X-ray diffraction exercises

Dr. Sharon Mitchell and Prof. Javier Prez-Ramrez

Institute for Chemical and Bioengineering, ETH Zurich, Switzerland E-mail: jpr@chem.ethz.ch http://www.perez-ramirez.ethz.ch

Characterization of catalysts and surfaces

Thermal methods

Problem 1
Using the 2D lattice given below draw planes corresponding to a) (010) b) (200), c) (110), and d) (120).
a) b)

b a c) d)

Introduction to thermal analysis

X-ray diffraction excercises

Problem 2
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.

= 1.315 .
2 = 50.5

Braggs law n=2dsin

d = /2sin d = 1.54

= 25.25

Note: In order to calculate the d-spacing using Excel, theta must be in radians.

Introduction to thermal analysis

X-ray diffraction excercises

Problem 3
X-rays with wavelength 1.54 are reflected from the (1 1 0) planes of a cubic crystal with unit cell a = 6 . Calculate the Bragg angle, , for orders of reflection, n = 1-5.

Introduction to thermal analysis

X-ray diffraction excercises

Problem 3

n 1 2 3 4 5

/ radians
0.183 0.372 0.576 0.813 1.139

2 /
10.5 21.3 33.0 46.6 65.2

Introduction to thermal analysis

X-ray diffraction excercises

Problem 4
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, how might 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?

Introduction to thermal analysis

X-ray diffraction excercises

Problem 4
+ 1) Sample. 2) Background + 3) Noise

Crystallinity/disorder Quantity Multiple phases Amorphous Particle size

Variation of intensity
with Bragg angle.

Fluctuations in intensity of
incident X-rays.

Detector dependent e.g. Bragg-Brentano

geometry greater divergence of X-ray beam at higher 2.
Incident beam

Inelastic scattering /
absorbance.

Introduction to thermal analysis

X-ray diffraction excercises

Problem 4
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?

Introduction to thermal analysis

X-ray diffraction excercises

Problem 4

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.

Introduction to thermal analysis

X-ray diffraction excercises

Problem 5
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?

Bobs = Binstr + Bsample = Binstr + Bsize + Bstrain

Binstr -Dependent on experimental set up e.g. Monochromaticity of incident beam, beam divergence etc. -Direct relationship with . - Determined by measurement of suitable reference.
Introduction to thermal analysis

Bsample = Bsize + Bstrain -Crystals have finite size (not infinitely periodic) Bsize Lattice imperfections (e.g. vacancies, substitutions, dislocations) Bstrain
X-ray diffraction excercises

Problem 5
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?

Bobs = Binstr + Bsample = Binstr + Bsize + Bstrain

Possible to gain information about sample if instrumental parameters are known. Scherrer equation relates peak width to crystalline domain size K = Scherrer constant, L = apparent size of the crystalline domain / B = Full width half maximum /

K Bsize 2 L cos
strain 0

= Wavelength /

Bsize 1/cos Bstrain tan

X-ray diffraction excercises

Bstrain Frequently assumed to have the following dependence: 0 = d/d B (2) = 4 tan
Introduction to thermal analysis

Problem 5
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 .
ii) For the reflection at 2 = 76.452, the FWHM, B, is found to be 1.0886 after correction for instrumental contributions. Using the Scherrer equation estimate the size of the nano-crystalline domains.

K Bsize 2 L cos

K L Bsize cos

Assuming K = 0.89 (i.e. for spherical crystalline domains). Then the size of the crystalline domains perpendicular to (331), L(331) = 1.6 .

Introduction to thermal analysis

X-ray diffraction excercises

Problem 5
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? Crystalline domains may not be spherical.

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.

Introduction to thermal analysis

X-ray diffraction excercises

Problem 5
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 K1 and K2 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).
Introduction to thermal analysis

Intensity K1 > K2.

X-ray diffraction excercises

Problem 6
In an effort to design catalysts for the CO2 reforming of methane, Co-Ce1xZrxO2 catalysts with various ratios of Ce/Zr were prepared by the co-precipitation method from the corresponding metal nitrates. Ce(NO3)36H2O, Zr(NO3)45H2O and Co(NO3)26H2O 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 CeO2, the cubic and tetragonal phases of ZrO2 and the catalytic phase Co3O4 identified by the authors are shown in Figure B. 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 ZrO2. 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.
N. Wang, W. Chu, L. Huang, T. Zhang, J. Natural Gas Chem. 19 (2010), 117.

Co3O4

Introduction to thermal analysis

X-ray diffraction excercises

Problem 6
In an effort to design catalysts for the CO2 reforming of methane, Co-Ce1xZrxO2 catalysts with various ratios of Ce/Zr were prepared by the co-precipitation method from the corresponding metal nitrates. Ce(NO3)36H2O, Zr(NO3)45H2O and Co(NO3)26H2O 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 CeO2, the cubic and tetragonal phases of ZrO2 and the catalytic phase Co3O4 identified by the authors are shown in Figure B.

ii) Based on the information in Figure B, assign the reflections in Figure A as far as you can.

Co3O4 and CeO2,

ZrO2

Introduction to thermal analysis

X-ray diffraction excercises

Problem 6
In an effort to design catalysts for the CO2 reforming of methane, Co-Ce1xZrxO2 catalysts with various ratios of Ce/Zr were prepared by the co-precipitation method from the corresponding metal nitrates. Ce(NO3)36H2O, Zr(NO3)45H2O and Co(NO3)26H2O 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 CeO2, the cubic and tetragonal phases of ZrO2 and the catalytic phase Co3O4 identified by the authors are shown in Figure B.
iii) Are any reflections unaccounted for? What might be the origin of these reflections?

Circled reflections unaccounted for in reported phase assignment

Introduction to thermal analysis

X-ray diffraction excercises

Problem 6
In an effort to design catalysts for the CO2 reforming of methane, Co-Ce1xZrxO2 catalysts with various ratios of Ce/Zr were prepared by the co-precipitation method from the corresponding metal nitrates. Ce(NO3)36H2O, Zr(NO3)45H2O and Co(NO3)26H2O 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 CeO2, the cubic and tetragonal phases of ZrO2 and the catalytic phase Co3O4 identified by the authors are shown in Figure B. iv) By looking at the variation in peak broadening, what can we tell about the variation in crystallinity with composition? Narrowest reflections observed for single phase oxides (e.g. CeO2 or ZrO2). 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-Ce1xZrxO2 ) the reflections are broadened. Substitution of Zr into the CeO2 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
In an effort to design catalysts for the CO2 reforming of methane, Co-Ce1xZrxO2 catalysts with various ratios of Ce/Zr were prepared by the co-precipitation method from the corresponding metal nitrates. Ce(NO3)36H2O, Zr(NO3)45H2O and Co(NO3)26H2O 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 CeO2, the cubic and tetragonal phases of ZrO2 and the catalytic phase Co3O4 identified by the authors are shown in Figure B. v) At which composition might the catalytic Co3O4 phase have the smallest crystallite size? Content of CoO during coprecipitation is fixed at 16 wt.%. Extent of incorporation into the Ce1xZrxO2 structure dependent on the phase diagram and on the relative rates of precipitation of the crystalline components. Reflections of Co3O4 phase most intense for materials with high ZrO2 contents. (larger) crystalline domains of Co3O4. Assuming that all Co(NO3)26H2O is precipitated the smallest reflection observed for CeO2:ZrO2 = 4:1 probably smallest crystallite size.
Introduction to thermal analysis X-ray diffraction excercises

Problem 7
The (hydrothermal) reaction of MgO and Al2O3 is a green chemistry route for the preparation of hydrotalcite, a layered metal hydroxide and commonly used precursor for the preparation of MgxAlO a 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, Al2O3, and H2O. 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? 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?
S. Mitchell, I.R. Baxendale, W. Jones, Green Chem. 10 (2008), 629.

Introduction to thermal analysis

X-ray diffraction excercises

Problem 7
The (hydrothermal) reaction of MgO and Al2O3 is a green chemistry route for the preparation of hydrotalcite, a layered metal hydroxide and commonly used precursor for the preparation of MgxAlO a 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, Al2O3, and H2O. 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.

(hkl) (003) (006) (101) (012) (104) (015) (107) (108) (1010) (110) (113)

PolytypeA PolytypeB 2 / Intensity 2 / Intensity 11.6 Strong 12.1 Strong 23.3 Strong 24.2 Strong 34.2 Medium 34.9 Strong 37.9 Strong 39.3 Medium 45.0 Weak 46.8 Medium 53.0 Weak 54.0 Weak 60.7 Medium 60.7 Medium 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 .

Introduction to thermal analysis

X-ray diffraction excercises