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logo ROCK SOLEIL

ROCK : Rocking Optics for Chemical Kinetics
ROCK time-resolved X-ray absorption spectroscopy (XAS) beamline Energy range 4 - 40 keV

 

 

The purpose of this EQUIPEX project is to build within the existing SOLEIL synchrotron facility and to operate for the benefit of academic and private research projects a new time-resolved X-ray absorption spectroscopy (XAS) beamline based on the quick-scanning energy principle, the so called QuEXAFS

label investissement d'avenirThe ROCK beamline (ROCK being the acronym for Rocking Optics for Chemical Kinetics) is devoted to the study of fast kinetic processes in nanomaterials used in catalysis and batteries. The objective is to contribute to the development of more efficient catalysts and batteries which should find successful industrial applications in the field of energy generation and storage in compliance with the protection of public health and environment. The better knowledge at the atomic scale of nanomaterials involved in catalysis or energy storage provided by time-resolved XAS is recognized by the concerned communities as mandatory for establishing synthesis strategies leading to important breakthroughs in the production of energy from renewable sources and in the development of advanced energy storage devices. 

Team

BARTHE
BARTHE Laurent
Assistant Ingénieur de Ligne De Lumière
BELIN
BELIN Stephanie
Scientifique de Ligne De Lumière
BRIOIS
BRIOIS Valerie
Responsable de Ligne De Lumière
LA FONTAINE
LA FONTAINE Camille
Scientifique de Ligne De Lumière
POSSATO
POSSATO Luiz-Gustavo

Collaborator

IADECOLA Antonella (RS2E CNRS)
    01 69 35 94 68
antonella.iadecola@synchrotron-soleil.fr

Technical data

Energy range

from 4.5 to 40 keV

Energy resolution (∆E/E)

2 10-4 to 5 10-5

Source

bending magnet (Ec = 8.65 keV)

Flux

Si(111) @ 8.0 keV : 2 1012ph/s
Si(220) @ 20 keV : 5 1011ph/s

Optics

Collimating toroidal mirror of Si  with a coating of Ir (50nm) ;

2 QuEXAFS (Si111 and Si220) monochromators  between a flat mirror and a  collimating mirror both in Si with three stripes (Pd, Pt and B4C) for harmonic rejection

Sample environment

Catalysis devices (ovens, gas rack distribution, mass spectrometer ...)
Electrochimical thermostable cells multichannel potentiostat
Raman and UV-visible spectrometers
Differential Scanning Calorimetry

Beam size

horizontal : from 350 µm to 4.9 mm (FWHM)
vertical : from 190 µm to 2.2 mm  (FWHM)

Detectors

OKEN ionization chambers
Avalanche photodiode

Scientific opportunities

Nanomaterials used in catalysis and batteries

 

More information : on the optics (mirrors and monochromators) of the optical hutch, and on the description of the EXAFS experimental hutch.

Optical Hutch

Storage ring : Toroidal collimating mirror M1 (CINEL/Winlight X)

enceinte M1 anneau ROCK

M1

Fixed Grazing Incidence : 2.5 mrad
Ir (50 nm)
Roughness 5 Å <
Tangential slope error: 0.5 μrad RMS
Sagittal slope error : 20 μrad RMS
Water Cooled
Total absorbed power : 87 W
Absorbed power density : 4 mW/mm 2

Collimating principeCollimating principe :

 

 

Optical hutch :  Mirrors M2a and M2b harmonic rejection and vertical focusing (IRELECALCEN/Winlight X)

 

M2aM2a

M2bM2b

Acceptance 1.5 (H) x 1.0 (V) mrad2 1.5 (H) x 1.0 (V) mrad2
Source distance 16.82 m 22.44 m
Optical active area 47 mm x 1100 mm 47 mm x 1100 mm
Coating 3 stripes Pt layer 50 nm, Pd layer 50 nm and B4C layer 5 nm  3 stripes Pt layer 50 nm, Pd layer 50 nm and B4C layer 5 nm
Roughness less than 3 Ǻ RMS less than 3 Ǻ RMS
Longitudinal slope error 1 µrad RMS/best spherical fit 1 µrad RMS/best spherical fit
Sagittal slope error 5 µrad RMS 5 µrad RMS
Orientation Reflecting vertically upward Reflecting vertically qownward
Working pitch angle

1.75 mrad to 5.2 mrad

1.75 mrad to 5.2 mrad
Shape Flat mirror : R > 20 km Bending radius range : 1.5 km < R < 20 km
Cooling system Water cooling No cooling
Maximum total absorbed power 78 W -
Maximum absorbed power density 19 mW/mm2 -

 

Quick-EXAFS monochromator

Expected flux at the focusing point

The SOLEIL designed Quick-EXAFS monochromators are made of two independent channel-cut crystals (Si(111) and Si(220)) and was first used on SAMBA beamline. Each channel-cut crystal is mounted on a cam driven tilt table allowing it to oscillate periodically with amplitude θ(t) around an average fixed Bragg angle θB. The amplitude can be tune from 0.1 to 4° by an original SOLEIL in vacuum variable cam design. The θB Bragg angle is selected by one of the two goniometers holding the oscillating tilt tables. The 4.5 to 40 keV energy range is available using both Quick-EXAFS monochromators. The channel-cut crystal can be changed by the other one in few seconds during an experiment allowing to record quick-EXAFS data at absorption edges very far in energy. For instance the XAS study of a bimetallic catalyst at both edges during the same catalytic reaction is now possible with the ROCK’s QuEXAFS set-up, even if the edge energies of those elements are covered by two distinct crystals.

Quick-exafs monochromator

Maximum performance of the Quick-EXAFS mechanics in terms of oscillation frequency of the channel-cut is 40 Hz for two recorded spectra: one with the Bragg angle collection in the downward direction and the other with the Bragg angle collection in the upward direction. Due to the photon flux available at the sample position at the SAMBA beamline in QuEXAFS configuration ((flux ~ 1011 ph/s at 8 keV) the optimal time resolution of experiments on real concentrated and not too absorbing samples is around 100 ms. On ROCK we expect to reach 1012 ph/s in 50 ms.

(left) Absorption of stacked Cr and Mn metallic foils measured over an amplitude of 3.6 °. Data are the average of 10 spectra each collected at 1Hz. (right) k2 weighted Quick-EXAFS are compared to standard scans taken in almost 15 min.

 

Related publications:

The SAMBA Quick-EXAFS monochromator: XAS with edge jumping
E. Fonda, A. Rochet, M. Ribbens, S. Belin, L. Barthe, V. Briois
Journal of Synchrotron Radiation (2012), 19, p 417 - 424

 

EXAFS Hutch

 ►Quick-exafs Mode

 

Crystal type : Si111 Si220 Si311 (4 to 40 keV)
Beam size : from 350 x 79 µm2 to 4.9 x 2.2 mm2
Flux ~ 1012 ph/s at 8 keV


Transmission

Oken ionization chambers

Fluorescence

Avalanche Photo Diode (APD)

TEY

Ni K edge XAS signal (up) collected in a TEY detection mode on a Proton Exchange Membrane Fuel Cell thick film in the Quick-EXAFS mode after correction of glitches. The presented spectrum is not averaged (5s of time acquisition).The frequency of oscillation of the Si(111) channel-cut was 0.1 Hz (5s per spectrum) with an oscillation amplitude of 1.6°.

No picture. The sample must be electrical conductor otherwise a thin layer of graphite may be evaporated. 

Edge Jump

Large energie range from 4 keV (Si111) to 37 keV (Si311) in 30s
The remote selection of the monochromator crystals, Si(111) or Si(311), allowing users to permanently access energies between 4 and 37 keV in Quick-exafs mode. 

E. Fonda, A. Rochet, M. Ribbens, S. Belin, V. Briois The SAMBA quick-EXAFS monochromator: XAS with edge jumping J. Synchrotron Rad. 2012, 19, 417 – 424.

Example of the energy range accessible with Si111 cam=4°

Set-up and combined experiments

 

CombinedTechniques

ROCK's experimental station EXAFS is characterised by a lot of techniques combined to XAS, such as Differential Scanning Calorimetry, Raman Spectroscopy and UV-Visible Spectroscopy.

XAS with Raman spectroscopy

Kosi RXN1-785 Kaiser

Iexc. = 785 nm or 532 nm 
CCD: 100-3450cm-1 or 200-4000 cm-1 
Optical fibers
with probehead 
Seceral Long Working Distance
objectives (150 mm to 35 mm)
XAS with UV-visible spectroscopy

Cary 50 VARIAN

With optical fibers
190 < I < 1100 nm
VScan < 24000 nm/min
XAS cell with mylar or PP windows for optical fiber used in transmission
or immersion probe : 2 or 10 mm
or cuvettes Quartz, Glass, PMMA, PS
XAS with Raman and UV-Visible spectroscopies  
XAS with Differential Scanning Calorimeter (DSC) 
DSC 111 Setaram :

Calvet type differential scanning calorimeter 
-120 to 800°C 

* Phase transition (fusion, crystallization, glass transition, polymerization, degradation)
*  Cp Evaluation
*  Monitoring of reactions (oxidation, reduction, dehydration...)

 

Catalysis

Retrouvez ci-dessous les différents environnements échantillons catalyseurs à votre disposition sur la station EXAFS.

Polyvalent SOLEIL development for fluorescence, transmission and Raman coupling

La Fontaine, C., Barthe, L., Rochet, A., & Briois, V.
X-ray absorption spectroscopy and heterogeneous catalysis: Performances at the SOLEIL's SAMBA beamline. Catalysis Today, 2013, 205: 148–158

Two ovens/capillaries set-up collaboration MAX IV/SOLEIL designed by L. Barthe

Characteristics    Lytle-type cell

  • RT 600°C +/- 0.5°C
  • Atmospheric pressure
  • Powdered catalyst gently pressed into the cavity of the sample hoolder (thickness 2, 4 and 6 mm, 0.10 - 0.25 cm3)

 

 

 

 

 

Characteristics 2 capillaries oven

  • RT 1000°C +/-0.5°C

High pressure cell for transmission and Raman coupling

A. Rochet et al. Catalysis Today (2011) vol 171 186-191 
A. Rochet et al. Diamond Light Source Proceedings (2011) 1, e130 1-4

Characteristics  Lytle-type cell

  • RT 600°C +/- 0.5°C
  • 50 bar
  • Powdered catalyst gently pressed into the cavity of the sample holder (thickness 2 mm)


Commercial cell Harrick for fluorescence and Raman coupling

C. La Fontaine et al. Harrick Scientific Products (Ed.), Application Note n°91201 (2010).

Characteristics

  • RT 500°C
  • Atmospheric pressure
  • Powdered catalyst (≈50 mg) gently pressed into the sample holder cavity
  • Catalyst pellet (6 mm dia.) disposed onto a BN bed

Gas distribution system

  • Complex mixtures
  • Saturator for liquid reactants
  • Heated lines (120°C)
  • Patm --> 20 bar
  • Remote control

Mass spectrometer

MKS Cirrus
LM99 Analyser

  • Tripple mass filter, 1-200amu or 1-300amu
  • Faraday and SEM detector
  • Maximum operating pressure Faraday 2x10-5 mBar

Low temperature

With the courtesy of SAMBA beamline

Helium Cryostat He cryostat suitable for transmission and fluorescence detection 
(20 K to Room Temperature)
Nitrogen Cryostat Liquid nitrogen (80 K) cryostat suitable for transmission and fluorescence detection

Liquid Cells

We have different cells with fixed or variable optical path available for basic or acidic solution. Two of them are thermostatically controlled. Note Kapton, Mylar, PP or PTFE can be used as windows depending of the nature of the solution.

Liquid cell with variable optical path for transmission Thermostated liquid cell (PTFE) with  adjustable optical paths (10 µm to 6 mm)  suitable for the combination of  transmission XAS with UV-Vis spectroscopies (design SPECA)
Liquid cell for transmission Liquid cells PTFE with fixed optical paths
(0.5<o.p.<5mm)
Liquid cell for fluorescence mode Liquid cell (PCTFE) for fluorescence detection
(design F. Villain)
Liquid cell for biological sample

PTFE sample-holder for He cryostat 
(two samples ~ 50µl) available for 
transmission and fluorescence detection

With the courtesy of SAMBA beamline

Thermostated liquid cell

Thermostated liquid cell (PCTFE) with adjustable optical paths (100µm to 10mm) suitable for the combination of transmission XAS with Raman and/or UV-Vis spectroscopies
(design F. Villain)

 

 

Thermostated liquid cell (PTFE) with adjustable optical paths (10µm to 6mm) suitable for the combination of transmission XAS with UV-Vis spectroscopies (design SPECA) 

Energy Science

Setup for Li/Na batteries

VMP3 Bio-logic Multi-channel Potentiostat 

16 independent channels, 6 already equipped (+/-400mA) whose one for impedance measurement

ANR  Electrochemical cell dedicated to operando XAS
J. B. Leriche et al. J. Electrochem. Soc., 157, (5) A606-A610 2010
Multicell support
Furnace RT to 90°C
for 2 electrochemical cells for example
Thermostated support

 

Notices

EXAFS :                                    

PDF icon gnuplothowto.pdf (114.69 KB - pdf) (114.69 KB)
Media Folder: 
GnuplotHOWTO.pdf                 

QuickExafs        

         

TBT_cryostats.pdf 

Information for the users, help for preparation and submission of proposal.

Help for project submission

 How to prepare your Beamtime application ?

Project must be written in english and submissions must comply to the following framework : 

Online submission of the web form to give general information 

  1. Description of the scientific background and experimental part 
  2. Figures or images in annex (format .jpeg .png)
  3. Description of experimental conditions with special safety measure
  4. Submission of the proposal

(If the application constitutes the project continuation, filing in a report of the previous experiment in the SunSet and mention of related publications are necessary) 

Also,

- It is strongly advised to contact one of the beamline scientist, they will assist in the definition of the setups necessary for the desired experiment and in the assessment of the best conditions. 
- The justification of the required beamtime is required. 

Do not forget to mention your related publications in the sunset

For more informations : The general User's guide  

 

 

Préparation des échantillons

Gaz

The application for the use of specialty gases must be stipulated in your proposal in order that the security service can assess the associated risks. Specialty gases must be commanded 8 weeks before your experiment, also you have to prevent your local contact well in advance, for common gases (helium, argon, nitrogen, hydrogen, air and oxygen) only 2 weeks are sufficient.  

Helium liquid

The application for the use of helium liquid must be stipulated in your proposal and recalled to your local contact in such a way to order sufficiently in advance the suitable volume.