Nuclear Instruments and Methods in Physics Research A 649 (2011) 213–215

Contents lists available at ScienceDirect

Nuclear Instruments and Methods in

Physics Research A
journal homepage: www.elsevier.com/locate/nima

Combined XRD and XAS

S.N. Ehrlich a,n, J.C. Hanson b, A. Lopez Camara b, L. Barrio b, M. Estrella b, G. Zhou b, R. Si b,
S. Khalid a, Q. Wang c
a
NSLS, Brookhaven National Laboratory, Upton, NY 11973, USA
b
Chemistry Department, Brookhaven National Laboratory, Upton, NY 11973, USA
c
Synchrotron Catalysis Consortium, University of Delaware, Newark, DE 19716, USA

a r t i c l e in f o abstract

Available online 24 November 2010 X-ray diffraction (XRD) and X-ray absorption fine structure (XAFS) are complementary techniques for
Keywords: investigating the structure of materials. XRD probes long range order and XAFS probes short range order.
XRD We have combined the two techniques at one synchrotron beamline, X18A at the NSLS, allowing samples
XAFS to be studied in a single experiment. This beamline will allow for coordinated measurements of local and
Combined XRD/XAFS long range structural changes in chemical transformations and phase transitions using both techniques.
Quick XAFS & 2010 Elsevier B.V. All rights reserved.
Time-resolved XRD

1. Introduction
Structural characterization is essential to understand materials.
XRD provides long range information of the atomic arrangement of
crystalline systems, whereas XAFS provides an element-specific
probe of the electronic information and local structure of amor-
phous samples as well as ordered phases [1]. The combination of
these two complementary methods offers possibilities for obtain-
ing a more complete structural view. Recent developments in time-
resolved detectors [2] and in-situ reactors [3] as well as fast data
acquisition hardware and software [4] make it possible to follow
the dynamic and mechanistic changes of a reaction system in-situ
and under realistic conditions using combined time-resolved
techniques [5,6]. We present in this manuscript the recent upgrade
of the NSLS X18A beamline, which features the capability for
combined XRD and XAFS. The potential applications of such a setup
are demonstrated in selected examples.
2. Experimental equipment
The X18A bending magnet beamline at the NSLS, formerly a
scattering and diffraction beamline, was upgraded recently with an
energy scanning monochromator designed to do XAFS and quick XAFS
[7,8]. The monochromator uses a channel cut Si(1 1 1) crystal with an
energy range of  5–40 keV. A Rh-coated, toroidal, focusing mirror
reduces the upper energy to 25 keV. The monochromator (Fig. 1) can
be driven with a 5-phase stepping motor for scanning at standard
speeds for regular XAFS. It can also be driven quickly through a given
n
Corresponding author.
E-mail address: ehrlich@bnl.gov (S.N. Ehrlich).
energy range with a tangent arm at 0.1–1.2 Hz, using a cam and DC
motor, for performing quick XAFS. The monochromator angle is
measured independently with a high speed Heidenhain RON905
rotary encoder capable of 0.000051resolution.
2.1. XAFS setup
Ion chambers can be mounted before and after the sample to
perform XAFS measurements. A fluorescence detector can also be
mounted. Signals from the ion chambers are sent through Keithley
428 current amplifiers, and then through V-F convertors, before
being collected by a VME based scaler, along with that of the
fluorescence detector. XDAC [9] and SPEC softwares are available
for data acquisition.
Quick XAFS (XANES or EXAFS) allows one full scan to be
completed in as short as 0.5 s for concentrated samples, while
for dilute ( o  1%) samples the typical scan time for XANES and
EXAFS are 5 and 15 s, respectively. The quality of data collected in
0.5 s is sufficient to observe any changes in XANES or EXAFS for
concentrated samples, with an incident flux of about 1011 photons/s
at X18A [7].
2.2. Diffraction setup
We have used a variety of detectors for diffraction at the X18A
beamline. These include a point detector (NaI, SiLi or APD),
position-sensitive proportional counter, a silicon position-sensi-
tive detector and an area detector.
A PerkinElmer amorphous silicon area detector [10] is
409.6 mm2 with 2048  2048 pixels and a 200 mm pixel size. Data
from the area detector is collected by a PCI-X frame grabber board
in a Windows computer. The area detector can be mounted on the

0168-9002/$ - see front matter & 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.nima.2010.11.076
214 S.N. Ehrlich et al. / Nuclear Instruments and Methods in Physics Research A 649 (2011) 213–215

monochromator software [9] to collect XAFS data and SPEC commands to accumu-
late a series of diffraction patterns from the SiLD detector. (2) If we
use the PerkinElmer area detector, we can alternate under SPEC
inter-process control of the PerkinElmer detector with QXRD
software [11] and SPEC stepped energy scans. (3) We can manually
x-ray beam alternate the SPEC inter-process control of the PerkinElmer detec-
tor with QXRD and the QEXAFS programs [4].
encoder

tangent arm 3. Applications

stepping motor
cam & DC motor Combined XRD and XAS at beamline X18A have been demon-
strated in regular mode by the following two examples, where we
Fig. 1. Monochromator is shown with a direct-drive using the stepping motor or
a quick cam drive with a DC motor. followed the reduction of metal oxide catalysts using both
techniques.

3.1. Reduction of CuFe2O4

CuFe2O4 has an inverse spinel structure in which Cu2 + and Fe2 +

ions occupy octahedral sites, whereas Fe3 + are found at the
tetrahedral sites. Copper and iron oxides are good catalysts for

Fresh sample (lower curve)

After CO reduction at 200 oC
1500
Cu0
CuFe2O4
Intensity / a.u.

1000

Fig. 2. PerkinElmer 2D detector for XRD and ion chambers (It and Iref) for XAFS. I0
is to right of sample (not shown). X-ray beam is coming from right.
500

2y arm of the diffractometer, usually 42 cm from the sample

position. It can measure a total angular range of approximately
501 at this distance. 0
A Silicon Diode Linear Detector (SiLD) designed by the NSLS 20 25 30 35 40
Detector Group (D.P. Siddons) is 80 mm long with 640 channels, 2θ / degrees
each of 125 mm pitch  4 mm width. It has an energy resolution of
350 eV at 5.9 keV and can be controlled through EPICS/SPEC with a
speed of up to 30 full readouts/s. It can also be mounted on the 2y 1.5
arm, where it spans an angular range of 3.21.
Both of these detectors can be stepped in 2y for additional
angular range. The exposure time required for good quality spectra
Normalized Absorption Coefficient

for any of these detectors is 10 s, while the time required to see
changes in diffraction peaks is r1 s. Exposure times for these 1.0
detectors, of course, vary according to the diffracting power of the
sample and the incident X-ray flux.

2.3. Combined data acquisition

0.5
Fig. 2 shows a typical setup with the PerkinElmer area detector
mounted on the 2y arm of the diffractometer, as well as ion
RT
o
chambers used for XAFS measurements. The 2y arm is set at 401 to 150 C
allow the area detector to clear the ion chambers. At this angle, the o
0.0
200 C
area detector can measure from approximately 151 to 651 in 2y. The
area detector can be used at a lower angle if only fluorescence XAFS
data is collected (and the ion chambers are removed). 8960 8980 9000 9020 9040
Energy (eV)
Data collection for combined XRD and XAFS can be done in
various ways both manually and by software control. (1) If we use Fig. 3. (a) XRD patterns at RT and at 200 1C collected with SiLD detector and
the SiLD detector we can manually alternate between XDAC (b) XANES spectra at RT, 150 and 200 1C.
 S.N. Ehrlich et al. / Nuclear Instruments and Methods in Physics Research A 649 (2011) 213–215 215

3.2. Reduction of inverse Cu/Ceria catalyst

4500 The second example is an inverse CuO/CeO2 catalyst, which has

4000 been proven to be a very active and stable system for the WGS [13]
3500 and PROX [14] reactions. The CO reduction experiment was carried
out at isothermal conditions with 5% CO in He flowing through the
3000
reaction cell. Diffraction patterns were acquired with the Perki-
2500 nElmer area detector with acquisition times of 30 s per pattern.
2000 Fig. 4a shows the evolution of diffraction with time. Fig. 4b shows
1500 the XANES data collected before and after the series of powder
100 diffraction measurements during CO reduction of the catalyst at
80 200 1C. This XANES data demonstrates that the reduction occurred
no.

60 at the Cu site, confirming the conclusion of phase changes from CuO

n

40 to Cu in the time-resolved XRD. The complementary capabilities of

sco

20 20 XRD and XAFS are well illustrated by this example.

16 18
0 10 12 14
2theta
4. Conclusion

This manuscript presents the updated capability of NSLS beam-

line X18A. In-situ experiments of two catalyst systems are shown
to demonstrate the application, where both XRD and XAFS could be
applied in-situ to the same sample. The combination of the two
Normalized Absorption Coeffcient

1.2
complementary techniques at one beamline will make it possible to
investigate complex reaction systems under the same conditions
and, equipped with quick XAFS [7,8] and fast XRD detectors, will
provide the capability to do faster time-resolved studies in the
0.8 future. The increased intensity and brightness at NSLS-II will make
it possible to collect data at smaller time intervals while preserving
the quality of data. Such a setup will surely open many new
opportunities for a broad range of sciences, including those fast
0.4 developing areas such as catalysis and bio-catalysis.
Fresh
Reduced at 200°C Acknowledgements

0.0 We wish to thank A. Lenhard, S. Cheung, R. Greene, I. So and

J. Kirkland for their technical and software assistance. The work at
8960 8980 9000 9020 9040 the NSLS was supported by the US DOE Grant nos. DE-FG02–
Energy (eV) 03ER15688, DE-AC02–98CH10886 and DE-FG02-05ER15688.

Fig. 4. (a) Series of powder patterns collected with PerkinElmer area detector
o
at 2y ¼40 % . Exposures were 30 s, but were grouped in averages of 5 for clarity and
(b) XANES spectra of copper ceria catalyst at RT and 200 1C.
oxidation reactions, such as the water gas shift reaction; therefore
this CuFe2O4 spinel is a relevant system for in-situ studies [12]. We
have performed reduction under a 5% CO/He flow:
3CuFe2 O4 þ4CO-3Cu þ 2Fe3 O4 þ4CO2
We have alternately collected XRD patterns and full EXAFS for
both Cu and Fe K-edges under steady state conditions at 200 and
300 1C. XRD patterns shown in Fig. 3a were taken with the SiLD
detector. Typical acquisition times were 5 min to cover 301 of 2y
angles, whereas a single 3.21 shot of a representative region was
measured in 30 s. Cu K-edge EXAFS data (Fig. 3b) were acquired in
transmission mode and each spectrum was collected in 30 min.
Both techniques show the reduction of copper from Cu2 + in the
spinel structure to a metallic phase. The reduction occurs directly,
without the appearance of any intermediate oxide species, and
requires a temperature of 300 1C to be fully completed. In-situ XRD
followed the overall structural evolution during the reaction while
time-resolved XAFS on both the Fe and Cu edges probed local sites
of each element during the reaction, making it possible to obtain
the structure of intermediates with independent modeling of the
EXAFS data.
References
[1] J.E. Penner-Hahn, Coord. Chem. Rev. 249 (1–2) (2005) 161.
[2] W.A. Cabiebe, I. So, A. Lenhard, D.P. Siddons, Radiat. Phys. Chem. 75 (2006)
1962.
[3] Stefan Hannemann, Maria Casapu, Jan-Dierk Grunwaldt, Peter Haider,
Philippe Trussel, Alfons Baiker, Edmund Welter, J. Synchrotron Radiat. 14
(2007) 345.
[4] I. So, D.P. Siddons, W.A. Caliebe, S. Khalid, Nucl. Instr. and Meth. A 582 (2007)
190.
[5] Gopinathan Sankar, Paul A. Wright, Srinivasan Natarajan, John Meurig Thomas,
G.Neville Greaves, Andrew J. Dent, Barry R. Dobson, Christine A. Ramsdale,
Richard H. Jones, J. Phys. Chem. 97 (1993) 9550.
[6] Jan-Dierk Grunwaldt, Bjerne S. Clausen, Top. Catal. 18 (1–2) (2002) 37.
[7] S. Khalid, W. Caliebe, P. Siddons, I. So, T. Lenhard, J. Hanson, Q. Wang, N. Hould,
M. Ginder-Vogel, A. Ganjoo, Rev. Sci. Instrum. 81 (1) (2010) 015105.
[8] S. Khalid, S.N. Ehrlich, A. Lenhard, B. Clay, Nucl. Instr. and Meth. A (2010),
doi:10.1016/j.nima.2010.11.074.
[9] XDAC software, Acquisition Software Inc., Shoreham, NY.
[10] PerkinElmer model XRD 1621 CN3—EHS, a-Si sensor operating as a photodiode
array, Frame Rate of 15 fps.
[11] QXRD—Readout Software for Flat Panel X-Ray Detectors, Guy Jennings,
Argonne National Laboratory.
[12] M. Estrella, L. Barrio, G. Zhou, X.Q. Wang, Q. Wang, W. Wen, J.C. Hanson,
A. Frenkel, J.A. Rodriguez, J. Phys. Chem. C 113 (2009) 14411.
[13] L. Barrio, M. Estrella, G. Zhou, W. Wen, J.C. Hanson, A.B. Hungria, A. Hornés,
M. Fernandez-Garcıa, A. Martınez Arias, J.A. Rodriguez, J. Phys. Chem. C 114
(2010) 3580.
[14] A. Hornés, A.B. Hungrı, P. Bera, A. Lopez Camara, M. Fernandez-Garcıa,
A. Martınez Arias, L. Barrio, M. Estrella, G. Zhou, J.A. Fonseca, J.C. Hanson,
J.A. Rodriguez, J. Am. Chem. Soc. 132 (2010) 34.