Jentoft Diffusereflectance 250108

Modern Methods in Heterogeneous
Modern Methods in Heterogeneous

Catalysis Research
Catalysis Research
Diffuse Reflectance
Diffuse Reflectance
IR and UV
IR and UV
-
-
vis Spectroscopy
vis Spectroscopy
Abteilung Anorganische Chemie
Fritz-Haber-Institut der Max-Planck-Gesellschaft
Faradayweg 4-6, 14195 Berlin
January 25, 2008
Friederike Friederike C. Jentoft C. Jentoft

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Outline
Outline
1. Introduction & Challenges
2. Fundamentals of Transmission and Reflection Spectroscopy
- Lambert-Beer law
- Scattering and reflection phenomena
- Schuster-Kubelka-Munk theory
3. Experimental
- Integrating spheres
- Mirror optics
- Fiber optics
4. Applications
- Bulk structure
- Surface species / functional groups
- Probing surface sites
- Reaction intermediates and products
- Gas phase analysis

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MIR
MIR
-
-
NIR
NIR
vis
vis
UV
UV
electronic transitions, vibrations (rotations)
Type of
transition
Spectral range
Molecular rotation
Electronic
excitation
X-ray
radiation
Infrared
Radio waves
Micro waves
F M N
vis vis UV
Mid IR (MIR) Near IR (NIR) UV-vis
Wavenumber
/ cm
-1
3300 to 250 12500 to 3300 50000 to 12500
Wavelength /
nm
3000 to
(25000-40000)
(700-1000) to
3000
200 to 800
Energy / eV 6.2 to 1.5
Molecular
vibrations

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Spectroscopy with Powder Samples
Spectroscopy with Powder Samples
How to measure spectra of a powderous solid?
Absorption as a function of wavelength, qualitatively and
quantitatively

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Interaction of Light with Sample
how to extract absorption properties from transmitted light?
how to deal with reflection and scattering?
incident light
reflection at phase boundaries
transmitted light
scattered light
absorption of light
(luminescence)

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How to Deal with Phase Boundary Reflection
How to Deal with Phase Boundary Reflection
fraction of reflected light can be eliminated through reference
measurement with same materials (cuvette+ solvent)
incident light
transmitted light

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Absorption properties from transmitted light?
incident light transmitted light
absorption of light

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Transmitted Light and Sample Absorption
Properties
Properties
separation of variables and integration
sample thickness: l

=
l I
I
dl c
I
dI
0
0
decrease of I in an
infinitesimally thin layer
l c
I
I
=
0
ln
dl c I dl k I dI = =
c: molar concentration of absorbing species [mol/m
-3
]
: the molar napierian extinction coefficient [m
2
/mol]
I
0
I
0
I
I
=
: transmittance

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Properties
Properties

= = =

1
0
l c
e
I
I
) ln( = = = l c B A
e
) log(
10
= = l c A
extinction E (means absorbed + scattered light)
absorbance A (A
10
or A
e
)
optical density O.D.
all these quantities are DIMENSIONLESS !!!!
Lambert-Beer Law
standard spectroscopy
software uses A
10
!
(decadic) absorbance
dekadische Absorbanz
napierian absorbance
Napier-Absorbanz

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incident light
transmitted light
scattered light
absorption of light
(luminescence)

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Scattering
Scattering
Scattering is negligible in molecular disperse media (solutions)
Scattering is considerable for colloids and solids when the
wavelength is in the order of magnitude of the particle size
Wavenumber Wavelength
Mid-IR (MIR) 3300 to 250 cm
-1
3 to (25-40) m
Near-IR (NIR) 12500 to 3300 cm
-1
(700-1000) to 3000 nm
UV-vis 50000 to 12500 cm
-1
200 to 800 nm
Scattering is reduced through embedding
of the particles in media with similar
refractive index: KBr wafer (clear!)
technique, immersion in Nujol

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1100 1000 900 800 700
0
20
40
60
Wavenumbers (cm
-1
)
1083
1073
1059
983
960
896
862
788

(NaCl)
(KBr)
(CsCl)
T
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m
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(
%
)
But.Reaction with Material Used for
But.Reaction with Material Used for
Embedding
Embedding
H
4
PVMo
11
O
40
Reaction with diluent possible
Dilution usually not suitable for experiments at high T/ with reactive gases

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Limitations of Transmission Spectroscopy
Limitations of Transmission Spectroscopy
5000 4500 4000 3500 3000 2500 2000 1500
0
1
2
3
4
5
6
7
sulfated ZrO
2
after activation at 723 K

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m
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(
%
)
Wavenumber / cm
-1
Sulf-supporting wafer

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Can We Use the Reflected Light?
Can We Use the Reflected Light?
Instead of measuring the transmitted light, we could measure the
reflected light
Can we extract the absorption properties of our sample from the
reflected light?
D
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Specular
Specular
Reflection (Non
Reflection (Non
-
-
Absorbing Media)
Absorbing Media)
fraction of reflected light increases with
depends on and ratio of the refractive indices (Snell law)
insignificant for non-absorbing media, for air/glass about 4%
incident beam
reflected beam
n
0
n
1
>n
0
refracted beam
n
1
surface SIDE VIEW

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Diffuse Reflection
Diffuse Reflection
Intensity of diffusely reflected light
independent of angle of incidence
Result of multiple reflection, refraction, and
diffraction (scattering) inside the sample

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Diffuse Reflection
Diffuse Reflection
Randomly oriented crystals in a powder:
light diffusely reflected
Flattening of the surface or pressing of a
pellet can cause orientation of the crystals,
which are elementary mirrors
Causes glossy peaks if angle of observation
corresponds to angle of incidence
Solution: roughen surface with (sand)paper or
press between rough paper, or use different
observation angle!

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Specular
Specular
& Diffuse Reflection
& Diffuse Reflection
Reflection of radiant
energy at boundary
surfaces
mirror-type
(polished) surfaces
mat (dull, scattering)
surfaces
mirror-type reflection
mirror reflection
surface reflection
specular reflection
regulre Reflexion
gerichtete Reflexion
reflecting power called
reflectivity
reflecting power called
reflectance
multiple reflections at
surfaces of small
particles

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Light scattering
deflection of electromagnetic or corpuscular
radiation from its original direction
Raman-
scattering
Compton-
scattering
Brillouin-
scattering
elastic
Scattering
Scattering
Rayleigh-scattering
> d
wavelength dependent: 1/
4
no preferred direction
Mie-scattering
d
wavelength independent
preferentially in forward (and
backward) direction
inelastic

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Rayleigh
Rayleigh
-
-
and
and
Mie
Mie
-
-
Scattering
Scattering
Quelle: RMPP on line
d >> : Mie-Theory approaches laws
of geometric optics
h
d < : Rayleigh-Scattering
isotropic distribution
d = : Mie-Scattering
in forward and backward directions
d > : Mie-Scattering
predominantly in forward direction

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Typical Catalyst Particles
Typical Catalyst Particles
Need theory that treats light transfer in an absorbing and scattering
medium
Want to extract absorption properties!
ZrO
2
ca. 20 m
scanning electron microscopy image

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A Simplified Derivation of the
A Simplified Derivation of the
Schuster
Schuster
-
-
Kubelka
Kubelka
-
-
Munk
Munk
(or Remission) Function
(or Remission) Function
I
J
I
J
R =
dl S J dl S I dl K I dI + =
dl S I dl S J dl K J dJ + =
with K, S: absorption and scattering
coefficient [cm
-1
]
Divide equations by I or J , respectively, separate variables,
introduce R=J /I
Integrate via partial-fraction expansion

=
+ +
R
R
l
dl S
S
K
R R
dR
0
0
2
1 ) 1 ( 2
2

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A Simplified Derivation of the SKM Function
A Simplified Derivation of the SKM Function
S
K
R
R
R F =
2
) 1 (
) (
2
2 constants are needed to describe the reflectance:
absorption coefficient K
scattering coefficient S
Kubelka-Munk function
remission function
Assume black background, so that R
0
= 0
Make sample infinitely thick, i.e. no transmitted light (typical sample
thickness in experiment ca. 3 mm)
) 2 ( S K K S K
S
R
+ + +
=
for K0 (no absorption) R
1, i.e. all light reflected

for S0 (no scattering) R
0, i.e. all light transmitted or absorbed

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Transmission vs. Reflection Spectroscopy
T A ln =
R
R
R F
2
) 1 (
) (
2
=
0.0 0.2 0.4 0.6 0.8 1.0
0
1
2
3
4
5
6
Kubelka-Munk-function
Absorbance

A
b
s
o
r
b
a
n
c
e

/

K
u
b
e
l
k
a
-
M
u
n
k
Transmittance / Reflectance
For quantification and to be able to calculate difference spectra:
calculate absorbance / Kubelka-Munk function

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200 400 600 800
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
or R
C+A
T
C+A
T
C+A

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a
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o
r

R
e
f
l
e
c
t
a
n
c
e
Wavelength / nm
or R
C+A
T A ln =
R
R
R F
2
) 1 (
) (
2
=
200 400 600 800
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
higher reflectance
lower reflectance

K
u
b
e
l
k
a

M
u
n
k

f
u
n
c
t
i
o
n
Wavelength / nm
200 400 600 800
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
higher transmission
lower transmission

A
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b
a
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c
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Wavelength / nm

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Spectroscopy in Transmission
Spectroscopy in Transmission
reference nothing
= void, empty cell, cuvette
with solvent
Catalyst
Light
Source
Detector
spectrum:
transmission of
catalyst vs.
transmission of
reference
Double beam spectrometer: direct comparison sample - reference
Single beam spectrometer: consecutive measurement

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Diffuse Reflectance Spectroscopy
Diffuse Reflectance Spectroscopy
reference
white standard
Catalyst
Light
Source
Detector
spectrum:
reflectance of
sample (catalyst)
vs. reflectance of
standard
Need element that collects diffusely reflected light
Need to avoid specularly reflected light
Need reference standard (white standard)

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White Standards
White Standards
Spectralon thermoplastic resin, excellent reflectance in UV-vis region
KBr: IR (43500-400 cm
-1
)
BaSO
4
: UV-vis
MgO: UV-vis
Spectralon: UV-vis-NIR

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Specular
Specular
Reflection: Angular Distribution
Reflection: Angular Distribution
the intensity of the specularly reflected light is largest at an azimuth
of 180
incident beam
reflected beam
surface
TOP VIEW
azimuth
180
azimuth
<180

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Integrating
Integrating
Sphere
Sphere
Image: Rmpp on-line
Sample
Source
Detector
Gloss trap
Screen
the larger the sphere the smaller errors from the ports
the larger the sphere the lower the intensity onto the detector
typically 60-150 mm diameter
coatings: BaSO
4
, Spectralon (for UV-vis), Au

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How to Avoid
How to Avoid
Specular
Specular
Reflection
Reflection
Specular reflection is strongest in forward direction
Collect light in off-axis configuration
sample surface
SIDE VIEW
TOP VIEW
sample surface
90
120

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Mirror
Mirror
Optical
Optical
Accessory
Accessory
First ellipsoidal mirror focuses beam on sample
Second ellipsoidal mirror collects reflected light
20% of the diffusely reflected light is collected
can be placed into the normal
sample chamber (in line with
beam), no rearrangement
necessary
Source
Detector

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Fiber
Fiber
Optics
Optics
for
for
UV
UV
-
-
vis
vis
Light conducted through total reflectance
Fiber bundle with 6 around 1 configuration: illumination through 6 (45),
signal through 1
Avoids collection of specularly reflected light
Bilder: Hellma (http://www.hellma-worldwide.de) and CICP (http://www.cicp.com/home.html)

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Methods in Catalysis Research
Methods in Catalysis Research
UV-vis spectroscopy
[Transmission]
UV-vis spectroscopy
Diffuse Reflectance
Diffuse reflectance UV-vis spectroscopy
(DR-UV-vis spectroscopy or DRS)
Collecting Elements:
- Mirror optics
- Fiber optics
IR spectroscopy
Transmission
Fourier-transform infrared
spectroscopy (FTIR
spectroscopy)
Diffuse Reflectance
Diffuse reflectance
Fourier-transform infrared
spectroscopy (DRIFTS)
Collecting elements:
- Mirror optics

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Possible Transitions
Transitions/
Contribution
from
Vibrations Electronic transitions
Catalyst bulk Lattice, structural units Band gap energy of
semiconductors
Catalyst surface Stretching and deformation
modes of functional groups,
vibrations of supported
species: metal complexes
Charge transfer and d-d
transitions of metal
complexes, metal particles
Probing of surface
properties (functional
groups), adsorbed reactants
Probing of surface
properties, adsorbed
reactants
In situ: adsorbed reaction
intermediates / products
In situ: reaction
intermediates
Adsorbates
Gas phase Can be unwanted
Product analysis

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Transitions/
Contribution
from
semiconductors
Probing of surface
Probing of surface
reactants
In situ: reaction
intermediates
Adsorbates
Product analysis

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Limitations of Transmission IR Spectroscopy
Limitations of Transmission IR Spectroscopy
5000 4000 3000 2000 1000
0.00
0.01
0.02
0.03
0.04
0.05
0.06
0.07

sulfated ZrO
2

T
r
a
n
s
m
i
t
t
a
n
c
e
Wavenumber / cm
-1

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5000 4000 3000 2000 1000
0.00
0.01
0.02
0.03
0.04
0.05
0.06
0.07

sulfated ZrO
2

T
r
a
n
s
m
i
t
t
a
n
c
e
Wavenumber / cm
-1
5000 4000 3000 2000 1000
0.00
0.01
0.02
0.03
0.04
0.05
0.06
0.07
0.0
0.2
0.4
0.6
0.8
1.0
1.2
sulfated ZrO
2

T
r
a
n
s
m
i
t
t
a
n
c
e
Wavenumber / cm
-1

R
e
f
l
e
c
t
a
n
c
e
Transmission: self-supporting wafer
Reflectance: powder bed
Spectra can have very different appearance
Transmittance decreases, reflectance increases with increasing wavenumber
Comparison
Comparison
Transmission
Transmission
-
-
Diffuse Reflectance (IR)

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Comparison
Comparison
Transmission
Transmission
-
-
Vibrations of surface species may be more evident in DR spectra
5000 4000 3000 2000
3.0
3.2
3.4
3.6
3.8
4.0
4.2
4.4
4.6
4.8
5.0
0.0
0.2
0.4
0.6
0.8
1.0
A
b
s
o
r
b
a
n
c
e

A
N
a
p
i
e
r
Wavenumber / cm
-1

K
u
b
e
l
k
a
-
M
u
n
k

F
u
n
c
t
i
o
n
sulfated ZrO
2
Transmission: self-supporting wafer
Reflectance: powder bed
OH vibrations
SO vibrations

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Transitions/
Contribution
from
semiconductors
Probing of surface
Probing of surface
reactants
In situ: reaction
intermediates
Adsorbates
Product analysis

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F
H
I

B
e
r
l
i
n

2
0
0
8
Band Gap Determination (DR
Band Gap Determination (DR
-
-
UV
UV
-
-
vis)
vis)
Approximate composition C
6
N
8
H
z
Friedel-Crafts Acylation
0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0 5.5 6.0 6.5
0
500
1000
1500
2000
2500
3000
G
Line fit of Data1_G

(
F
(
R
)

*

E
)
2
Energy / eV
E
g
= 2.92 eV
SN3055, RT, after treatment at 473 in N
2
200 300 400 500 600 700 800
0.0
0.2
0.4
0.6
0.8
1.0
Catalyst: F. Goettmann, MPI KG Golm
Band gap determination: Weber, J . Catal. 1996

R
e
f
l
e
c
t
a
n
c
e
Wavelength / nm
25C_air_c1
26C_N2_c19, after heating to 473 K
SN 3055 sample
29.09.2006

F
.
C
.

J
e
n
t
o
f
t

F
H
I

B
e
r
l
i
n

2
0
0
8
Dispersed
Dispersed
V
V
x x
O
O
y y
Species (DR
Species (DR
-
-
UV
UV
-
-
vis)
vis)
Kondratenko and Baerns, Appl. Catal. 2001
9.5 wt% VO
x
/ Al
2
O
3
0.5 wt% VO
x
/Al
2
O
3
+
CT bands at 359 and 376 nm: isolated octahedrally co-ordinated V
5+
species
CT bands at 468 and 535 nm: octahedraly co-ordinated V
5+
species in
V
2
O
5
clusters (XRD shows crystalline form of V
2
O
5
)

F
.
C
.

J
e
n
t
o
f
t

F
H
I

B
e
r
l
i
n

2
0
0
8
Transitions/
Contribution
from
semiconductors
Probing of surface
Probing of surface
reactants
In situ: reaction
intermediates
Adsorbates
Product analysis

F
.
C
.

J
e
n
t
o
f
t

F
H
I

B
e
r
l
i
n

2
0
0
8
CO Adsorption at RT on Cu/ZrO
CO Adsorption at RT on Cu/ZrO
2 2
Identification of copper oxidation states based on CO
frequency can be ambiguous
2200 2150 2100 2050 2000 1950
0.0
0.5
1.0
1.5
2.0
2.5
Cu
0
300C / 2% H
2
300C / 20% O
2
450C / 15% H
2

K
u
b
e
l
k
a

M
u
n
k

f
u
n
c
t
i
o
n
Wavenumber / cm
-1
2111
2106
2098
Cu
+
?

F
.
C
.

J
e
n
t
o
f
t

F
H
I

B
e
r
l
i
n

2
0
0
8
CO Desorption at RT on Cu/ZrO
CO Desorption at RT on Cu/ZrO
2 2
Identification via stability of Cu-CO complex
0 50 100 150 200 250 300 350
0
20
40
60
80
100
after 20% O
2
after 2% H
2

n
o
r
m
.

I
n
t
e
n
s
i
t
y
Purging time / min

F
.
C
.

J
e
n
t
o
f
t

F
H
I

B
e
r
l
i
n

2
0
0
8
Transitions/
Contribution
from
semiconductors
Probing of surface
Probing of surface
reactants
In situ: reaction
intermediates
Adsorbates
Product analysis

F
.
C
.

J
e
n
t
o
f
t

F
H
I

B
e
r
l
i
n

2
0
0
8
Hammett Indicators Adsorbed on Solids
Hammett Indicators Adsorbed on Solids

F
.
C
.

J
e
n
t
o
f
t

F
H
I

B
e
r
l
i
n

2
0
0
8
Example
Example
450 500 550 600 650 700 750 800
0.0
0.1
0.2

A
b
s
o
r
b
a
n
c
e
Wavelength / nm
450 500 550 600 650 700 750 800
0.0
0.2
0.4
0.6
0.8
1.0
1.2

A
b
s
o
r
b
a
n
c
e
Wavelength / nm
Methylene blue adsorbed on TiO
2
Methylene blue in aqueous solution

F
.
C
.

J
e
n
t
o
f
t

F
H
I

B
e
r
l
i
n

2
0
0
8
Transitions/
Contribution
from
semiconductors
Probing of surface
Probing of surface
properties
In situ: reaction
intermediates
Adsorbates
Product analysis

F
.
C
.

J
e
n
t
o
f
t

F
H
I

B
e
r
l
i
n

2
0
0
8
Origin of Surface and Gas Phase Contributions
Origin of Surface and Gas Phase Contributions
HEATER
Incident light
Diffusely reflected light
IR transparent window

F
.
C
.

J
e
n
t
o
f
t

F
H
I

B
e
r
l
i
n

2
0
0
8
DRIFTS:
DRIFTS:
n
n
-
-
Butane Isomerization
CH
3
CH
3
CH
2
CH
2
CH
3
CH
3
CH
CH
3
3500 3000 2500 2000 1500
0.0
0.2
0.4
0.6
0.8
1.0
1.2
1.4
1.6
1.8
2.0

K
u
b
e
l
k
a

M
u
n
k

f
u
n
c
t
i
o
n
Wavenumber / cm
-1
Sulf. ZrO
2
, 5 kPa n-C
4
in N
2
, 373 K
Time on stream
CH stretching
ads. H
2
O

F
.
C
.

J
e
n
t
o
f
t

F
H
I

B
e
r
l
i
n

2
0
0
8
250 300 350
0
1
2
3
4 18 h
4 h
1 h
activated

K
u
b
e
l
k
a
-
M
u
n
k

f
u
n
c
t
i
o
n
Wavelength / nm
295
400 500 600
0.00
0.02
0.04
0.06
0.08
0.10

380
450

DR
DR
-
-
UV
UV
-
-
vis:
vis:
n
n
-
-
CH
3
CH
3
CH
2
CH
2
CH
3
CH
3
CH
CH
3
Sulf. ZrO
2
, 5 kPa n-C
4
in N
2
, 373 K
Time on
stream
+
+
+
300 nm
350-370 nm
430-440nm

F
.
C
.

J
e
n
t
o
f
t

F
H
I

B
e
r
l
i
n

2
0
0
8
Transitions/
Contribution
from
semiconductors
Probing of surface
Probing of surface
reactants
In situ: reaction
intermediates
Adsorbates
Product analysis

F
.
C
.

J
e
n
t
o
f
t

F
H
I

B
e
r
l
i
n

2
0
0
8
DRIFTS: Preferential Oxidation of CO (PROX)
DRIFTS: Preferential Oxidation of CO (PROX)
3500 3000 2500 2000
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7

K
u
b
e
l
k
a
-
M
u
n
k

f
u
n
c
t
i
o
n
Wavenumber / cm
-1
CO + O
2
CO
2
in excess H
2
1% Pt/CeO
2
at T = 383 K, 1% CO/1% O
2
in H
2
Time on
stream

F
.
C
.

J
e
n
t
o
f
t

F
H
I

B
e
r
l
i
n

2
0
0
8
IR Gas Phase Analysis: PROX
IR Gas Phase Analysis: PROX
2500 2400 2300 2200 2100 2000 1900 1800
0.0
0.1
0.2
0.3
0.4

K
u
b
e
l
k
a
-
M
u
n
k

f
u
n
c
t
i
o
n
Wavenumber / cm
-1
Gas phase CO
2
Pt-CO
0.0E+00
5.0E-10
1.0E-09
1.5E-09
2.0E-09
2.5E-09
3.0E-09
3.5E-09
4.0E-09
0 1 2 3 4
CO
2
signal IR
C
O
2

s
i
g
n
a
l

M
S
IR band area of CO
2
vibration corresponds to CO
2
MS signal in
effluent gas
Quantification of gas phase composition possible
Analysis by Detre Teschner

F
.
C
.

J
e
n
t
o
f
t

F
H
I

B
e
r
l
i
n

2
0
0
8
Transitions/
Contribution
from
semiconductors
Probing of surface
Probing of surface
properties
In situ: reaction
intermediates
Adsorbates
Product analysis

F
.
C
.

J
e
n
t
o
f
t

F
H
I

B
e
r
l
i
n

2
0
0
8
Literature
Literature
W. WM. Wendlandt, H.G. Hecht, Reflectance Spectroscopy,
Interscience Publishers/J ohn Wiley 1966
G. Kortm, Reflectance Spectroscopy / Reflexionsspektroskopie
Springer 1969

Jentoft Diffusereflectance 250108

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Jentoft Diffusereflectance 250108

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Modern Methods in Heterogeneous

Modern Methods in Heterogeneous

for K0 (no absorption) R

1, i.e. all light reflected

0, i.e. all light transmitted or absorbed

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