Raman

Spectroscopy

Dr. Davide Ferri

Paul Scherrer Institut
 056 310 27 81
 [email protected]
 Raman spectroscopy

Raman
MIR NIR
FIR

Infrared Visible UV

Microwave X-Ray

Radio Gamma

Wavelength 5 x 109 10000 500 250 0.5 5 x 10-4 nanometers

Energy 2.48 x 10-7 0.124 2.48 4.96 2480 2.45 x 106 eV

 Raman spectroscopy

Chandrasekhara Venkata Raman (1888 – 1970)

February 28, 1928: discovery of the Raman effect

Nobel Prize Physics 1930 “for his work on the scattering of

light and for the discovery of the effect named after him”

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
Importance of Raman spec. in catalysis

IR

Raman

NMR

XAFS

UV-Vis

EPR

0 200 400 600 800 1000 1200

Number of publications

Number of publications containing in situ, catalysis, and respective method

Source: ISI Web of Knowledge (Sept. 2008)
 Raman spectroscopy

incident light

scattered light

E0 E Evib = E0 – E
Raman shift
sample

elastic scattering = Rayleigh scattering

inelastic scattering = Raman scattering (ca. 1 over 107 photons)
 Classic mechanics approach

Electric field of exciting radiation: E = E0cos(20t)

Induced dipole: in = E = E0cos(20t)
Induced change of :  = 0 + cos(2vibt)

in = E = [0 + cos(2vibt)]E0cos(20t)

in = 0E0cos(20t) + E0cos(2vibt)cos(20t)

and in = 0E0cos(20t) + /2E0cos[2(0+vib)t] + /2E0cos[20-vib)t]}

Rayleigh Anti-Stokes Stokes

cosx·cosy = 1/2 [cos(x+y)+cos(x–y)]

 Quantum mechanics approach

Raman spectrum
electronic level

106 Rayleigh

Raman intensity
virtual level

h0 h(0-vib)
Anti-
Stokes
h0 h0 Stokes
1

vibrational levels h0 h(0+vib)

vib vib
v = 1 (final)
hvib
v = 0 (initial)
0– 0 0+
Rayleigh Stokes Anti-Stokes Raman shift (cm-1)

 Same information contained in Stokes and Anti-Stokes signals

 Same distance from Rayleigh line whatever 0
 Quantum mechanics theory

 Classical theory inadequate: same intensity for Anti-Stokes and Stokes

lines is predicted

excited population
= e-E/kT
relaxed population

Stokes lines more intense than Anti-Stokes lines (factor 100)

 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

 E0 = incident beam irradiance

  = polarizability of the particle (ease of distortion of the electron cloud)
  = wavelength of the incident radiation
  = angle between incident and scattered ray

 More scattering at low wavelength (at higher frequency)

 Raman effect

 Polarizability, 

2 (1+cos2)
Esc = E0
4

- properties of molecules
- strength/nature of bonds

covalent bond STRONG Raman signals

ionic bond WEAK Raman signals

 Raman vs. Infrared

Infrared Raman

Absorption of IR light Inelastic scattering of light

 Raman vs. Infrared
Selection rules
2 2
∂ ∂
≠0 ≠0
∂Q ∂Q

 high absorption for polar bonds  high absorption for easily

(C=O, H2O, NH, etc.) polarizable bonds
 large electron clouds
 not polar
 H2O is a very weak Raman
scatterer
 C=C double bonds strong
Raman scatterers
 Raman vs. Infrared
CO2
- + -

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)

Raman shift (cm-1)

 Raman vs. Infrared

O
Cl

Cl
 Raman vs. Infrared

 Metal oxides

 <700 cm-1: covalent bond character, strong signals in Raman

 >100 cm-1: low polarizability of light elements (Si, Al, O) and ionic character:
weak signals in Raman
 Raman more suitable than IR in low wavenumber range (M-O-M) but
complementary in high wavenumber range (M=O)
Wachs, Catal. Today 27 (1996) 437
 Raman vs. Infrared
H-ZSM-5

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

 Both applicable in a wide range of

conditions
→ suitable for in situ studies

courtesy by M. Signorile, UniTO

 Raman vs. Infrared

 Metal oxides
12 wt% V2O5/Al2O3-TiO2

5 wt% V2O5/Al2O3-TiO2
overtone region (2(V=O)) fundamental mode region ((V=O))

1026
2042 FTIR

1025 890 Raman

monomer polymer 845
300
O O O O
V V V V
O O
O
O
HO O O O
O O
Ti

Vuurman et al., J. Chem. Soc. Faraday Trans. 92 (1996) 3259; Concepcion et al., PCCP 1 (1999) 3031
 Raman vs. Infrared
 Simple optics
 Versatile design of cells (quartz & glass allowed)
 Fiber optics
Advantages

 Almost no limitation in temperature

 Very small amount (picog) of sample possible
 Water no problem
 Sensitive to microcrystals (< 4 nm)
 Sample of phase not critical
 Spatial resolution (1 m)
 No contribution from gas phase
Disadvantages

 Relatively expensive instruments

 Low spectral resolution (UV and Vis)
 Difficult quantification (limited to heterogeneous catalysis)
 Structure of analyte affected by high energy of laser (e.g. UV Raman)
 Fluorescence
 Fluorescence and Raman signals
Fluorescence Emission of visible light during
a time posterior to the sample
UV Raman Vis Raman FT Raman irradiation

excitation
line Esc proportional to 4
Fluorescence proportional to 
Raman
signals

Solution
 IR excitation
 UV excitation
 Pulsed Lasers

frequency/energy
UV Vis NIR

107 stronger than Raman scattering

 Fluorescence and Raman signals

Fan et al., Acc. Chem. Res. 43 (2009) 378

 Applications

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)

Rh/Al2O3, coked 500°C in naphtha

5 mW, 257 nm 100 mW, 514.5 nm

intensity

intensity

0 400 800 1200 1600 2000 0 400 800 1200 1600 2000
Raman shift (cm-1) Raman shift (cm-1)

Stair et al., J. Vacuum Technol. A 15 (1997) 1679

 Resonance Raman spectroscopy
 Raman scattering is strongly enhanced (factor 106 !) if the excited state is
not virtual, but an electronically excited state
 Vibrations related to an electronic transition are excited
 This can be tuned by changing the laser wavelength

 Example organic molecules:

resonance with a π→π* transition enhances stretching modes of the π-
bonds involved with the transition, while the other modes remain
unaffected
 Resonance Raman spectroscopy
 Multiwavelength approach to achieve different resonances
Raman
perfect defective highly defective
highly 1 244 nm 3
defective
3 2
UV-vis
266 nm
2
defective
perfect
Ti4+-O 1 1064 nm

• 244 nm → perfect sites

• 266 nm → defect sites, perfect sites + ligands
• 1064 nm (out of resonance) → SiO2 framework, bulk TiO2 TS-1

courtesy of M. Signorile, UniTO

 Applications

 UV resonance as

 s

488
325

Ti Si

X X

Additional detailed structural information not available upon vis irradiation

Li et al., Angew. Chemie 38 (1999) 2220
 Applications

MOx/M’OX used in a number of industrial chemical

processes (dehydrogenation, oxidation,
amoxidation…)

Question: nature of MOx and the role in catalysis?

 Applications

 Monolayer (monomeric) & polymeric species

MOx surface species
O
O O
O O
1030-990 cm-1
M
M
M O O
O MOx
O O
950-750 cm-1 O O νas = 900 cm-1
monomers νs = 600 cm-1
δ = 200 cm-1
-1
0 cm
950-75 O
O O
crystalline phase O
O
O
M
O
M
M M
+ ev. polymers O
O O M O
O

M O O
MOx O
-1
cm
50
-75
0
O O O O M
9
O
M O
O O O O
O O
M
O polymers
O
 Applications

 Monomeric & polymeric species

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

MoO3/Al2O3 300
dehydrated at 500°C

Wachs, Catal. Today 27 (1996) 437

 Applications

 Monomeric & polymeric species

UV-laser vis-laser
244 nm 488 nm

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

Wu et al., J. Phys. Chem. B 109 (2005) 2793

 Applications
 Reactivity of V/TiO2 after oxidative treatment
V5+Ox

VxOy VxOy

air flow @ 450°C

O2/C3H8 @ 20°C V5+ → V4+
@ 100°C
@ 150°C
@ 200°C

TiO2: 402 cm-1

V2O5: 996 cm-1

Brückner et al., Catal. Today 113 (2006) 16

 Examples for in situ studies

M/MOX (M= Pd, Pt, Rh; MOx= Al2O3, ZrO2, CeO2…)

used for total and partial oxidation reactions

Question: what is the state of Pd during reaction?

Examples: Pd for CH4 combustion

Rh for CH4 partial oxidation
 Applications

 Resonance Raman – State of the metal in Pd/Al2O3

624
273 431 as prepared
+
300°C
3 min O2
intensity

624
300°C, O2

300°C, H2

200 400 600 800 1000 1200

Raman shift (cm-1)

2 wt% Pd/Al2O3, red. 400°C (3 h) + calcined 600°C (3 h)

Demoulin et al., PCCP 5 (2003) 4394

 Applications

 Resonance Raman – Methane oxidation over Pd/Al2O3

PdO
CH4 + 2O2 → CO2 + 2H2O

CH4 conv.

feed CH4/O2 (1:10)

500°C 24 %
near PdO mode
objective+
intensity

450°C 15 % 532 nm

425°C 4%
PdO 400°C 2%
↑ 400°C, H2
Pd(0) reduced Pd out in

200 400 600 800 1000 1200

Raman shift (cm-1)

2 wt% Pd/Al2O3, red. 400°C (3 h) + calcined 600°C (3 h) Demoulin et al., PCCP 5 (2003) 4394
 Applications

 Resonance Raman – Methane oxidation over Pd/ZrO2

90000

gas-phase 650→630 cm-1

combustion T (°C)
80000 70
PdO→Pd 200
change in PdO 300
70000 400
stoichiometry ?
Pd→PdO 500
600

Intensity
700
60000
800
860

50000
514 nm inlet reactor cell

40000
outlet

30000

20000
200 400 600 800 1000 1200

oven Raman shift (cm-1)

1 vol% CH4/4 vol.% O2/He

10 wt.% Pd/ZrO2
 Applications

 (Polyaromatic) Coke formation and characterization

D-band

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)

Stair, Adv. Catal. 51 (2007) 75

 Applications

 (Polyaromatic) Coke formation and characterization

Coke classification
1D topology, chain-like
2D topology, sheet-like
Coke from:
H-MFI: methanol-to-hydrocarbons (MTH)
CrOx/Al2O3: C3H8 dehydrogenation (ODH)

Stair, Adv. Catal. 51 (2007) 75

 Applications
 Fluidized bed reactor cell

Chua et al., J. Catal. 196 (2000) 66

 Applications
 Fluidized bed reactor cell
hydrodesulfurization

MoS2, 6 min
full power, FB

MoS2, 6 min
1/8 power

MoS2, 1 min
full power
* -MoO3 MoS2, 6 min
full power

Beato et al., Catal. Today 205 (2013) 128

 Applications
 Fluidized bed reactor cell
CH3OH steam reforming (r.t.) on H-ZSM5 Sulfuric acid V2O5/pyrosulfate catalyst
= 244 nm = 514 nm
V-O-V
CH3OH
V-O-S
polym. species
FB

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

Beato et al., Catal. Today 205 (2013) 128

 Applications
 Fixed bed reactor
ethane ODH on MoOx/Al2O3
1 mm Al2O3 spheres

violet/MoO2
fiber optics; spatial resolution, 1 mm

full O2 conv.  monitoring of reaction in fixed bed

max. C2H4 conc.
reactor (Raman/MS)
 partial reduction MoO3→MoO2
with decreasing O2 content
yellow/MoO3  MoO3 vanishes when no O2 is
present (point , 19 mm)

Geske et al., Catal. Sci. Technol. 3 (2013) 169