Basic principles
- Resonance Raman scattering
- Surface Enhanced Raman Scattering (SERS)
Instrumentation
- Spectrometer
- Excitation sources
Raman in catalysis
- In situ cells
- In situ Raman (of working catalysts)
C. Hess, 2006
Introduction
Why Raman spectroscopy?
Information on rotational and vibrational levels
Raman effect small but accessible by use of lasers
Complementary information to IR spectroscopy
p homonuclear diatomic molecules, low frequency range
In situ analysis of organic and inorganic compounds
Analysis of aqueous solutions and solids (powders)
Using resonance and surface enhancement effects ~1010
p Trace gas/single molecule analysis - molecular structure
C. Hess, 2006
Classical description
Spatial charge separation under influence of electric field E
p induced dipole moment :
=E
(1)
: polarizability
C. Hess, 2006
C. Hess, 2006
C. Hess, 2006
Classical description
Spatial charge separation under influence of electric field E
p induced dipole moment :
=E
(1)
: polarizability
Electric field E due to electromagn. wave with frequency 0
E = E0 cos 2 0t
(2)
p = E0 cos 2 0t
(3)
2
dt
* =
(4)
C. Hess, 2006
Classical description
Internal vibrational motion with Eigenfrequency vM
q = q0 cos 2 Mt
(5)
(6)
p=E
(7)
Stokes/Anti-Stokes
C. Hess, 2006
Q.M. description
p harmonic oscillator: v = 1
inelastic impact
elastic impact
inelastic impact
EM > 0
EM = 0
EM < 0
= 0
= 0 vib < 0
h0
~~~~
h0
~~~~
h(0 - vib)
~~~~
Stokes
h0
~~~~
= 0 vib > 0
h0
~~~~
h0
~~~~
h(0 + vib)
~~~~
h0
~~~~
=1
=1
=1
=1
=0
=0
=0
=0
Rayleigh
Anti-Stokes
C. Hess, 2006
Q.M. description
Raman intensity?
p Is = Ni R(if) IL
(8)
(9)
Q.M. description
80000
514nm excitation
neat CHCl3
Intensity
60000
40000
20000
0
Anti-Stokes
-800
-400
Stokes
0
400
800
-1
C. Hess, 2006
Basic principles
- Resonance Raman scattering
- Surface Enhanced Raman Scattering (SERS)
Instrumentation
- Spectrometer
- Excitation sources
Raman in catalysis
- In situ cells
- In situ Raman (of working catalysts)
C. Hess, 2006
resonance
virtual level
Vis
Stokes
g1
g0
Vis
e
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p
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tin
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-rin
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cu
Stokes
g1
g0
s
a
G
ev
e
l
w
resonant Raman
non-resonant Raman
1 g1 ev ev g 0
=
h v wev,g0 w0 + iev
C. Hess, 2006
Example: -Carotin
electronic
resonance
virtual level
resonance
virtual level
Absorbance
Vis
514nm
Vis
Stokes
v=1
v=0
non-resonant Raman
Stokes
632nm
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w
v=1
v=0
resonant Raman
Wavelength (nm)
C. Hess, 2006
Example: -Carotin
-carotin, 9mW, 20s exp
514nm excitation
632nm excitation
Intensity
30000
C=C stretch
enhancement
factor = 10
20000
10000
0
0
400
800
1200
1600
2000
-1
Basic principles
- Resonant Raman spectroscopy
- Surface Enhanced Raman Scattering (SERS)
Instrumentation
- Spectrometer
- Excitation sources
Raman in catalysis
- In situ cells
- In situ Raman (of working catalysts)
C. Hess, 2006
Introduction to SERS
Normal Raman scattering
N molecules with R,free
I(L)
I(S)
C. Hess, 2006
I(L) A(L
)2
N with R,ads, N N
Rough surface
e.g. metal nanostructure
Molecule
r
metal
I(S) A(S)2
ISERS(S) = N
I(L) A(L)2
A(S)2 R,ads
EM()
A() =
E0()
SERS substrate
SEM images of the silver nanowire ML on Si wafer
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SERS substrate
UV-VIS absorption spectra of silver nanowire ML
transverse
longitudinal
Raman
s
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CH2
twist/
scissor
CH2
wag
(C-C)
CH3
rock
(C-S)t
s
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p
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lw
D EF = 2 105
C. Hess, 2006
s
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C. Hess, 2006
Basic principles
- Resonant Raman spectroscopy
- Surface Enhanced Raman Scattering (SERS)
Instrumentation
- Spectrometer
- Excitation sources
Raman in catalysis
- In situ cells
- In situ Raman (of working catalysts)
C. Hess, 2006
Raman spectrometer
Challenges to record (good) spectra
Separate inelastically scattered from Rayleigh (99.99999%) light
Collect the maximum number of inelastically scattered photons
Triple spectrograph
first 2 gratings subtractive
p removal Rayleigh (40% E)
grating 3/4 creates dispersion
detection: diode array
Fourier Transform (FT) - Raman
Michelson interferometer
(Jacquinot, multiplex)
NIR (1.064 m) excitation,
p less fluorescence
p self absorption
Detector
(CCD)
Dispersion
grating
Notch
filter
Light source
(Laser)
sample
sampling
optics
(objective,
immersion probe)
Basic principles
- Resonant Raman spectroscopy
- Surface Enhanced Raman Scattering (SERS)
Instrumentation
- Spectrometer
- Excitation sources
Raman in catalysis
- In situ cells
- In situ Raman (of working catalysts)
C. Hess, 2006
Basic principles
- Resonant Raman spectroscopy
- Surface Enhanced Raman Scattering (SERS)
Instrumentation
- Spectrometer
- Excitation sources
Raman in catalysis
- In situ cells
- In situ Raman (of working catalysts)
C. Hess, 2006
{
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Gas outlet
Laser excitation at
low laser power to
minimize heating
Quartz window
Sample
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Heating wire
Quartz wool
High-temperature
cement
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O-ring
Plug-flow reactor
Gas inlet
Quartz chips
Thermocouple well
C. Hess, 2006
Particle motion
p reduces laser
beam exposure
Raman cell mimics
fluidized bed reactor:
gases flow through
catalyst bed
~200 mg sample
UV laser excitation
Sample rotation
p reduces laser
beam exposure
Gas flow over
catalyst bed
Requires pellets
~200 mg sample
Basic principles
- Resonant Raman spectroscopy
- Surface Enhanced Raman Scattering (SERS)
Instrumentation
- Spectrometer
- Excitation sources
Raman in catalysis
- In situ cells
- In situ Raman (of working catalysts)
C. Hess, 2006
O2
NO2
Pt
NO
BaNO 3
BaO
BaO
O2
NO2
Pt
Support
C. Hess, 2006
{
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High-temperature
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Sample
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O-ring
Quartz chips
Thermocouple well
C. Hess, 2006
200 nm
1327
Minutes:
20.0
2+
Ba -NO 2
1200
1400
-1
Raman shift (cm )
9.0
7.5
Ba(NO 3 ) 2
134
731
Ba(NO 2 )
822
1% NO2
400 C
1337
50
30
259
es
10
1327
2+
Ba -NO2
Min
ut
1337
10.0
Minutes:
6.0
7.5
8.0
8.5
9.0
C. Hess, 2006
1049
151
Ba(NO 3 ) 2
135
1048
724 814
Ba(NO 2 )
733
825
1337
30
253
20
10
1335
60
30
10
1327
Minu
tes
259
Minute
s
1% NO2
300 C
1327
2+
2+
Ba -NO2
Ba -NO2
1% NO2
400 C
1% NO2
400 C
1336
10
Ba -NO2
5
1052
Minut
es
2+
1048
Ba(NO 3 ) 2
134
730
20
15
10
1052
5
2+
Ba -NO2
500
1000
-1
1500
500
1000
1500
-1
Minut
es
1052
140
1% NO2 / 20% O2
300 C
1048
Ba(NO 3 ) 2
Ba(NO 3 ) 2
730
732
30
20
10
Minut
1337
es
824
Ba(NO 2 )
5
0
utes
10
136
M in
134
1049
BaO
+ NO2 /He
NO 2
Ba 2+
O
He
+ O2 /He
BaO 2
+ NO2 /He
+ NO2 /He
+ NO2 /He
NO
Ba(NO 3 ) 2
400 C
500 C
400 C/O2
300 C/O2
C. Hess, 2006
C. Hess, 2006
Raman
C=C (coke)
W=O
250C
S(2-methylbutane)
~30%
I o R (1 + R )
s
(1 R )
I 0
s
G ( R )
cv 4 I o R (v)[1 + R (v)]
(v ) =
[1 R (v)]
s
cI 0
( [{ }] ) = G[R (v)] 4
s
R (v) : can be measured by
corrected data
plasma line
OH
O O
O
O O
O
O
alumina
Preferential excitation
of structurally different
VxOy species possible?
Visible laser
LMCT:
OpV
4.4 V/nm2
1.2 V/nm2
0.03 V/nm2
V=O in:
Vis
V2O5 VxOy
UV
1018
1030
O
O O
O
O
alumina
OH
O O
MeOH/O2 = 3
Ag=O Ag-O-Ag
decreasing
Ag-O-Ag int
in MeOH/O2
p active site?
p assignment?
p subsurface?
p thermal cycles
p 2 diff. atomic O species
(isotope shifts ~20 cm-1)
Questions?