a synchrotron high-energy X-ray diffraction technique coupled with atomic pair function analysis and X-ray absorption fine structure spectroscopy as well as X-ray photoelectron spectroscopy, the atomic-scale structural and chemical ordering in nanoalloy catalysts prepared by the oxidative–reductive thermochemical treatments were examined. A phase transition has been observed, showing an fcc-type structure of the as-prepared and the lower-temperature-treated particles into an fct-type structure for the particles treated at the higher temperature. The results reveal a thermochemically driven evolution of the nanoalloys from a chemically disordered state into chemically ordered state with an enhanced degree of alloying. The increase in the chemical ordering and shrinking of interatomic distances as a result of thermochemical treatment at increased temperature is shown to increase the catalytic activity for oxygen reduction reaction, exhibiting an optimal activity at 600 °C. It is the alloying and structural perfection that allows the optimization of the catalytic performance in a controllable way, highlighting the significant role of atomic-scale structural and chemical ordering in the design of nanoalloy catalysts.

Citation: 
Wanjala BN, B Fang, S Shan, V Petkov, P Zhu, R Loukrakpam, Y Chen, J Luo, J Yin, L Yang, M Shao, and CJ Zhong.2012."Design of Ternary Nanoalloy Catalysts: Effect of Nanoscale Alloying and Structural Perfection on Electrocatalytic Enhancement."Chemistry of Materials 24(22):4283–4293. doi:10.1021/cm301613j
Authors: 
BN Wanjala
B Fang
S Shan
V Petkov
P Zhu
R Loukrakpam
Y Chen
J Luo
J Yin
L Yang
M Shao
CJ Zhong
Volume: 
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Publication year: 
2012

Magnetic Separation Dynamics of Colloidal Magnetic Nanoparticles.

Abstract: 

Surface functionalized magnetic nanoparticles (MNPs) are appealing candidates for analytical separation of heavy metal ions from waste water and separation of actinides from spent nuclear fuel. This work studies the separation dynamics and investigates the appropriate magnetic-field gradients. A dynamic study of colloidal MNPs was performed for steady-state flow. Measurements were conducted to record the separation time of particles as a function of magnetic field gradient. The drag and magnetic forces play a significant role on the separation time. A drop in saturation magnetization and variation of particle size occurs after surface functionalization of the MNPs; these are the primary factors that affect the separation time and velocity of the MNPs. The experimental results are correlated to a theoretical one-dimensional model.

Citation: 
Kaur M, H Zhang, and Y Qiang.2013."Magnetic Separation Dynamics of Colloidal Magnetic Nanoparticles."IEEE Magnetics Letters 4:4000204. doi:10.1109/LMAG.2013.2271744
Authors: 
M Kaur
H Zhang
Y Qiang
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2013

Effect of Co/Ni ratios in cobalt nickel mixed oxide catalysts on methane combustion.

Abstract: 

A series of cobalt nickel mixed oxide catalysts with the varying ratios of Co to Ni, prepared by co-precipitation method, were applied to methane combustion. Among the various ratios, cobalt nickel mixed oxides having the ratios of Co to Ni of (50:50) and (67:33) demonstrate the highest activity for methane combustion. Structural analysis obtained from X-ray diffraction (XRD) and extended X-ray absorption fine structure (EXAFS) evidently demonstrates that CoNi (50:50) and (67:33) samples consist of NiCo2O4and NiO phase and, more importantly, NiCo2O4spinel structure is largely distorted, which is attributed to the insertion of Ni2+ions into octahedral sites in Co3O4spinel structure. Such structural dis-order results in the enhanced portion of surface oxygen species, thus leading to the improved reducibility of the catalysts in the low temperature region as evidenced by temperature programmed reduction by hydrogen (H2TPR) and X-ray photoelectron spectroscopy (XPS) O 1s results. They prove that structural disorder in cobalt nickel mixed oxides enhances the catalytic performance for methane combustion. Thus, it is concluded that a strong relationship between structural property and activity in cobalt nickel mixed oxide for methane combustion exists and, more importantly, distorted NiCo2O4spinel structure is found to be an active site for methane combustion.

Citation: 
Lim TH, SJ Cho, HS Yang, MH Engelhard, and DH Kim.2015."Effect of Co/Ni ratios in cobalt nickel mixed oxide catalysts on methane combustion."Applied Catalysis. A, General 505:62-69. doi:10.1016/j.apcata.2015.07.040
Authors: 
H Mark
Lim TH
SJ Cho
HS Yang
MH Engelhard
DH Kim
Volume: 
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Publication year: 
2015

Effects of Si/Al Ratio on Cu/SSZ-13 NH3-SCR Catalysts: Implications for the active Cu species and the Roles of Brønsted Acidity

Abstract: 

Cu/SSZ-13 catalysts with three Si/Al ratios of 6, 12 and 35 were synthesized with Cu incorporation via solution ion exchange. The implications of varying Si/Al ratios on the nature of the multiple Cu species that can be present in the SSZ-13 zeolite are a major focus of this work, as highlighted by the results of a variety of catalyst characterization and reaction kinetics measurements. Specifically, catalysts were characterized with surface area/pore volume measurements, temperature programmed reduction by H2 (H2-TPR), NH3 temperature programmed desorption (NH3-TPD), and DRIFTS and solid-state nuclear magnetic resonance (NMR) spectroscopies. Catalytic properties were examined using NO oxidation, ammonia oxidation, and standard ammonia selective catalytic reduction (NH3-SCR) reactions on selected catalysts under differential conditions. Besides indicating possible variably active multiple Cu species for these reactions, the measurements are also used to untangle some of the complexities caused by the interplay between redox of Cu ion centers and Brønsted acidity. All three reactions appear to follow a redox reaction mechanism, yet the roles of Brønsted acidity are quite different. For NO oxidation, increasing Si/Al ratio lowers Cu redox barriers, thus enhancing reaction rates. Brønsted acidity appears to play essentially no role for this reaction. For standard NH3-SCR, residual Brønsted acidity plays a significant beneficial role at both low- and high-temperature regimes. For NH3 oxidation, no clear trend is observed suggesting both Cu ion center redox and Brønsted acidity play important and perhaps competing roles. The authors gratefully acknowledge the US Department of Energy (DOE), Energy Efficiency and Renewable Energy, Vehicle Technologies Office for the support of this work. The research described in this paper was performed in the Environmental Molecular Sciences Laboratory (EMSL), a national scientific user facility sponsored by the DOE’s Office of Biological and Environmental Research and located at Pacific Northwest National Laboratory (PNNL). PNNL is operated for the US DOE by Battelle.

Citation: 
Gao F, NM Washton, Y Wang, M Kollar, J Szanyi, and CHF Peden.2015."Effects of Si/Al Ratio on Cu/SSZ-13 NH3-SCR Catalysts: Implications for the active Cu species and the Roles of Brønsted Acidity ."Journal of Catalysis 331:25–38. doi:10.1016/j.jcat.2015.08.004
Authors: 
M Nancy
Janos Szanyi
Gao F
NM Washton
Y Wang
M Kollar
J Szanyi
CHF Peden
Volume: 
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Publication year: 
2015

Infrared Multiphoton Dissociation Spectroscopy of a Gas-Phase Complex of Uranyl and 3Oxa-Glutaramide: An Extreme Red-Shift of

Abstract: 

The gas-phase complex UO2(TMOGA)22+ (TMOGA = tetramethyl-3-oxa-glutaramide) prepared by electrospray ionization was characterized by infrared multiphoton dissociation (IRMPD) spectroscopy. The IRMPD spectrum from 700–1800 cm–1 was interpreted using a computational study based on density functional theory. The predicted vibrational frequencies are in good agreement with the measured values, with an average deviation of only 8 cm–1 (<1%) and a maximum deviation of 21 cm–1 (<2%). The only IR peak assigned to the linear uranyl moiety was the asymmetric ν3 mode, which appeared at 965 cm–1 and was predicted by DFT as 953 cm–1. This ν3 frequency is red-shifted relative to bare uranyl, UO22+, by ca. 150 cm–1 due to electron donation from the TMOGA ligands. Based on the degree of red-shifting, it is inferred that two TMOGA oxygen-donor ligands have a greater effective gas basicity than the four monodentate acetone ligands in UO2(acetone)42+. The uranyl ν3 frequency was also computed for uranyl coordinated by two TMGA ligands, in which the central Oether of TMOGA has been replaced by CH2. The computed ν3 for UO2(TMGA)22+, 950 cm–1, is essentially the same as that for UO2(TMOGA)22+, suggesting that electron donation to uranyl from the Oether of TMOGA is minor. The computed ν3 asymmetric stretching frequencies for the three actinyl complexes, UO2(TMOGA)22+, NpO2(TMOGA)22+ and PuO2(TMOGA)22+, are comparable. This similarity is discussed in the context of the relationship between ν3 and intrinsic actinide-oxygen bond energies in actinyl complexes.

Citation: 
Gibson JK, H Hu, MJ Van Stipdonk, G Berden, J Oomens, and J Li.2015."Infrared Multiphoton Dissociation Spectroscopy of a Gas-Phase Complex of Uranyl and 3?Oxa-Glutaramide: An Extreme Red-Shift of the [O=U=O]2+ Asymmetric Stretch."Journal of Physical Chemistry A 119(14):3366–3374. doi:10.1021/jp512599e
Authors: 
JK Gibson
H Hu
MJ Van Stipdonk
G Berden
J Oomens
J Li
Facility: 
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Publication year: 
2015

Isolation of the Copper Redox Steps in the Standard Selective CatalyticReduction on Cu-SSZ-13.

Abstract: 

Operando X-ray absorption experiments and density functional theory (DFT) calculations are reported that elucidate the role of copper redox chemistry in the selective catalytic reduction (SCR) of NO over Cu-exchanged SSZ-13. Catalysts prepared to contain only isolated, exchanged CuII ions evidence both CuII and CuI ions under standard SCR conditions at 473 K. Reactant cutoff experiments show that NO and NH3 together are necessary for CuII reduction to CuI. DFT calculations show that NO-assisted NH3 dissociation is both energetically favorable and accounts for the observed CuII reduction. The calculations predict in situ generation of
Brønsted sites proximal to CuI upon reduction, which we quantify in separate titration experiments. Both NO and O2 are necessary for oxidation of CuI to CuII, which DFT suggests to occur by a NO2 intermediate. Reaction of Cu-bound NO2 with
proximal NH4 + completes the catalytic cycle. N2 is produced in both reduction and oxidation half-cycles.

Citation: 
Paolucci C, AA Verma, SA Bates, VF Kispersky, JT Miller, R Gounder, N Delgass, F Ribeiro, and WF Schneider.2014."Isolation of the Copper Redox Steps in the Standard Selective CatalyticReduction on Cu-SSZ-13."Angewandte Chemie International Edition 53(44):11828–11833. doi:10.1002/anie.201407030
Authors: 
C Paolucci
AA Verma
SA Bates
VF Kispersky
JT Miller
R Gounder
N Delgass
F Ribeiro
WF Schneider
Volume: 
Issue: 
Pages: 
Publication year: 
2014

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Dr. Bowden joined EMSL in 2009 and currently manages EMSL's optical spectroscopy and diffraction, subsurface flow and transport, and microfabrication and deposition capabilities. He is responsible for the X-ray diffraction facility and assists...