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Spectroscopy
Kalachakra Mandala of Tibetian Buddhism
Literature:
M.A. Banares, Raman Spectroscopy, in In situ spectroscopy of catalysts (Ed. B.M.
Weckhuysen), ASP, Stevenson Ranch, CA, 2004, pp. 59-104
Ingle, Crouch, Spectrochemical Analysis, Prenctice Hall 1988
Handbook of Spectroscopy (Ed. Gauglitz, Vo-Dinh), Wiley, Vol. 1
http://www.kosi.com/raman/resources/tutorial/index.html
Raman spectroscopy
Raman
MIR NIR
FIR
Infrared Visible UV
Microwave X-Ray
Radio Gamma
IR
Raman
NMR
XAFS
UV-Vis
EPR
incident light
scattered light
E0 E Evib = E0 – E
Raman shift
sample
Raman spectrum
electronic level
106 Rayleigh
Raman intensity
virtual level
h0 h(0-vib)
Anti-
Stokes
h0 h0 Stokes
1
excited population
= e-E/kT
relaxed population
Measure of Temperature:
4
I (Anti-Stokes) 0+vib
= e-h
vib /kT
I (Stokes) 0–vib
Raman effect
Change in polarizability,
Intensity of Raman signals depends on
2 (1+cos2)
Esc = E0
4
Polarizability,
2 (1+cos2)
Esc = E0
4
- properties of molecules
- strength/nature of bonds
Infrared Raman
as
2349 cm-1 667 cm-1
s
1340 cm-1
667 cm-1
Raman active
degenerate modes
Raman vs. Infrared
Acetone
(C-H)
(C-H)
Intensity
(C=O)
(CH3)
O
Cl
Cl
Raman vs. Infrared
Metal oxides
Transmission FTIR IR
– suitable for M-OH vibrational
modes
Raman
– characterization of bulk (i.e.
framework modes)
→ structural information
Raman – possibility to exploit resonances
→ moiety selective
excitation
line Esc proportional to 4
Fluorescence proportional to
Raman
signals
Solution
IR excitation
UV excitation
Pulsed Lasers
frequency/energy
UV Vis NIR
0.8
Aqueous solutions 785 nm
0.7
Environmental chemistry & trace
analysis
0.6
Semiconductor technology
Intensity
0.5
Biochemical and biomedical
0.4
Pharmaceutical industry
0.3
Heterogeneous catalysis
1064 nm
Forensic science
0.2
Polymer science 0.1
3500 3000 2500 2000 1500 1000 500
Food science Raman shift (cm-1)
Art conservation
Reaction monitoring
Applications
UV-Raman
No fluorescence
(only few molecules fluoresce below 260 nm)
intensity
0 400 800 1200 1600 2000 0 400 800 1200 1600 2000
Raman shift (cm-1) Raman shift (cm-1)
UV resonance as
s
O
488
325
Ti Si
X X
M O O
MOx O
-1
cm
0-7
50
O O O O M
95
O
M O
O O O O
O O
M
O polymers
O
Applications
1002
815
940
Advantage over IR
280
665
Very weak signals from surface MoO3
support oxides as SiO2 and
Al2O3 at 800–1100 cm-1
crystalline MoO3
870
300
MoO3/Al2O3
dehydrated at 500°C
V2O5
14.2 V2O5
14.2
8
4.4 8
1.2 4.4
0.16 1.2
0.03
0.16
0.01
γ-Al2O3 γ-Al2O3
intensity
624
300°C, O2
400°C, O2
300°C, H2
200 400 600 800 1000 1200 200 400 600 800 1000 1200
CH4 conv.
450°C 15 % 532 nm
425°C 4%
PdO 400°C 2%
↑ 400°C, H2
Pd(0) reduced Pd out in
Intensity
700
60000
800
860
50000
514 nm inlet reactor cell
40000
outlet
30000
20000
200 400 600 800 1000 1200
UV G-band
H-MFI
CrOx/Al2O3
Coke classification
1D topology, chain-like
2D topology, sheet-like
Coke from:
H-MFI: methanol-to-hydrocarbons (MTH)
CrOx/Al2O3: C3H8 dehydrogenation (ODH)
Coke classification
1D topology, chain-like
2D topology, sheet-like
Coke from:
H-MFI: methanol-to-hydrocarbons (MTH)
CrOx/Al2O3: C3H8 dehydrogenation (ODH)
MoS2, 6 min
full power, FB
MoS2, 6 min
1/8 power
MoS2, 1 min
full power
* -MoO3 MoS2, 6 min
full power
no conv.
zeolite (V4+O)3(SO4)54-
CH3OH CH3OH
ca. 30%
conv.
FB off V5+
SO42-
Laser induced CH3OH decomposition active species: mono- & dimeric V5+
oxosulfate species
violet/MoO2
fiber optics; spatial resolution, 1 mm