X-ray diffraction exercises

Dr. Sharon Mitchell and Prof. Javier Prez-Ramrez

Institute for Chemical and Bioengineering, ETH Zurich, Switzerland
E-mail: [email protected] http://www.perez-ramirez.ethz.ch
Characterization of catalysts and surfaces Thermal methods
a) b)
c) d)
b
a
Problem 1
Introduction to thermal analysis X-ray diffraction excercises
Using the 2D lattice given below draw planes corresponding to a) (010) b) (200), c) (110),
and d) (120).
Problem 2
Introduction to thermal analysis X-ray diffraction excercises
The diffraction pattern of copper metal was measured with X-ray radiation of wavelength of
1.315 . The first order Bragg diffraction peak was found at an angle 2 of 50.5 . Calculate the
d-spacing between the diffracting planes in the copper metal.
Braggs law n=2dsin
= 1.315 .
2 = 50.5
= 25.25
d = /2sin
d = 1.54
Note: In order to calculate the d-spacing using Excel, theta must be in radians.
Problem 3
Introduction to thermal analysis X-ray diffraction excercises
X-rays with wavelength 1.54 are reflected fromthe (1 1 0) planes of a cubic crystal with unit
cell a = 6 . Calculate the Bragg angle, , for orders of reflection, n = 1-5.
Problem 3
Introduction to thermal analysis X-ray diffraction excercises
n / radians 2 /
1
0.183 10.5
2
0.372 21.3
3
0.576 33.0
4
0.813 46.6
5
1.139 65.2
Problem 4
Introduction to thermal analysis X-ray diffraction excercises
The quality of the experimental pattern shown below is very poor and only the strongest
reflections are visible. Why might the signal to noise ratio be so low? If this is due to a bad data
collection strategy, howmight this be improved?
Intensity of simulated pattern is
arbitrary, scaled for ease of
visualization cannot directly
compare intensities with
experimental pattern.
Why is it important to obtain a
good signal to noise ratio?
What factors contribute to an
experimental pattern?
Problem 4
Introduction to thermal analysis X-ray diffraction excercises
1) Sample. 2) Background 3) Noise
+ +
Crystallinity/disorder
Quantity
Multiple phases
Amorphous
Particle size
Variation of intensity
with Bragg angle.
Detector dependent
e.g. Bragg-Brentano
geometry greater
divergence of X-ray beam
at higher 2.
Incident beam
Fluctuations in intensity of
incident X-rays.
Inelastic scattering /
absorbance.
Problem 4
Introduction to thermal analysis X-ray diffraction excercises
How could we improve the data collection strategy?
Sample preparation:
Flat sample surface.
Ensure sample fully
illuminated by incident X-ray
beam.
Instrumental:
Ensure incident beam monochromatic.
Focusing of incident and diffracted beam using slits.
Choice of wavelength.
Higher incident beam intensity (synchrotron).
Measurement parameters:
Reduction of step size.
Increased collection time.
Mo K (= 0.71073 ) and Cu K (= 1.54178 ) most
common laboratory X-ray sources. What influence does
have on diffraction pattern?
Problem 4
Introduction to thermal analysis X-ray diffraction excercises
MoK (= 0.71073 )andCuK (= 1.54178)mostcommonlaboratoryXray
sources.Whatinfluence does haveondiffractionpattern?
Shorter lessabsorption Mopreferred forstronglyabsorbingsamples.
Shorter reflections closertogether (Bragg relationship). morereflections are
observablefor2 <90.
SowhyisMonotthepreferred Xraysource?
Brighter incidenceXraybeamproducedfromaCuXraytubethatfromMoatthe
samepower level.
Problem 5
Introduction to thermal analysis X-ray diffraction excercises
Figure 1 shows the X-ray diffraction pattern of nanocrystalline silicon (n-Si) which exhibits
significant line broadening with respect to that of bulk silicon (shown for comparison). Data
was collected using Cu K radiation, = 1.54178 .
i) Describe what factors might contribute to the line
broadening. How could this data be used to
estimate the size of the nano-crystallites?
B
obs
= B
instr
+ B
sample
= B
instr
+ B
size
+ B
strain
B
instr
-Dependent on experimental set up
e.g. Monochromaticity of incident
beam, beam divergence etc.
-Direct relationship with .
- Determined by measurement of
suitable reference.
B
sample
= B
size
+ B
strain
-Crystals have finite size (not infinitely periodic)
B
size
Lattice imperfections (e.g. vacancies, substitutions,
dislocations) B
strain
Problem 5
Introduction to thermal analysis X-ray diffraction excercises
Figure 1 shows the X-ray diffraction pattern of nanocrystalline silicon (n-Si) which exhibits
significant line broadening with respect to that of bulk silicon (shown for comparison). Data
was collected using Cu K radiation, = 1.54178 .
i) Describe what factors might contribute to the line
broadening. How could this data be used to
estimate the size of the nano-crystallites?
B
obs
= B
instr
+ B
sample
= B
instr
+ B
size
+ B
strain
Scherrer equation relates peak width to crystalline domain size
B
strain
Frequently assumed to have the following dependence:
B
strain
(2) = 4
0
tan
Possible to gain information about sample if instrumental
parameters are known.
B
size
1/cos
B
strain
tan

cos
2
L
K
B
size

K = Scherrer constant, L = apparent size of the crystalline domain /
B = Full width half maximum /
= Wavelength /

0
= d/d
Problem 5
Introduction to thermal analysis X-ray diffraction excercises
Figure 1 shows the X-ray diffraction pattern of nanocrystalline silicon (n-Si) which exhibits
significant line broadening with respect to that of bulk silicon (shown for comparison). Data
was collected using Cu K radiation, = 1.54178 .

cos
2
L
K
B
size

cos size B
K
L
Assuming K = 0.89 (i.e. for spherical crystalline domains).
Then the size of the crystalline domains perpendicular to (331), L
(331)
= 1.6 .
ii) For the reflection at 2 = 76.452, the FWHM, B, is
found to be 1.0886after correction for instrumental
contributions. Using the Scherrer equation estimate
the size of the nano-crystalline domains.
Problem 5
Introduction to thermal analysis X-ray diffraction excercises
Figure 1 shows the X-ray diffraction pattern of nanocrystalline silicon (n-Si) which exhibits
significant line broadening with respect to that of bulk silicon (shown for comparison). Data
was collected using Cu K radiation, = 1.54178 .
iii) Why might the size you calculated differ from the average
particle size observed by electron microscopy?
Size of crystalline domain might not be clear from electron
microscopy studies.
Crystalline domain
size may not be
homogeneous.
Gives average value perpendicular to reflection
studied. May not be the same in all directions.
Inaccuracies based on calculation e.g. incorrect
estimation of instrumental / strain broadening etc.
Crystalline domains may not be
spherical.
Problem 5
Introduction to thermal analysis X-ray diffraction excercises
Figure 1 shows the X-ray diffraction pattern of nanocrystalline silicon (n-Si) which exhibits
significant line broadening with respect to that of bulk silicon (shown for comparison). Data
was collected using Cu K radiation, = 1.54178 .
iv) Explain why the reflections of the (400) and (331) planes
are observed as a doublet in the powder pattern of the bulk
sample.
Bulk sample has larger and more ordered crystalline domains reflections are narrower.
Two electronic transitions K
1
and K
2
contribute to K

radiation of similar wavelengths. Each gives rise to a

reflection.
In the nano sample these reflections are broadened and overlap appearing as a single peak.
Most monochromators unable to separate such a small difference.
Effect most observable at higher 2 (Bragg relationship). Intensity K
1
> K
2
.
Introduction to thermal analysis X-ray diffraction excercises
In an effort to design catalysts for the CO
2
reforming of methane, Co-Ce
1x
Zr
x
O
2
catalysts with various ratios
of Ce/Zr were prepared by the co-precipitation method fromthe corresponding metal nitrates. Ce(NO
3
)
3
6H
2
O,
Zr(NO
3
)
4
5H
2
O and Co(NO
3
)
2
6H
2
O in stoichiometric ratios. The CoO content was fixed at 16 wt.%. The PXRD of
the materials obtained is shown in Figure A. The PXRD patterns of the 4 crystalline phases, cubic fluorite
structure of CeO
2
, the cubic and tetragonal phases of ZrO
2
and the catalytic phase Co
3
O
4
identified by the
authors are shown in Figure B.
N. Wang, W. Chu, L. Huang, T. Zhang, J. Natural Gas Chem. 19 (2010), 117.
Co
3
O
4
i) Comparing the reflections in Figure B, what are the
best reflections:
a) to identify the presence of each phase?
b) to differentiate between the tetragonal and cubic
forms of ZrO
2
.
Problem 6
To assign diffraction patterns of multi-phase materials
easiest to identify the most intense reflections first.
Reflection should not overlap with that of another
possible phase.
If a phase is present all reflections should be present, but weaker reflections
may not be visible if signal to noise ratio is low.
Introduction to thermal analysis X-ray diffraction excercises
Problem 6
ii) Based on the information in Figure B, assign the reflections in Figure A as far as you can.
In an effort to design catalysts for the CO
2
reforming of methane, Co-Ce
1x
Zr
x
O
2
catalysts with various ratios
of Ce/Zr were prepared by the co-precipitation method from the corresponding metal nitrates.
Ce(NO
3
)
3
6H
2
O, Zr(NO
3
)
4
5H
2
O and Co(NO
3
)
2
6H
2
O in stoichiometric ratios. The CoO content was fixed at 16
wt.%. The PXRD of the materials obtained is shown in Figure A. The PXRD patterns of the 4 crystalline
phases, cubic fluorite structure of CeO
2
, the cubic and tetragonal phases of ZrO
2
and the catalytic phase
Co
3
O
4
identified by the authors are shown in Figure B.
Co
3
O
4
and CeO
2
, ZrO
2
Introduction to thermal analysis X-ray diffraction excercises
Problem 6
iii) Are any reflections unaccounted for? What might be the origin of these reflections?
Circled reflections
unaccounted for in
reported phase
assignment
In an effort to design catalysts for the CO
2
reforming of methane, Co-Ce
1x
Zr
x
O
2
catalysts with various
ratios of Ce/Zr were prepared by the co-precipitation method from the corresponding metal nitrates.
Ce(NO
3
)
3
6H
2
O, Zr(NO
3
)
4
5H
2
O and Co(NO
3
)
2
6H
2
O in stoichiometric ratios. The CoO content was fixed at 16
wt.%. The PXRD of the materials obtained is shown in Figure A. The PXRD patterns of the 4 crystalline
phases, cubic fluorite structure of CeO
2
, the cubic and tetragonal phases of ZrO
2
and the catalytic phase
Co
3
O
4
identified by the authors are shown in Figure B.
Introduction to thermal analysis X-ray diffraction excercises
Problem 6
iv) By looking at the variation in peak broadening, what can we tell about the variation in crystallinity with
composition?
In an effort to design catalysts for the CO
2
reforming of methane, Co-Ce
1x
Zr
x
O
2
catalysts with various
ratios of Ce/Zr were prepared by the co-precipitation method from the corresponding metal nitrates.
Ce(NO
3
)
3
6H
2
O, Zr(NO
3
)
4
5H
2
O and Co(NO
3
)
2
6H
2
O in stoichiometric ratios. The CoO content was fixed at 16
wt.%. The PXRD of the materials obtained is shown in Figure A. The PXRD patterns of the 4 crystalline
phases, cubic fluorite structure of CeO
2
, the cubic and tetragonal phases of ZrO
2
and the catalytic phase
Co
3
O
4
identified by the authors are shown in Figure B.
Narrowest reflections observed for single phase oxides (e.g. CeO
2
or
ZrO
2
).
Assuming identical synthesis conditions in all cases this is unlikely
to be due to large differences in crystal domain size as time for
crystal growth would be equivalent Greater crystallinity.
At intermediate compositions (solid solutions of Co-Ce
1x
Zr
x
O
2
) the
reflections are broadened.
Substitution of Zr into the CeO
2
lattice or vice versa causes
imperfections in the infinite lattice (due to differing size) strain
broadening.
Introduction to thermal analysis X-ray diffraction excercises
Problem 6
v) At which composition might the catalytic Co
3
O
4
phase have the smallest crystallite size?
In an effort to design catalysts for the CO
2
reforming of methane, Co-Ce
1x
Zr
x
O
2
catalysts with various
ratios of Ce/Zr were prepared by the co-precipitation method from the corresponding metal nitrates.
Ce(NO
3
)
3
6H
2
O, Zr(NO
3
)
4
5H
2
O and Co(NO
3
)
2
6H
2
O in stoichiometric ratios. The CoO content was fixed at 16
wt.%. The PXRD of the materials obtained is shown in Figure A. The PXRD patterns of the 4 crystalline
phases, cubic fluorite structure of CeO
2
, the cubic and tetragonal phases of ZrO
2
and the catalytic phase
Co
3
O
4
identified by the authors are shown in Figure B.
Content of CoO during coprecipitation is fixed at 16 wt.%.
Extent of incorporation into the Ce
1x
Zr
x
O
2
structure dependent on
the phase diagram and on the relative rates of precipitation of the
crystalline components.
Reflections of Co
3
O
4
phase most intense for materials with high
ZrO
2
contents. (larger) crystalline domains of Co
3
O
4
.
Assuming that all Co(NO
3
)
2
6H
2
O is precipitated the smallest
reflection observed for CeO
2
:ZrO
2
= 4:1 probably smallest
crystallite size.
Introduction to thermal analysis X-ray diffraction excercises
Problem 7
The (hydrothermal) reaction of MgO and Al
2
O
3
is a green chemistry route for the preparation of hydrotalcite, a
layered metal hydroxide and commonly used precursor for the preparation of Mg
x
AlOa well known solid base
catalyst. The PXRD patterns compared below show the PXRD patterns of the materials obtained following
hydrothermal reaction under three different conditions: 1) Reaction in conventional oven at 100C, 2) reaction
in a microwave oven at 100C and 3) Reaction in a microwave oven at 180C. Each reaction was undertaken
for 120 minutes with equivalent quantities of MgO, Al
2
O
3
, and H
2
O.
S. Mitchell, I.R. Baxendale, W. Jones, Green Chem. 10 (2008), 629.
Same reflections observed in both diffraction patterns No
variation in phase selectivity with heating method.
Reflections in the material obtained by conventional heating
broader than those observed in the material prepared using
microwave irradiation.
Use of microwave irradiation larger crystallite size/ higher
crystallinity.
Improved heating (rapid and homogeneous faster
nucleation and growth?
i) Comparing the PXRD pattern of the materials obtained under conditions 1 and 2, what can we say about the
influence of the heating method (conventional or microwave oven) on the reaction?
Introduction to thermal analysis X-ray diffraction excercises
Problem 7
The (hydrothermal) reaction of MgO and Al
2
O
3
is a green chemistry route for the preparation of hydrotalcite, a
layered metal hydroxide and commonly used precursor for the preparation of Mg
x
AlOa well known solid base
catalyst. The PXRD patterns compared below show the PXRD patterns of the materials obtained following
hydrothermal reaction under three different conditions: 1) Reaction in conventional oven at 100C, 2) reaction
in a microwave oven at 100C and 3) Reaction in a microwave oven at 180C. Each reaction was undertaken
for 120 minutes with equivalent quantities of MgO, Al
2
O
3
, and H
2
O.
ii) By comparison of the reaction under conditions 2 and 3, what can we determine about the influence of
temperature on the materials obtained?
New reflections observed on increasing the temperature
to 180C.
Change in phase selectivity. New phase formed at high
temperature (e.g. thermal stability).
Although similar in appearance closer observation shows
that some reflections shifted to higher diffraction angles,
some to lower and some remain in the same position.
Structural differences in materials obtained at 100 and
180C.
Introduction to thermal analysis X-ray diffraction excercises
Problem 7
iii) The layers in hydrotalcite may stack with different arrangements leading to polytypes which may be
identified by PXRD. The positions and relative intensities of the reflections expected for the two most common
arrangements (A and B) are summarized in the table below. Try to confirm if hydrotalcite was formed in any of
the reactions and if so in which polytype.
PolytypeA PolytypeB
(hkl) 2 / Intensity 2 / Intensity
(003) 11.6 Strong 12.1 Strong
(006) 23.3 Strong 24.2 Strong
(101) 34.2 Medium
(012) 34.9 Strong
(104) 37.9 Strong
(015) 39.3 Medium
(107) 45.0 Weak
(108) 46.8 Medium
(1010) 53.0 Weak 54.0 Weak
(110) 60.7 Medium 60.7 Medium
(113) 62.1 Medium 62.2 Medium
Polytype A formed at 100C.
At 180C predominant phase formed is polytype B.
Some reflections corresponding to polytype A also
observed.
Introduction to thermal analysis X-ray diffraction excercises
Problem 7
iv) This data was collected using monochromated Cu K

radiation ( = 1.5418 ). Using the Bragg relationship

(n = 2dsin) calculate the d-spacing associated with the (003) reflection of hydrotalcite.
For the (003) reflection 2 = 11.6.
d=n/2sin
d=7.63 .
How does this relate to the lattice parameter, c,
for this hydrotalcite?
c = 3*d = 22.88 .