Jentoft Diffusereflectance 101204

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)
incident light reflection at phase boundaries
transmitted light
v fraction of reflected light can be eliminated through reference measurement with same materials (cuvette+ solvent)
How to Deal with Reflection (2)
incident light
transmitted light
reflection at phase boundaries 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 3300 to 250 cm-1 12500 to 3300 cm-1 50000 to 12500 cm-1 Wavelength 3 to (25-40) m (700-1000) to 3000 nm 200 to 800 nm
Mid-IR (MIR) Near-IR (NIR) UV-vis
v scattering is reduced through embedding of the particles in media with similar refractive index: KBr wafer (clear!) technique, immersion in Nujol
Transmittance
I I0
I0 Sample I
if luminescence and scattering are negligible: 1=++ (T) absorptance, absorption factor, Absorptionsgrad transmittance, transmission factor, Transmissionsgrad reflectance, reflection factor, Reflexionsgrad
if we manage to eliminate reflection: 1=+ in this case, the absorption properties of the sample can be calculated from the transmitted light
Transmitted Light and Sample Absorption Properties
I0 I
I I0
dI = I c dl
dI = c dl I I0 0
I l
decrease of I in an infinitesimally thin layer c: molar concentration of absorbing species [mol/m-3] : the molar napierian extinction coefficient [m2/mol] separation of variables and integration sample thickness: l
I ln = c l I0
Transmitted Light and Sample Absorption Properties
I = = e c l = 1 I0 Ae = B = c l = ln(1 ) A10 = c l = log(1 )
Lambert-Beer Law napierian absorbance Napier-Absorbanz (decadic) absorbance dekadische Absorbanz standard spectroscopy software uses A10!
extinction absorbance
E (means absorbed + scattered light) A (A10 or Ae)
optical density O.D. all these quantities are DIMENSIONLESS !!!!

Limitations of Transmission Spectroscopy

50
self-supporting wafers
40
2118 2036
H4PVMo11O40 Cs2H2PVMo11O40 Cs3HPVMo11O40 Cs4PVMo11O40 1379
Transmission (%)
30
2119 2040
10
1934
1632
0 4000 3500 3000 2500 2000

-1
1500
1612
1625
1257
20
CaF2WindowAbsorption
1000
Wellenzahl (cm )
But.Reaction with Material Used for Embedding

H4PVMo11O40
Transmission (%) 60
(NaCl) (KBr) (CsCl)
40
20
1083 1073 1059 896 862 788
983 960
1100
1000
900
-1
800
700
Wavenumbers (cm )
v reaction with diluent possible

Limitations of Transmission Spectroscopy

0.07 0.06 Transmittance 0.05 0.04 0.03 0.02 0.01 0.00 5000 4000 3000 2000
-1
sulfated ZrO2 after activiton at 723 K
1000
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 (polished) surfaces
mat (dull, scattering) surfaces
mirror-type reflection mirror reflection surface reflection specular reflection regulre Reflexion gerichtete Reflexion reflecting power called reflectivity
multiple reflections at surfaces of small particles
reflecting power called reflectance
Specular Reflection (Non-Absorbing Media)
incident beam
reflected beam n0 n1>n0
surface SIDE VIEW
n1
refracted beam
v fraction of reflected light increases with v depends on and ratio of the refractive indices (Snell law)
Specular Reflection: Angular Distribution
incident beam
azimuth 180 azimuth <180 surface TOP VIEW
reflected beam
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 > v light partially reflected on elementary mirrors (crystal facets) inclined statistically at all possible angles to the macroscopic surface v light penetrates into sample, undergoes numerous reflections, refractions and diffraction and emerges finally diffusely at the surface particle diameter d v scattering occurs v Mies theory for single scattering says distribution is not isotropic v multiple scattering should produce isotropic distribution
The Rayleigh Scattering Theory
v according to Rayleigh (Gans, Born) v electromagnetic wave induces vibrating dipole in molecule (i.e. d << ), electrons assumed to be in phase, molecular antenna v dipole emits electromagnetic waves in all directions, i.e. the primary wave is being scattered
I scat
1 4 0
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 m
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
(1 R ) k F ( R ) = = 2 R s
Kubelka-Munk function remission function
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) 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):
c ) 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
A = ln T
6
(1 R) 2 F ( R) = 2R
Kubelka-Munk-function
Absorbance / Kubelka-Munk
5 4 3 2 1 0 0.0
Absorbance
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 0.7 0.6 0.5 0.4 0.3 0.2 0.1 0.0 200 400
TC+A
TC+A
A = ln T
1.0 0.9 0.8 0.7 0.6 0.5 0.4 0.3 0.2 0.1 0.0 200
600
1.0 0.9 0.8 0.7 0.6 0.5 0.4 0.3 0.2 0.1 0.0
800
(1 R ) 2 F ( R) = 2R
Wavelength / nm
lower transmission
Kubelka Munk units
Absorbance
lower reflectance
higher transmission
higher reflectance
400
600
800
200
400
600
800
Wavelength / nm
Wavelength / nm
Spectroscopy in Transmission
Catalyst
Light Source
Detector
reference nothing = void, empty cell, cuvette with solvent
spectrum: transmission of 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
Catalyst
reference white standard spectrum: reflectance of sample (catalyst) vs. reflectance of standard
Detector
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: v BaSO4: v MgO:
IR (43500-400 cm-1) UV-vis 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 Reflectance % 80 60 40 20 0
"20%=" 20Sp vs. Sp. "50%=" 50Sp vs. Sp. 100%= Sp vs. Sp.
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 W P K 2 F 1 K
F total internal surface of sphere fm,,fM relative fractions of measuring surface and opening aperture W absolute reflectance of wall P absolute reflectance of sample K absolute reflectance of sphere S screen blocks regular reflection
f + fE + fP fP K = 1 M + P W 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 1.4 5 vol% n-butane
0.8 Reflectance 0.6 0.4 0.2 0.0 300 difference 400 500 600 700 800 after activation after reaction
250 200 150 100 50 0 0
1.2 1.0 0.8 0.6 0.4 0.2
60
120
180
240
300
360
0.0
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
Band area at 310 nm / a.u.
sulfated zircona, 378 K 5 vol% n-butane
-1 h-1 Rate of formation / mol g
1.0
300 isobutane propane
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

80 70 % Reflectance 60 50 40 30 20 10 0 0 500 1000 1500 2000 2500 Wavelength / nm
tilted mirror in sampling position
BC (100%): empty versus empty CBM=90 integration time NIR=0.24, UVvis=0.2 data points 1 per 1 nm (ca. 240 nm/min) slit 2 nm, gain (NIR) 1
8 June, 2004, Lambda 950, PERKIN ELMER Alignment Harrick Praying Mantis
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

80 70 60 % Reflectance 50 40 30 20 10 0 0 500 1000 1500 2000 2500
Wavelength / nm
tilted mirror in sampling position reaction chamber with spectralon and dome
BC (100%): empty versus empty CBM=90 integration time NIR=0.24, UVvis=0.2 data points 1 per 1 nm (ca. 240 nm/min) slit 2 nm, gain (NIR) 1
8 June, 2004, Lambda 950, PERKIN ELMER Alignment Harrick Praying Mantis
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 % Reflectance 7 6 5 4 3 2 1 0 0 500 1000 1500 2000 2500
tilted mirror in sampling position reaction chamber with spectralon and dome
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 cat.: AH222, heating in N2 from 50-500C (5 K/min)
Temperature / C 64 66 100 125 148 170 197 222 244 267 292 314 344 366 393 416 441 465 488 498 500 500
160 120 80 40 0
BC with different parameters!
% Reflectance
BC (100%): spectralon + dome versus 10%T CBM=90 integration time NIR=0.08, UVvis=0.08 data points 1 per 1 nm (ca. 570 nm/min) slit 2 nm, gain (NIR) 2
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 0.06 Transmittance 0.05 0.04 0.6 0.03 0.02 0.01 0.00 5000 4000 3000 2000
-1
sulfated ZrO2 after activation at 723 K
1.2 Transmission: self-supporting wafer Reflectance: powder bed 1.0 0.8 Reflectance
0.4 0.2 0.0 1000 Wavenumber / cm
v spectra can have completely different appearance v transmission decreases, reflectance increases with increasing wavenumber
Comparison Transmission - Diffuse Reflectance

5.0 4.8 4.6 4.4 4.2 4.0 3.8 3.6 3.4 3.2 3.0 5000 0.0 4000 3000
-1
sulfated ZrO2 after activation at 723 K
Transmission: self-supporting wafer 1.0 Reflectance: powder bed

0.8 0.6 0.4
Absorbance ANapier
OH vibrations
SO vibrations
0.2
2000
Wavenumber / cm
v vibrations of surface species may be more evident in DR spectra

Kubelka-Munk Function
n-Butane Isomerization over MnSZ: In Situ DRIFTS

1.2 Kubelka-Munk units 1.0 0.8 0.6 0.4 0.2 0.0 1700 1650 1600 -1 Wavenumber / cm 1550 1630 1600
-1
1 kPa n-C4 323 K

Time on stream
250 200 150 100 50 0 0 10 20 30 40

-1
50 2% Mn-promoted sulfated zirconia, 323 K 40 30 20 sulfated zirconia, 358 K 10 0 50

-1
Isobutane formed / mol g h
-1
60
Band area (1600+1630 cm ) / cm
v bands at 1600 and 1630 cm-1 increase
v Rate of isomerization proportional to the amount of water formed v also range of C=C stretching vibrations, (induction period) but corresponding CH vibrations not ob
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 2004 F.C. Jentoft, Fritz-Haber-Institut der Max-Planck-Gesellschaft
Summary
Literature
v W. WM. Wendlandt, H.G. Hecht, Reflectance Spectroscopy, Interscience Publishers/John Wiley 1966, FHI: 22 E 13 v G. Kortm, Reflectance Spectroscopy / Reflexionsspektroskopie Springer 1969, FHI: missing

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AC

Diffuse Reflectance IR and UV-vis Spectroscopy

December 10, 2004

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

UV- vis- NIR MIR

Interaction of Light with Sample

How to Deal with Reflection (1)

incident light reflection at phase boundaries

How to Deal with Reflection (2)

Mid-IR (MIR) Near-IR (NIR) UV-vis

Transmitted Light and Sample Absorption Properties

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

Transmitted Light and Sample Absorption Properties

I = = e c l = 1 I0 Ae = B = c l = ln(1 ) A10 = c l = log(1 )

E (means absorbed + scattered light) A (A10 or Ae)

optical density O.D. all these quantities are DIMENSIONLESS !!!!

Limitations of Transmission Spectroscopy

H4PVMo11O40 Cs2H2PVMo11O40 Cs3HPVMo11O40 Cs4PVMo11O40 1379

0 4000 3500 3000 2500 2000

But.Reaction with Material Used for Embedding

1083 1073 1059 896 862 788

v reaction with diluent possible

Limitations of Transmission Spectroscopy

sulfated ZrO2 after activiton at 723 K

Can We Use the Reflected Light?

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

Specular & Diffuse Reflection

mirror-type (polished) surfaces

mat (dull, scattering) surfaces

multiple reflections at surfaces of small particles

reflecting power called reflectance

Specular Reflection (Non-Absorbing Media)

reflected beam n0 n1>n0

surface SIDE VIEW

Specular Reflection: Angular Distribution

azimuth 180 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

Light Reflection from Powders: Why is the Distribution Isotropic?

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

The Rayleigh Scattering Theory

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

The Mie Scattering Theory

Typical Catalyst Particles

The Schuster-Kubelka-Munk Theory

Kubelka-Munk function remission function

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

Deviations from & Limitations of the Kubelka-Munk Theory

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

Transmission vs. Reflection Spectroscopy

Transmission vs. Reflection Spectroscopy

Kubelka Munk units

reference nothing = void, empty cell, cuvette with solvent

spectrum: transmission of catalyst vs. transmission of reference

v KBr: v BaSO4: v MgO:

IR (43500-400 cm-1) UV-vis UV-vis

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

White Standard MgO

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

White Standard BaSO4

v reflects well in range 335 1320 nm v humid!

White Standard Spectralon