Extreme Pair-Distribution-Function Measurements · 2012-08-20 · Extreme...
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Extreme Pair-Distribution-Function Measurements
Peter J. Chupas
Chemistry, Environmental, and Polymer Science GroupX-ray Science Division
Argonne National Laboratory
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Talk Overview
(1) PDF Instrumentation (at the APS)
(2) Emerging scientific opportunities- “Time Resolved” measurements
- Measurements requiring high sensitivity & applications in Hydrogen research
-Fossil Fuels- PDF at High Pressures (DAC)
- Spatially resolved measurements
(3) Potential instrumental advances &future opportunities
-Where do we go from here?
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11-ID-B, 11-ID-C
1-ID
6-ID
13-ID
5-BM-D
High Energy X-rays at the APS
Dedicated HEX facilities:1-ID, 11-ID-B, 11-ID-C
Dedicated PDF facility:11-ID-B (since 2005-3)
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High Energy X-Rays at beamline 11-ID at the APS
11-IDThree simultaneously operating stations;
11-ID-D Time Dependent11-ID-C High Energy Scattering11-ID-B Dedicated PDF Beamline
2 Undulators2.3 cm device used by 11-ID-B and -C3.3 cm device utilized by 11-ID-D
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Overview of 11-ID at the APS
11-ID-BPDF measurements
11-ID-CHigh Energy Scattering
11-ID-DTime-Dependent pump-probe XAFS, SAXS, WAXS
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High Energy X-rays at the APS
Available Photon Energies:~59KeV (Si311)~91KeV (Si 511), ~127KeV (Si 711), Monochromator: Laue crystal (Fixed Bragg Angle: 3.8o)Max beam size: 3 x 2 mm2
Flux: 1012 Photons/s
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Dedicated PDF facility at the APS
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The Pair Distribution Function Method
0 10 20 30Q
Inte
nsity
Measured Diffraction Intensity
0 2 4 6 8 10
G(r) = 4πr[ρ(r)-ρ0]
G(r)G(r
)/ Å
-2
r / Å
Si-O 1.6Å
O…O 2.6Å
Si…Si 3.2Å
I(Q) S(Q)
=4πsinθ/λ
FourierTransform
– The structure factor S(Q) can be measured as a function of diffraction angle using monochromatic X-rays
– Application of area detector to yield more rapid measurements by collecting all data simultaneously
P.J. Chupas, X. Qiu, J.C. Hanson, P.L. Lee, C.P. Grey, S. Billinge, J. Applied Cryst., 2003, 36, 1342-1347.
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High Real Space Resolution PDFs:The Need for High Q Measurements
2 4 6 8 10 12 14r(Å)
Qmax = 10 Å-1
Qmax = 15 Å-1
Qmax = 20 Å-1
Qmax = 25 Å-1
2 4 6 8 10 12 14r(Å)
Qmax = 10 Å-1
Qmax = 15 Å-1
Qmax = 20 Å-1
Qmax = 25 Å-1
Qmax=4πsinθ/λ
for Cu Kα, λ=1.54Å, 2θ=180o
Qmax = 4πsin90/1.54 = 8 Å-1
We typically use wavelengths between 0.20 and 0.08 Å
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In situ reduction: PtIVO2 → Pt0
Chupas, Chapman, Lee J. Appl. Crystallogr., 2007, 40, 463-470
Data can be collected in only 30 ms
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In-situ measurements: The reduction of PtO2 to Pt
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Can we probe the structure of weakly bound guest molecules?
Are open metal sites important for binding H2?
Seeing hydrogen with X-rays?!
Hydrogen Storage inPorous Coordination Frameworks
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Open Metal Sites in Prussian Blue Analogues
e.g. MnII
3[CoIII(CN)6]2
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Open Metal Sites in Prussian Blue Analogues
e.g. MnII
3[CoIII(CN)6]2
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Gas Inlet
Sample
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Differential PDF
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Differential PDF
Chapman, Chupas, Kepert J. Am. Chem. Soc. 127, 2005, 11232-11233
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Differential PDF
N-N distance in N2 moleculeChapman, Chupas, Kepert J. Am. Chem. Soc. 127, 2005, 11232-11233
11-ID-B
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Differential PDF
N-framework & N-N interactionsChapman, Chupas, Kepert J. Am. Chem. Soc. 127, 2005, 11232-11233
11-ID-B
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Differential PDF
Chapman, Chupas, Kepert J. Am. Chem. Soc. 127, 2005, 11232-11233
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Hydrogen Differential PDF
H2-framework interactionsChapman, Chupas, Maxey, Richardson Chem. Commun. 2006, 4013-4016
Contribution from disordered H2evident from
X-ray scattering
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Structural Models
Binding at open metal sites
van der Waals interactions only
Chapman, Chupas, Maxey, Richardson Chem. Commun. 2006, 4013-4016
11-ID-B
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GPPD, IPNSStructural Models
Binding at open metal sites
van der Waals interactions only
Chapman, Chupas, Maxey, Richardson Chem. Commun. 2006, 4013-4016
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Enhancing Sorption
Smaller Pores
GreaterΔ
Hsorption
Tune compositionie. pore size M3[Co(CN)6]2
Chapman, Chupas, Maxey, Richardson Chem. Commun. 2006, 4013-4016
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Energy Related Issues from Fossil Fuels
-CO2 management
-Energy security
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High-pressure experiments: The Paris-Edinburgh press
Large sample volume: 3.5 mm diameterRetain microstructure – core sampleNo fluid pressure media
Sample
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High-pressure experiments: The Paris-Edinburgh press
Large sample volume: 3.5 mm diameterRetain microstructure – core sampleNo fluid pressure media
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Applications of Micro-focused High-Energy X-rays(currently available at 1-ID at the APS)
-High pressure Studies from Diamond Anvil Cells
-Spatially Resolved Measurements
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Bent Laue MonochromatorFocusing Lens
(Si saw-tooth type*)
Focusing High-Energy X-Rays at 1-ID
*S. D. Shastri et al., J. Synchrotron Rad., 14, 204 (2007)
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PDF at High Pressures
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PDF of Gold in the DAC and Measured ex-situ
Martin, Antao, Chupas, Lee, Shastri, Parise Applied Physics Letters 86 (2005) 061910.
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High Pressure PDF
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Gold at High Pressures
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Time Resolved Studies:
Supported Metal CatalystsFollowing the kinetics formation of catalytic particles
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TiO2 Substrate
H2/200oC 200oC
Forming Supported Nanoparticles
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Pt4+ + 4 e- → Pt0
H2 → 2H+ + 2e-
Forming Supported Nanoparticles
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Gas in Gas out
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Reduction of 5% Pt4+ on TiO2 Under H2
•Reduction at constant temperature, 200 ˚C
Ti-O
O-OPt-Pt
5wt % Pt on TiO2(via aqueous impregnation with H2PtCl6)
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In situ reduction: Pt4+ on TiO2 → Pt0
Chupas, Chapman, Jennings, Lee, Grey J. Am. Chem. Soc., 2007, 129, 13822-13824.
G(r)Pt/TiO2− G(r)TiO2
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Tracking the Kinetics of Particle Formation
Pt-Cl correlation
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Tracking the Kinetics of Particle Formation
Pt-Cl correlation
zero-order reactionr = k
The rate is independent of concentration for a zero-order reaction.
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High Temperature Measurements
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Ceria as a Support/Catalyst
Ceria is a major component of Three Way Catalysts: Which Simultaneously treat the reducing pollutants CO and CxHy, and the oxidizing pollutant NOx
Oxidation: 2 CO + O2 → CO2
CxHy + O2 → CO2 + H2O
Reduction 2 CO + 2 NO → 2CO2 + N2
CxHy + NO → CO2 + H2O + N2
Ceria acts as an oxygen reservoir to stabilize the air/fuel ratio
Fluorite structure with variable composition
CeOx 1.75<x<2.0
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In-situ Reduction of CeriaPreviously identifieddefect ordered phases (Ray, et al.)α-CeO2δ-CeO1.817ξ-CeO1.770ι-CeO1.714 25 ºC
600 ºC700 ºC
0 2 4 6
Tem
p.
H2 O2 H2 O2 H2
Time (hours)
25 ºC
600 ºC700 ºC
0 2 4 6
Tem
p.
H2 O2 H2 O2 H2
25 ºC
600 ºC700 ºC
0 2 4 6
Tem
p.
25 ºC
600 ºC700 ºC
0 2 4 6
Tem
p.
H2 O2 H2 O2 H2
Time (hours)
S.P. Ray, A.S. Nowick, D.E. Cox. J. Solid State Chem., 15, 344-351, (1975)
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Studying Local Structure During Chemical Reactions
600 ºC
700 ºC
O2 O2H2H2 H2
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Frenkel Defects in nano-CeO2
O1
O2
Mamontov and Egami Journal of Physics and Chemistry of Solids 61 (2000) 1345.
Complementary Methods17O MAS NMR
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0 1 2 3 4 5 6
700
500
300
100
Time (hours)
Temp.(ºC
)
460
430
400
Inte
nsity
Nano-CeO2: Changing Oxygen Content
Inte
gral
Pea
k In
tens
ity 3
.85
Å
Oxygen is removed from the 01 site in nano-Ceria on Reduction
H2 H2 H2
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What are the opportunities…
(1) Simultaneous measurements-combine PDF, SAXS, (maybe even EXAFS ???)
(2) Chemically Resolved Measurements-resonant scattering
(3) Energy Resolved Measurements-Discriminating Compton Scattering
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Common Instrumentation Configurations
e− orbit
double crystalmonochromator
ionchamber
slitssample
diffractometer
analysercrystal
detector
e− orbit
double crystalmonochromator
ionchamber
slitssample
area detector
beam stop
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Rapid Energy Resolved Measurements?
Beno and Knapp Review of Scientific Instruments (1995) 60, 1308-1310.
Cs2Ge4O9
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Combined PDF and SAXS measurements
e− orbit
double crystalmonochromator
ionchamber
slitssample
area detector
beam stop
area detector
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High Energy Resolution Optics for High-Energy X-rays:
Potential for Anomalous PDF Measurements
S. D. Shastri, J. Synchrotron Rad., 11, 150 (2004)
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Example of High-Energy Resonant Scattering
Distribution of Pb and Bi in Pb5Bi6Se14
Bi and Pb distributed over 11 crystallographically unique sites
Zhang, Wilkinson, Lee, Shastri, Shu, Chung, Kanatzidis, J. Applied Crystall., 38, 433 (2005)
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Acknowledgements
Karena W. Chapman (XSD, ANL)Randy Winans (XSD ANL)Peter L. Lee (XSD ANL)Guy Jennings (XSD, ANL)Clare P. Grey (Stony Brook)Evan R. Maxey (XSD, ANL)James Richardson (IPNS, ANL)Jon Hanson (BNL)Jose Rodriuguez (BNL)
Peter L. Lee (XSD, ANL)Mark Beno (XSD, ANL)Sarvjit Shastri (XSD-ANL)John B. Parise (Stony Brook)C. David Martin (XSD, ANL)Gabrielle Long (XSD, ANL)John W. Cahn (NIST)Leo Bendersky (NIST)
Work performed at the Advanced Photon Source was supported by the U.S. Department of Energy, Office of Science, Basic Energy Sciences, under Contract No. DE-AC02-06CH11357.