Diffuse Reflectance IR and UV-vis Spectroscopy: AC AC AC

AC
FHI
Diffuse Reflectance
IR and UV-vis Spectroscopy
Modern Methods in Heterogeneous Catalysis

Friederike Jentoft
December 10, 2004

Outline
I. Background
1. UV-vis, NIR and IR spectroscopy
2. Transmission
3. Specular & Diffuse Reflectance
4. Mie and Rayleigh Scattering Theories
5. Kubelka-Munk Theory
II. Experimental & Examples
1. White Standards
2. Integrating Spheres
3. Mirror Optics
4. Fiber Optics
© 2004 F.C. Jentoft, Fritz-Haber-Institut der Max-Planck-Gesellschaft

UV- vis- NIR – MIR
v electronic transitions, vibrations (rotations)

v Diffuse reflectance UV-vis spectroscopy (DR-UV-vis spectroscopy or DRS)
v Diffuse reflectance Fourier-transform infrared spectroscopy (DRIFTS)
Interaction of Light with Sample
scattered light
incident light transmitted light
reflection at phase boundaries

absorption of light
v how to extract absorbing properties from transmitted light?

v how to deal with reflection and scattering?
How to Deal with Reflection (1)
v fraction of reflected light can be eliminated through reference

measurement with same materials (cuvette+ solvent)
How to Deal with Reflection (2)
v fraction of reflected light can be eliminated through variation of

sample thickness: number of phase boundaries remains the same

Scattering
v scattering is negligible in molecular disperse media (solutions)

v 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) µm
Near-IR (NIR) 12500 to 3300 cm-1 (700-1000) to 3000 nm
UV-vis 50000 to 12500 cm-1 200 to 800 nm
v scattering is reduced through embedding

of the particles in media with similar
refractive index: KBr wafer (clear!)
technique, immersion in Nujol

Transmittance
I
τ =
I0
I0 I
Sample
if luminescence and scattering are negligible:
1=α+τ+ρ
α absorptance, absorption factor, Absorptionsgrad
τ(T) transmittance, transmission factor, Transmissionsgrad
ρ reflectance, reflection factor, Reflexionsgrad
if we manage to eliminate reflection:

1=α+τ
in this case, the absorption properties of the sample can be calculated
from the transmitted light
Transmitted Light and Sample Absorption Properties
I
τ =
I0
I0 I
decrease of I in an infinitesimally thin layer

dI = −I κ c dl
c: molar concentration of absorbing species [mol/m-3]
κ: the molar napierian extinction coefficient [m2/mol]
I l
dI
∫I I = − ∫0 κ c dl separation of variables and integration
sample thickness: l
0
I
ln = − κ c l
I0
Transmitted Light and Sample Absorption Properties
I
τ = = e− κ c l = 1 − α Lambert-Beer Law
I0
Ae = B = κ c l = − ln(1 − α ) napierian absorbance
Napier-Absorbanz
A10 = ε c l = − log(1 − α ) (decadic) absorbance

dekadische Absorbanz
standard spectroscopy
software uses A10!
extinction E (means absorbed + scattered light)

absorbance A (A10 or Ae)
optical density O.D.
all these quantities are DIMENSIONLESS !!!!
Limitations of Transmission Spectroscopy
50 self-supporting wafers H4PVMo11O40

Cs2H2PVMo11O40
Cs3HPVMo11O40
40 Cs4PVMo11O40
2118
1379
Transmission (%)
2036
30
CaF2-
20 Window-
1257
2040
2119
Absorption
1625
1934
10
1632
1612
0
4000 3500 3000 2500 2000 1500 1000

-1
Wellenzahl (cm )
But…….Reaction with Material Used for Embedding
(NaCl)
H4PVMo11O40 (KBr)
60 (CsCl)
Transmission (%)
40
1083
20
1073 896
983
1059 862 788
960
0
1100 1000 900 800 700
-1
Wavenumbers (cm )
v reaction with diluent possible

Limitations of Transmission Spectroscopy
0.07
sulfated ZrO2 after activiton at 723 K
0.06
Transmittance 0.05
0.04
0.03
0.02
0.01
0.00
5000 4000 3000 2000 1000
-1
Wavenumber / cm
v transmission can become very low! even in IR regime!

v catalysts are fine powders (high surface area)
v embedding (KBr) not desirable for in situ studies (heating, reaction)
Can We Use the Reflected Light?
v instead of measuring the transmitted light, we could measure the

reflected light
v can we extract the absorption properties of our sample from the
reflected light?
Detector

Specular & Diffuse Reflection
Reflection of radiant
energy at boundary
surfaces
mirror-type mat (dull, scattering)
(polished) surfaces surfaces
mirror-type reflection multiple reflections at

mirror reflection surfaces of small
surface reflection particles
specular reflection
reguläre Reflexion
gerichtete Reflexion
reflecting power called reflecting power called

“reflectivity” “reflectance”
Specular Reflection (Non-Absorbing Media)
α
incident beam reflected beam
n0
n1>n0
surface SIDE VIEW n1
β refracted beam
v fraction of reflected light increases with α

v β depends on α and ratio of the refractive indices (Snell law)
Specular Reflection: Angular Distribution
azimuth
180°
incident beam reflected beam
azimuth
<180°
surface
TOP VIEW
v the intensity of the specularly reflected light is largest at an azimuth

of 180°
Diffuse Reflection & Macroscopic Surface Properties
v randomly oriented crystals in a powder:

light diffusely reflected
v flattening of the surface or pressing of a pellet

can cause orientation of the crystals, which
are “elementary mirrors”
v causes “glossy peaks” if angle of observation
corresponds to angle of incidence
v solution: roughen surface with (sand)paper or
press between rough paper, or use different
observation angle!
Light Reflection from Powders:
Why is the Distribution Isotropic?
particle diameter d > λ particle diameter d ≤ λ

v light partially reflected on v scattering occurs
elementary mirrors (crystal facets) v Mie’s theory for single
inclined statistically at all possible scattering says distribution is
angles to the macroscopic surface not isotropic
v light penetrates into sample, v multiple scattering should
undergoes numerous reflections, produce isotropic distribution
refractions and diffraction and
emerges finally diffusely at the
surface

The Rayleigh Scattering Theory
v according to Rayleigh (Gans, Born)

v electromagnetic wave induces vibrating dipole in molecule
(i.e. d << λ), electrons assumed to be in phase, molecular antenna
v dipole emits electromagnetic waves in all directions, i.e. the primary
wave is being scattered
1
I scat ∝ 4
λ0

The Mie Scattering Theory
v rigorous theory for single scattering of a planar wave at spherical

particles, both dielectric and absorbing, of any size
v in the limit of infinite diameter, the Mie theory approaches a

scattering distribution as can be obtained from the law of geometrical
optics by dealing separately with reflection, refraction, and diffraction
v according to the Mie formula, there is no principle distinction

between reflection, refraction, and diffraction on one hand and
scattering on the other hand
Typical Catalyst Particles
ca. 20 µm
ZrO2
scanning electron microscopy image
v need theory that treats light transfer in an absorbing and scattering

medium
v want to extract absorption properties!
The Schuster-Kubelka-Munk Theory
Assumptions
v incident light diffuse
v isotropic distribution (Lambert cosine law valid) , i.e. no regular reflection
v particles randomly distributed
v particles much smaller than thickness of layer
2 constants are needed to describe the reflectance:

absorption coefficient k
scattering coefficient s
2
(1 − R∞ ) k Kubelka-Munk function
F ( R∞ ) = = remission function
2 R∞ s
Kubelka-Munk Function
v mostly we measure R’∞, i.e. not the absolute reflectance R∞

but the reflectance relative to a standard
v depends on wavelength F(R’∞)λ
v corresponds to extinction in transmission spectroscopy
v in case of a dilute species is proportional to the concentration of the
species (similar to the Lambert-Beer law):
εc
F ( R∞′ ) ∝
s

Deviations from & Limitations of the
Kubelka-Munk Theory
incident radiation
v should be diffuse and not directed, however, it is assumed that after
a few scattering events the distribution is isotropic
v directed incident radiation can be a problem on very rough surfaces:
shadowing effects
any regular reflection
v will cause deviation
low reflectance values
v applicability of Kubelka-Munk theory questionable
v smallest error between 0.2 < R∞ < 0.6

Transmission vs. Reflection Spectroscopy
v for quantification and to be able to calculate difference spectra:

calculate absorbance / Kubelka-Munk function
(1 − R) 2
A = − ln T F ( R) =
2R
6
Absorbance / Kubelka-Munk
5
Kubelka-Munk-function
2
Absorbance
1
0
0.0 0.2 0.4 0.6 0.8 1.0
Transmission / Reflectance

Transmission vs. Reflection Spectroscopy
1.0
Transmittance or Reflectance
0.9
0.8
TC+A
0.7
0.6
0.5
0.4 TC+A
0.3
(1 − R ) 2
A = − ln T 0.2
0.1
F ( R) =
0.0 2R
200 400 600 800
Wavelength / nm
1.0 1.0
0.9 0.9
0.8 0.8
Kubelka Munk units

lower transmission
0.7 0.7
0.6 0.6
Absorbance
0.5 0.5
0.4 0.4
0.3 0.3 lower reflectance
0.2 higher transmission 0.2
0.1 0.1
higher reflectance
0.0 0.0
200 400 600 800 200 400 600 800
Wavelength / nm Wavelength / nm
Spectroscopy in Transmission
Catalyst
Light
Detector
Source
reference „nothing“ spectrum:

= void, empty cell, cuvette transmission of
with solvent catalyst vs.
transmission of
reference
v in IR transmission is widely applied for solids
v in UV-vis transmission is rarely used for solids
Reflectance Spectroscopy
Light
Source
reference
„white standard“
Catalyst
spectrum:
reflectance of
sample (catalyst)
Detector vs. reflectance of
standard
v need element that collects diffusely reflected light

v need to avoid specularly reflected light
v need reference standard (white standard)
“White” Standards
v KBr: IR (43500-400 cm-1)

v BaSO4: UV-vis
v MgO: UV-vis
v Spectralon: UV-vis-NIR

White Standard MgO
v ages rapidly

White Standard BaSO4
100
90
% Reflectance
80
70
60
50
40
0 500 1000 1500 2000 2500

Wavelength / nm
v reflects well in range 335 – 1320 nm

v humid!

White Standard Spectralon®
Spectralon® thermoplastic resin, excellent reflectance in UV-vis region

„Gray“ Standards
100 100%=
Sp vs. Sp.
80
Reflectance %
60 "50%="
50Sp vs. Sp.
40
"20%="
20Sp vs. Sp.
20
0
0 500 1000 1500 2000 2500
Wavelength / nm

The Collection Elements
v integrating spheres (UV-vis-NIR)

v fiber optics (UV-vis-NIR)
v mirror optics (IR and UV-vis-NIR)

Integrating Spheres
v also called: photometer spheres, Ulbricht spheres
fm fM 1
I P = I 0 ρW ρ P ρK
F 2
1− ρK
F total internal surface of sphere

fm,,fM relative fractions of measuring
surface and opening aperture
ρW absolute reflectance of wall
ρP absolute reflectance of sample
ρK absolute reflectance of sphere
S screen blocks regular reflection
 f + fE + fP  fP
ρ K = 1 − M ρ
 W + ρP
 F  F
Integrating Spheres: Coatings
v BaSO4: UV-vis
v MgO: UV-vis
v Spectralon: UV-vis-NIR
v Au: 800 nm to MIR

In Situ Cell & Integrating Sphere
top view
v beam path equivalent for sample and reference beam

v spectrometer background correction can be used
v window (Suprasil or Infrasil): absorbs and reflects light
Catalyst Deactivation: in situ UV-vis Spectroscopy
sulfated zirconia, 358 K

1.0 300 1.4
Rate of formation / µmol g-1 h-1

sulfated zircona, 378 K 5 vol% n-butane
isobutane
Band area at 310 nm / a.u.

5 vol% n-butane 1.2
250 propane
0.8
after activation 200 1.0
Reflectance
0.6 after reaction

0.8
150
0.4 0.6
100
0.4
0.2 50
0.2
difference
0.0 0
0.0
300 400 500 600 700 800 0 60 120 180 240 300 360
Wavelength / nm Time on stream / min
v formation of additional bands during n-butane isomerization

v band at 310 nm, allylic cations? Analyzed using apparent absorption A=1-R
v spectroscopic and catalytic data can be correlated
Mirror Optics
v can be placed into the normal sample chamber (in line with beam),
no rearrangement necessary
v good in IR
v some disadvantages in UV-vis

How to Avoid Specular Reflection (1)
SIDE VIEW TOP VIEW
120°
90°
sample surface sample surface
v specular reflection is strongest in forward direction

v collect light in off-axis configuration

The Harrick Praying Mantis
v first ellipsoidal mirror focuses

beam on sample
v second ellipsoidal mirror
collects reflected light
v 20% of the diffusely reflected
light is collected
alignment can be tested

v align with flat mirror (= only specular reflection): minimize throughput
v align with tilted mirror: maximize throughput
Mirror Optics: Throughput in MIR Range
v throughput measured with tilted mirror

v mirror optics work well in the IR range….
Mirror Optics: Throughput in UV-vis-NIR Range
8 June, 2004, Lambda 950, PERKIN ELMER

80 Alignment Harrick Praying Mantis
70
60
% Reflectance
50
BC (100%): empty versus empty
CBM=90
40 integration time NIR=0.24, UVvis=0.2
data points 1 per 1 nm (ca. 240 nm/min)
slit 2 nm, gain (NIR) 1
30
20
tilted mirror in sampling position
10
0
0 500 1000 1500 2000 2500
Wavelength / nm
v aluminum coating of mirrors absorbs light! Here: 7 mirrors

v spectra will be more noisy in region of low throughput
The Harrick Praying Mantis Reaction Chamber
v quartz windows (high pressure version available)

v up to 873 K (lot T version with Dewar available)
v powder bed rest on stainless steel grid: flow through bed
v low dead volume
Mirror Optics: UV-vis-NIR Range with
Quartz Dome and Spectralon
8 June, 2004, Lambda 950, PERKIN ELMER
80 Alignment Harrick Praying Mantis
70
60 BC (100%): empty versus empty
CBM=90
% Reflectance
integration time NIR=0.24, UVvis=0.2

50 data points 1 per 1 nm (ca. 240 nm/min)
40
30
20 tilted mirror in sampling position
reaction chamber with spectralon and dome
10
0
0 500 1000 1500 2000 2500
Wavelength / nm
v very low light yield

v need spectrometer that works well under these conditions
Mirror Optics: UV-vis-NIR Range with
Quartz Dome and Spectralon
10
9
8
7
% Reflectance
tilted mirror in sampling position

6 reaction chamber with spectralon and dome
5
4
3
2
1
0
0 500 1000 1500 2000 2500
Wavelength / nm
v an attenuator may be necessary in the reference beam

v artifacts from change of optical components (gratings, filters,
detectors, lamps) may become visible
Example: Catalyst Activation
9 June, 2004, Lambda 950, PERKIN ELMER Temperature / °C

cat.: AH222, heating in N2 from 50-500°C (5 K/min) 64
66
100
160 BC with different parameters! 125
148
170
197
222
120
% Reflectance
244
267
292
314
344
80 366
393
416
441
465
40 BC (100%): spectralon + dome versus 10%T 488
CBM=90 498
integration time NIR=0.08, UVvis=0.08 500
data points 1 per 1 nm (ca. 570 nm/min) 500
0
0 600 1200 1800 2400
Wavelength / nm
v UV-vis NIR gives information on valences and water content

Diffuse Reflectance IR (DRIFTS): Graseby Specac
Selector Optics and Environmental Chamber
v ZnSe window (chemically resistant)

v up to 773 K
v no flow through be (rest in cup)
v large dead volume (est. 100 ml)
Comparison
Transmission - Diffuse Reflectance
0.07 Transmission:1.2
self-supporting wafer
sulfated ZrO2 after activation at 723 K
Reflectance: powder bed
0.06 1.0
0.05
Transmittance
Reflectance
0.8
0.04
0.6
0.03
0.4
0.02
0.01 0.2
0.00 0.0
5000 4000 3000 2000 1000
-1
Wavenumber / cm
v spectra can have completely different appearance

v transmission decreases, reflectance increases with increasing wavenumber
Comparison
Transmission - Diffuse Reflectance
Transmission: self-supporting wafer
5.0 1.0
sulfated ZrO2 after activation at 723 K Reflectance: powder bed
4.8
Kubelka-Munk Function
4.6 OH vibrations 0.8
Absorbance ANapier
4.4
4.2 0.6
4.0
3.8 0.4
3.6 SO vibrations
3.4 0.2
3.2
3.0 0.0
5000 4000 3000 2000
-1
Wavenumber / cm
v vibrations of surface species may be more evident in DR spectra

n-Butane Isomerization over MnSZ: In Situ DRIFTS
1 kPa n-C4 323 K 250 50

1.2
-1
Isobutane formed / µmol g h
2% Mn-promoted
-1
Time 40
200
Kubelka-Munk units
1.0 sulfated zirconia, 323 K

on stream
0.8
150 30
0.6
100 20
0.4
1600
1630 50 sulfated zirconia, 358 K 10
0.2
0.0 0 0
1700 1650 1600 1550 0 10 20 30 40 50 60
-1 -1 -1
Wavenumber / cm Band area (1600+1630 cm ) / cm
v bands at 1600 and 1630 cm-1 increase v Rate of isomerization proportional

v also range of C=C stretching vibrations, to the amount of water formed
but corresponding CH vibrations not ob (induction period)
served
v water bending vibration
Fiber Optics
v light conducted through total reflectance

v 6 around 1 configuration: illumination through 6 (45°), signal through 1
avoids collection of specularly reflected light
pictures: Hellma (http://www.hellma-worldwide.de) and CICP (http://www.cicp.com/home.html)
Fiber Optics
v fibers need to be coupled into spectrometer beam bath

v problems: losses at couplers
picture: Hellma (http://www.hellma-worldwide.de)

example shows transmission fiber
Summary

Literature
v W. WM. Wendlandt, H.G. Hecht, “Reflectance Spectroscopy”,

Interscience Publishers/John Wiley 1966, FHI: 22 E 13
v G. Kortüm, “Reflectance Spectroscopy” / “Reflexionsspektroskopie”
Springer 1969, FHI: missing

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AC

Modern Methods in Heterogeneous Catalysis

December 10, 2004

© 2004 F.C. Jentoft, Fritz-Haber-Institut der Max-Planck-Gesellschaft

v electronic transitions, vibrations (rotations)

incident light transmitted light

reflection at phase boundaries

v how to extract absorbing properties from transmitted light?

incident light transmitted light

reflection at phase boundaries

v fraction of reflected light can be eliminated through reference

incident light transmitted light

reflection at phase boundaries

v fraction of reflected light can be eliminated through variation of

© 2004 F.C. Jentoft, Fritz-Haber-Institut der Max-Planck-Gesellschaft

v scattering is negligible in molecular disperse media (solutions)

v scattering is reduced through embedding

© 2004 F.C. Jentoft, Fritz-Haber-Institut der Max-Planck-Gesellschaft

if we manage to eliminate reflection:

decrease of I in an infinitesimally thin layer

A10 = ε c l = − log(1 − α ) (decadic) absorbance

extinction E (means absorbed + scattered light)

50 self-supporting wafers H4PVMo11O40

4000 3500 3000 2500 2000 1500 1000

v reaction with diluent possible

v transmission can become very low! even in IR regime!

v instead of measuring the transmitted light, we could measure the

© 2004 F.C. Jentoft, Fritz-Haber-Institut der Max-Planck-Gesellschaft

mirror-type reflection multiple reflections at

reflecting power called reflecting power called

v fraction of reflected light increases with α

v the intensity of the specularly reflected light is largest at an azimuth

v randomly oriented crystals in a powder:

v flattening of the surface or pressing of a pellet

particle diameter d > λ particle diameter d ≤ λ

© 2004 F.C. Jentoft, Fritz-Haber-Institut der Max-Planck-Gesellschaft

v according to Rayleigh (Gans, Born)

© 2004 F.C. Jentoft, Fritz-Haber-Institut der Max-Planck-Gesellschaft

v rigorous theory for single scattering of a planar wave at spherical

v in the limit of infinite diameter, the Mie theory approaches a

v according to the Mie formula, there is no principle distinction

scanning electron microscopy image

v need theory that treats light transfer in an absorbing and scattering

2 constants are needed to describe the reflectance:

v mostly we measure R’∞, i.e. not the absolute reflectance R∞

© 2004 F.C. Jentoft, Fritz-Haber-Institut der Max-Planck-Gesellschaft

© 2004 F.C. Jentoft, Fritz-Haber-Institut der Max-Planck-Gesellschaft

v for quantification and to be able to calculate difference spectra:

© 2004 F.C. Jentoft, Fritz-Haber-Institut der Max-Planck-Gesellschaft

Kubelka Munk units

reference „nothing“ spectrum:

v need element that collects diffusely reflected light

v KBr: IR (43500-400 cm-1)

© 2004 F.C. Jentoft, Fritz-Haber-Institut der Max-Planck-Gesellschaft

© 2004 F.C. Jentoft, Fritz-Haber-Institut der Max-Planck-Gesellschaft

0 500 1000 1500 2000 2500

v reflects well in range 335 – 1320 nm

© 2004 F.C. Jentoft, Fritz-Haber-Institut der Max-Planck-Gesellschaft

Spectralon® thermoplastic resin, excellent reflectance in UV-vis region

© 2004 F.C. Jentoft, Fritz-Haber-Institut der Max-Planck-Gesellschaft

© 2004 F.C. Jentoft, Fritz-Haber-Institut der Max-Planck-Gesellschaft

v integrating spheres (UV-vis-NIR)

© 2004 F.C. Jentoft, Fritz-Haber-Institut der Max-Planck-Gesellschaft