XRD Applications in Relevant

Papers
Merve Ayvaz
Boazii University

Combined XRD and XANES studies of Re-promoted

Co/-Al2O3 catalyst at Fischer-Tropsch synthesis
conditions,
Ronning at al.,2010, Catalyst Today 155

Detecting changes in Co oxidation state and

crystallite size during the initial stages of the

FT reactions at industrail conditions.
Resutl of XRD:
Co dispersion depends on technique and it is 6-

9%
Particle size:11-16 nm

Reduction of Co and Crystallite Size

Co3O4 (spinel structure of the freshly calcined

Reduction of Co
catalyst)
CoO metastable phase
Co0 (fcc and hcp)
Heating rate and composition of the reducing
Most intense peaks are

gas mixture influence the crystallite

observed size
distribution.
16.54 for Co3O4
Phase transition is monitored
by for
XRD
with
18.93
CoO
sufficient time
resolution.
=0.70417
A
20.44
for Co
No Rhenium phase is not
detected- so, highly
dispersed.

X-Ray Line Boarding Analysis-Crystallite Size

Apply the Scherrer equation to maximum

intense peaks. (minimize overlapping peaks at

max. intensity)

Metallic cobalt crystallite size reduced 40%

comparing to initial state.

It is expected to decrease due to loss of
oxygen.

Crystallite Size
Co3O4 and CoO phases contain significant

amount of strain. (WilliamsonHall plots)

The diffraction peaks is not purely due to
finite crystallites.
Stacking faults in the metallic cobalt phases
may have contributed to the broadening of
the diffraction peaks.
The existence of other sample dependent
broadening effects implies that the crystallite
sizes calculated from the Scherrer equation
will be underestimated.

XANES Data- X-ray Absorption Near Edge

Structure (XANES)
DOR= the fraction of Co in the metallic state
The same sample after reduction show a degree of

reduction (DOR) in the range of 90%.

d(Cocpp)=
0.80d(Co3O4
)
CoO in the metallic cobalt particles may reduce the

calculated Scherrer size of the cobalt crystallites

Redispersion of cobalt crystallites during reduction can not
be excluded.
In contrast, all the Co3O4 is transformed.
The relatively small size of the CoO crystallites cannot be
explained solely by the existence of larger domains of Co 3+
-containing oxide inside the CoO particles.

XRD During FT Synthesis

FTS carried out 463K at 10 bar 2 hour.-Initial
Reaction
Reaction is monitored by on-line quadrople
mass spectrometer (MS) and XRD.
No visible
TOS= Ions currents during time on stream
changes are
detected in the
diffraction
peaks

Examination of the Diffractograms Before and After

Initial Reaction
The metallic cobalt peaks remain unchanged during

this initial stage of the reaction.

Crystallite sizes before and at the end of the reaction
were both 10.7 nm.
Change of wax peak may depend on variation in
product distribution and steam partial pressure from
the present reaction conditions.
WaxLHC

9.35
o

FTS @ 673K, 10K/min, 10 bar, 1 hour

FTS was subsequintly carried out at 673 K.
Increase in the Scherrer size of the cobalt

crystallites about 20% after 1 hour.

Particle growth seems to start immediately
after the applied conditions are reached.

FTS @ 483 K, 18 bar, 6 hours (industrially relevant conditions)

Liquid products were detected as an increase in the

scattering intensity at lower XRD angles.

Liquid products gradually fill the catalyst pores and
the reactor during the initial stages of the reaction.
No detectable changes in the cobalt crystallite size
during the reaction. (XRD line broadening analysis
showed)

Oxidation State of Cobalt by XANES

XANES spectra were recorded during reduction.
According to spectra cobalt in the catalyst sample

before reduction is present as Co3O4. During

reduction it is first transformed to CoO and further
to metallic cobalt.
Cobalt oxide is not completely reduced to cobalt
metal.
10% of the cobalt remains in the
T non-metallic
phase after reduction for 4 h at 673 K in Co
H 2.
The catalyst
Co3O4
maintained a
degree of
CoO
reduction close to
90%.

Oxidation of Co During the FTS by XANES

Oxidation of Cobalt during FTS (industrail) by XANES

No significant change in oxidation state of

cobalt during 6 hour.

Oxidation of Co during FTS (673 K,10

bar), by XRD
Decrease in the intensity of CoO peaks,

further reduction of Co.

Co crystallite size increase slightly.

Conclusion
A 20%Co-1%Re/g-Al2O3 catalyst characterised

by XRD and XANES methods at realistic

FischerTropsch conditions (483 K, 10 and 18
bar) in a plug flow reactor.
Conversion was monitored using an on-line
MS.
XRD and XANES are sensitive to structural
changes such as crystallite size and oxidation
state, respectively.
At 673 K further reduction of cobalt were
observed.

Characterization of K2CO3/Co-MoS2 catalyst by

XRD,SEM and EDS
Iranmahboob at al.,2001, Applied Surface Sciences 185
Utilization of XRD and XPS to characterize

MoS2,Co-MoS2 and K2CO3/Co-MoS2 catalyst.

Investigation of K2CO3/Co-MoS2 catalyst as a

function of dispersion of K on the surface by SEM

and EDS.

XRD Pattern of MoS2

33.50
d=2.6
7

39.50
d=2.2
8
500
d=1.8
2

590
d=1.5
6

Pattern is compared with literature

The absence of some XRD peaks confirm the amorphous

character of MoS3.
Rapid increase of temperature during reduction, increase
the surface area and presence of amorphous particles.

XRD Pattern of Co-MoS2

32.70 36.50
55.50
600
d=2.74d=2.46
0d=1.65
45.5
d=1.54
d=1.95

Diffraction lines of MoS2 are not change upon

addition of Co. (Co/Mo=0.5) However, new lines

are were observed.
With addition of Co no side product Co9S8 was
produced. No peak at 29.9o and 51.9o.

XRD Pattern of K2CO3/ Co-MoS2

320
37.50
d=2.7
d=2.6 53.50
0 9
26.5
7
d=1.7
d=3.3
1
6

The diffraction lines of Co-MoS2 did not changed.

Upon addition of K2CO3 new lines are observed.
Co-MoS2 is the primary phase in the catalyst.

XPS, comparison between MoS2/Co-MoS2 and K2CO3/Co-MoS2

O 1s peak of MoS2 shifted by about 1 eV to

higher BE for Co-MoS2

Oxygen was present on Co and MoS2; may be

due to the air exposure or incomplete

calcinations.
When potassium carbonate was added to the
system Mo and Co are shifted to the lower
energies.

SEM and EDS for K2CO3/Co-MoS2 Catalyst

Potassium distribution is

not uniform on the

surface. (SEM)
K and Mo+S (Mo and S
observed in the same BE)
peaks are different.
If K2CO3 and Co-MoS2 was
ground together and
exposed to syngas for 6
hours, catalyst achieved an
uniform distribution of K.

Conclusion
Co-MoS2 is the primary phase in K2CO3/Co-MoS2 .
Co9S8 phase is not present at Co/Mo mole ratio of

0.5.
XPS binding energy difference of molybdenum

sulfide (67.2 eV) is not changed for the MoS 2,

Co-MoS2, and K2CO3/Co-MoS2 catalyst.
The distribution of the potassium on the surface of

K2CO3/Co-MoS2 catalyst in not uniform when a

physical mixing method is used to prepare
catalyst.

An XRD and ESR study of V2O5/ZrO2 catalysts:

influence of the phase transitions of ZrO 2 on
the migration of V4+ ions in to zirconia
Adamski at al.,1998, Solid State Ionics 117
Determination of the catalytic properties of

potassium doped zirconia-supported V2O5

catalyst.

Phase Composition of ZrO2 matrix

Polymorphic forms are temperature

dependant.

Literature

1V/Zr

K-3V/Zr

Calcination of 1V/Zr Matrix

It is calcined at 853 K,

consist of 2 phases:
metastable tetragonal
and monoclinic.
K-3V/Zr calcined at 853
K. But the ratio of the
peak intensities
Upon
increasing the
(111)M/(111)temperature
T are
calcination
different
to
1253 K.
So
the phasephase
Tetragonal
composition
disapperingdepend
on
both temperature
Crystallite
size increases
and chemical

(111)M/(111)T Intensity Ratios

97
5
K
10
25
K

Strong interactions
between vanadia and
the supported
material stabilize
tetragonal zincoria in
the absence of alkali
additives up to 1025K
Beginnin
g of
phase
transitio
n

Temperature induce migration of V 4+ ions into zirconia

Vanadia (V5+ ) partially dissociates and loses some

oxygen depending on the calcinations temperature.

Leads to the formation of vanadium in lower
oxidation states.
V4+ ions can directly substitute Zr4+ ions in the
cationic sublattice of ZrO2 due to the same ionic
charge and similar cationic radius.

ESR-Zirconia supported
V2O5 catalyst with various
vanadia loadings

Spectra are more

intense when number

of V4+ ions increased.
Dipol-dipol
interaction between
them cause
broadening of the
spectral lines.
The intensity of the
signal due to Zr3+
defects decreases.

 Samples are calcined at gradually increasing

temperatures.
More information on the nature of V4+ species
responsible for the complex structure of the spectra.

1V/Zr, norrow and sharp signal

is related to the presence of
Zr3+ paramagnetic defects.
K3V/Zr, has intense and well
resolved samples g11=1.9247,
g_=1.9736 and A11=186.18,
A-=62.47 due to 51V hfs
observed.

Presence of V4+ Ions in ZrO2 Matrix

1V/Z
3V/Z
r Stepwise calcinations.
r
At temperatures above 1053 K, similar sequences of spectra
was recorded.
It indicates that in both cases V4+ ions occupy the same

Conclusion
Phase transitions are observed.

Metastable tetragonal
monoclinic
Phase transitions are influenced by additives.
(vanadium and potassium).
Vanadium stabilizes the metastable tetragonal
phase of zirconia.
Diffusion of the surface V4+ into ZrO2 matrix is
strongly accelerated by phase transition.

Thank you

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