Beamline practice at BL01B1 (XAFS)
In-situ XAFS measurement of catalyst samples
ver. 2014/08/26 K. Kato, K. Nitta, T. Uruga (JASRI), P. Fons (AIST/JASRI)

1. Introduction
The bending magnet beamline, BL01B1, is used for various applications of XAFS over a wide
energy range from 3.8 to 113 keV. In the practical training course, we plan to show how to measure
XAFS spectra, which covers alignment of X-ray optics and sample position. We will also
demonstrate in-situ time-resolved quick scanning XAFS measurement of catalyst samples underreaction condition.

2. Plan of practice
9:30-

Introduction of beamline, alignment of optics, measurement system and major scientificactivities at BL01B1.

10:00-

Alignment of the x-ray optics.

11:00-

Setup of the measurement system for Quick XAFS in transmission mode.

11:30-

X-ray energy calibration using standard sample.

12:00-

Introduction of preliminary process of XAFS spectra using software ATHENA.

12:30-------- Lunch -----------

13:30-

Introduction of in-situ XAFS experiment and sample preparation.

14:00-

Setup of in-situ XAFS experiment system.

15:00-Measurement of in-situ XAFS spectra of catalysts during reduction process.
During the measurement, data treatment and preliminary analysis of XAFS spectra.

17:00

Close.

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3. Alignment of x-ray optics and experimental stage
 Figure 1 shows schematic layout of BL01B1.
 Main operation in alignment of x-ray optics is follows.
 Switch of diffraction plane of monochromator crystals between Si(111), Si(311) andSi(511) to cover energy range for XAFS measurements.
 Change of glancing angle of mirror to remove higher-harmonic x-rays.
 Above operation slightly changes beam height downstream of monochromator.
 Fine adjustment of slits and mirrors in the optics hutch is done by measuring x-ray intensity
using 1st ionization chamber in the experimental hutch (Fig. 2).
 The height of experimental stage in the experimental hutch is adjusted to x-ray beam byscanning in vertical direction.
 Fixed beam condition is achieved by adjusting the rotation angle of 1st crystal of
monochromator around beam axis to 2nd crystal.
 The control program for operation of x-ray optics realizes following x-ray beam.
 Quite low contamination (<10-5) of higher harmonics.
 Fixed beam position during XAFS scans passing through the center of slits in theexperimental hutch.
 Focused beam in vertical direction (0.1-0.2 mm).
 In the BL practice, the participants will align the optics following the manual upped on theWEB site, http://bl01b1.spring8.or.jp/BL01B1opticsmanEng040213.html.

Optics hutch

Experimetal hutch
Measurement
systemX-ary

Fig. 1 Schematic layout of BL01B1

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4. Quick XAFS measurement in transmission mode
 Quick XAFS measurement is realized by data storage of x-ray detector output signals andBragg angles of monochromator in each memory board during continuous scanning.
 The arrangement and control system for transmission mode Quick XAFS measurements areshown in Figs. 2 and 3.
 Setup the ionization chambers.
 Select and flow adequate gases for ionization chamber.
 Gases are selected to have the following absorption ratio of incident x-rays; 10-30 % for I0
chamber and 70-90 % for I chamber, respectively.
 Gases are listed in the WEB site, http://bl01b1.spring8.or.jp/RatioI0.html andhttp://bl01b1.spring8.or.jp/RatioI1.html.
 Setup of measurement system
 Set the beam size incident on the sample by slit opening.
 Set the gain of current amplifiers (Amp) for each ionization chamber.
 Operation of program of Quick XAFS measurement
 Set the following parameters in the operation program

Energy range and step for a XAFS spectrum

Total measurement time for a XAFS spectrum.

5. Preliminary process of XAFS spectra using software ATHENA
 The row data of Quick XAFS spectra are processed to the ATHENA-readable data format.
 ATHENA processes the measured XAFS spectra, such as background removal and Fouriertransforms.
 ATHENA is one of most popular free software for processing XAFS data.
http://cars9.uchicago.edu/~ravel/software/ Model fitting of XAFS data is done by another software ARTEMIS including interfaces toATOMS and FEFF.

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I0 ionizationchamber

X-ray

SampleI1 ionizationchamberFig. 2 Setup of transmission mode XAFS

Monochromator

2nd Mirror

1st Mirror

X-rayθ axisEncoder
MemorySampleI0IAmpAmp

VFC

VFC
ScalarStepper motor
controller

MemoryBeamline
Work StationPCfor control andmeasurement

Piezo
DriverDACFig. 3 Control system of QXAFS measurement system in transmission mode4

6． Measurement of in-situ XAFS spectra in transmission mode
6.1 Sample preparation
 The sample for XAFS measurement is form into thin disks of 7 mm diameter by pressmachine with very weak pressing force.
 Put adequate number of disk samples (around 20) into sample holder to achieve edge jumpabsorbance around 1.

Fig. 4 Mount of disk sample into inner holder of sample cell5

6.2 Setup of in-situ XAFS equipments
 Experimental condition in this in-situ measurement Sample: Pd/USY catalyst
 Measurement energy: around Pd K-edge (24.3 keV) Sample temperature: room temperature Reaction gases: H2, O2, He and their mixture Set the sample cell including disk samples.
 Connect Q-mass to outlet of sample cell to monitor the concentration of each outlet gas.

Sample cellQ-mass

Fig. 5 Setup of in-situ XAFS equipments

66.3 In-stu XAFS measurement of catalyst during reduction process XAFS measurement of catalyst in initial state.
 Flow 100%-He 90 ccm into sample cell.
 Measure Quick XAFS spectra in transmission mode.
 The measurement time of each XAFS spectra during this experiment is about 30 s.
 XAFS measurement of sample during reduction process.
 Flow 8%-H2/He 90 ccm (H2: 7ccm, He: 83 ccm) into sample cell for 15-20 min.
 Measure Quick XAFS spectra every 30 s during gas flow.
 Check change of Fourier transform-XAFS spectra during reduction process usingATHENA.
 Stop 8%-H2/He flow.
 Flow 100%-He for 10-15 min until no residual H2 in sample cell (checking by Q-mass).
 Measure Quick XAFS spectra.
 Check the sample color.

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