Raman spectroscopy:

Basic principles and applications

Christian Hess

• Basic principles
- Resonance Raman scattering
- Surface Enhanced Raman Scattering (SERS)
• Instrumentation
- Spectrometer C.V. Raman (1928)
- Excitation sources
• Raman in catalysis
- In situ cells
- In situ Raman (of working catalysts)
• 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 μ:
μ=αE (1)
α: polarizability

p Example: polarizability changes during CO2 vibrations

C. Hess, 2006
Example: Polarizability changes CO2
Vibrational modes of CO2

C. Hess, 2006
Example: Polarizability changes CO2
Vibrational modes of CO2

C. Hess, 2006
Classical description

• Spatial charge separation under influence of electric field E

p induced dipole moment μ:
μ=αE (1)
α: polarizability

• Electric field E due to electromagn. wave with frequency ν0

E = E0 cos 2π ν0t (2)
p μ = α E0 cos 2π ν0t (3)
p emission of light at same frequency ν0
2
⎛d μ⎞
2
p I = (2/3c3) μ* μ* = ⎜⎜ ⎟
2 ⎟

= (16π4α2E02/3c3) ν04 ⎝ dt ⎠ (4)

C. Hess, 2006
Classical description

• Internal vibrational motion with Eigenfrequency vM

q = q0 cos 2π νMt (5)

• Polarizability α p develop in series

α = αq=0 + (∂α/∂q)q=0 q + higher order terms (6)

pμ=αE (7)
= (αq=0 + (∂α/∂q)q=0 q0 cos 2π νMt) E0 cos 2π ν0t
= αq=0 E0 cos 2π ν0t + ½ (∂α/∂q)q=0 q0 E0 [cos 2π (ν0 - νM)t
+ cos 2π (ν0 + νM)t

Rayleigh Stokes/Anti-Stokes
C. Hess, 2006
Q.M. description
p harmonic oscillator: Δv = ±1
inelastic impact elastic impact inelastic impact

ΔEM > 0 ΔEM = 0 ΔEM < 0

ν = ν0 – νvib < ν0 ν = ν0 ν‘ = ν0 – νvib > ν0

hν0 hν0 hν0 h(ν0 + νvib)

~~~~ ~~~~ ~~~~ ~~~~
hν0 h(ν0 - νvib) hν0 hν0
~~~~ ~~~~ ~~~~ ~~~~

ν=1 ν=1 ν=1 ν=1

ν=0 ν=0 ν=0 ν=0

Stokes Rayleigh Anti-Stokes

C. Hess, 2006
Q.M. description

Raman intensity?
p Is = Ni σR(i→f) IL (8)
Ni: initial state population
σR(i→f): Raman cross section for transition Ei→Ef
IL: Laser intensity

p thermal equilibrium: Boltzmann distribution for state Ni at T

Ni = N0 exp(-ihνvib/kT) (9)
p lower energy state: higher initial state population
I(Stokes) > I(Anti-Stokes)
p Example: Stokes/Anti-Stokes intensities of CHCl3
C. Hess, 2006
Q.M. description

80000 514nm excitation

neat CHCl3

60000
Intensity

40000

20000

0
Anti-Stokes Stokes
-800 -400 0 400 800
-1
Raman shift (cm )
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
Introduction to Resonance Raman scattering

electronic ev
resonance resonance
virtual level virtual level

Stokes Stokes
Vis Vis

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non-resonant Raman resonant Raman

p Polarizability tensor α (single e state):

1 ⎛⎜ g1 μˆα ev ev μˆ β g 0 ⎞
α αβ = ∑ ⎟
h v ⎜⎝ wev,g0 − w0 + iΓev ⎟
⎠
μˆα , μˆ β : Electric dipole moment operator
i.a. with incident/scattered light
C. Hess, 2006
Example: β-Carotin

electronic
resonance resonance
virtual level virtual level

Stokes 514nm 632nm

Stokes
Vis Vis
Absorbance

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v=1
v=0 v=0
non-resonant Raman resonant Raman

Wavelength (nm)
C. Hess, 2006
Example: β-Carotin

β-carotin, 9mW, 20s exp

30000 514nm excitation
632nm excitation C=C stretch

20000 enhancement
Intensity

factor = 10

10000

0 400 800 1200 1600 2000

-1
Raman shift (cm )

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
Introduction to SERS
‘Normal’ Raman scattering

N molecules with σR,free

I(νL)
I(νS)

INRS(νS) = N I(νL) σR,free

C. Hess, 2006
SERS mechanism - enhancement factors
Surface-enhanced Raman scattering Molecule
ε0
r
N’ with σR,ads, N’ ≤ N d

“Rough” surface ε
metal
I(νL) A(νL )2 e.g. metal nanostructure
I(νS) A(νS)2

EM(ν)
ISERS(νS) = N’ I(νL) A(νL)2 A(νS)2 σR,ads A(ν) =
E0(ν)

(1) E.m. field enhancement (2) Chemical enhancement

max. ~ 106 (isolated Ag,Au) max. 10-100
max. ~ 108 (coupled)
C. Hess, 2006
SERS substrate
SEM images of the silver nanowire ML on Si wafer

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D Deposited ML shows domains of aligned silver nanowires

A. Tao, F. Kim, C. Hess, J. Goldberger, R. He, Y. Sun, Y. Xia, P. Yang, Nano Lett. 3 (2003) 1229
SERS substrate
UV-VIS absorption spectra of silver nanowire ML
transverse longitudinal

Raman
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D Broadened extinction 500-600 nm due to wire-wire coupling

SERS example: 1-hexadecanthiol/Ag-LB film

ν(C-S)t

ν(C-C)

scissor
twist/
rock

CH2
CH3

CH2
wag
• Enhancement factor EF:
EF = [ISERS]/[IRaman] × [Mb]/[Mads]

• thiol head group (2.3 Å)2,

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closed-packed layer
D molecule conc. on surface:
2.5 × 1014/cm2
D 532nm, band at 1295 cm-1

D EF = 2 × 105

C. Hess, 2006
SERRS example: Rhodamine 6G/Ag-LB film

SERRS = Surface Enhanced Resonance Raman Scattering

• Linear relationship between

intensity and concentration
D surface not saturated
• Langmuir description using
Mads= Mads,max Ka0/(1+Ka0)
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yields ΔGads = 46 KJ/mol

• Large EF = 109 as result of

SERS and Resonant Raman

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 µm) excitation,
p less fluorescence
p self absorption
Modern Raman spectrometer
• holographic notch filters
Detector p 80% T of Raman light,
(CCD) 324 - 1339 nm available
• single transmission grating
p 0 - 4400 cm-1 (multiplex)
“clean”, no moving parts,
high light throughput
• cooled CCD (~ 40% QE)
p 400 - 1000 nm detection

sample
Dispersion Notch
grating filter sampling
optics
Light source (objective,
(Laser) 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
Laser excitation wavelengths

Fluorescence
(typical range) (organic samples/water)

choice of laser wavelength:

• scattering intensity ~ν4
• detectors
• resonance enhancement
• self-absorption of sample
• fluorescence (pNIR, UV)
• 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
In situ Raman cells
Raman-scattered light • Laser excitation at
low laser power to
minimize heating
Quartz window
Sample
• Raman cell design
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Heating wire reactor: gases flow
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High-temperature
through catalyst bed
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• 50 – 100 mg sample

• • O-ring

Plug-flow reactor
Gas inlet
Quartz chips

Thermocouple well C. Hess, 2006

In situ Raman cells

Fluidized bed reactor • Particle motion

p reduces laser
beam exposure
• Raman cell mimics
fluidized bed reactor:
gases flow through
catalyst bed
• ~200 mg sample
• UV laser excitation
In situ Raman cells

Rotating Raman cell • 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
The NOX storage-reduction concept
• Lower fuel consumption by use of engines operating with excess oxygen
€ Problem: Reduction of NOx
€ Solution: Storage of NOx followed by short rich periods for reduction

• Typical storage catalysts consist of storage material (BaO) and metal (Pt)

NO
NO
O2 O2
NO BaNO 3
NO2 NO2

Pt
BaO
BaO Pt
Support

• BaO/Al2O3 deactivates at higher temperatures (due to Ba-Al alloying)*

€ Focus on BaO/MgO which is stable up to at least 900°C
* Jang et al., Catal. Lett. 77 (2001) 1
C. Hess, 2006
Experimental setup: In situ Raman spectroscopy
Raman-scattered light
• Laser excitation at 532 nm,
low laser power of ~6 mW
Quartz window minimizes heating of sample
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bed (50 mg) at ~40 ml/min

• • O-ring

Gas inlet
Quartz chips

Thermocouple well C. Hess, 2006

Preparation of the 14 mol % BaO/MgO catalyst

• Impregnation of Ba(NO3)2 on MgO (Fisher)

• Drying at 100°C, heating at 120°C for 2h
• Heating to 900°C in He for 2h to decompose Ba(NO3)2 and BaCO3
• BaO formation confirmed by XRD

• TEM shows formation of

homogeneous BaO phase
• X-ray analysis confirms
the presence of BaO/MgO

200 nm Jeol 2010, 200 kV, x40k

C. Hess, 2006
In situ Raman spectra during NO2 exposure
1048 Minutes:
1327 20.0
2+
Ba -NO 2
10.0
Minutes:
6.0
7.5
8.0
9.0
8.5
1337 9.0 7.5

1200 1400 1020 1050 1080

-1
Raman shift (cm ) Ba(NO 3 ) 2 -1
Raman shift (cm )
134 1% NO2
731 +
Ba(NO 2 ) 400 C
822 1337
50
259 30
10

es
1327

ut
5

Min
2+
Ba -NO2
0

€ Formation of nitro species precedes that of nitrates C. Hess, 2006

In situ Raman spectra during NO2 exposure

Temperature dependence
1% NO2 1049 1% NO 2 1048
300 C 475 C
151
Ba(NO 3 ) 2
724 814 1337
30
253
135 + 20
Ba(NO 2 )
733
1335 10
825
60
30

s
Minute
10
259 5
tes 1327
Minu
1327 5
2+
2+ Ba -NO2
Ba -NO2 0 0

€ 300°C: Formation of nitro species precedes nitrates (as at 400°C)

€ 475°C: Higher rate of NO3- formation but smaller storage capacity
In situ Raman spectra after catalyst pre-oxidation
C. Hess, 2006
Dependence on pre-oxidation time
1% NO2 1% NO2 1048
400 C 400 C
25% O2 pre-flow: 1 min 25% O2 pre-flow: 4 min
Raman intensity (a.u.)

Raman intensity (a.u.)

Ba(NO 3 ) 2
134
1052 730
140
1336
20
10 15
10
2+
Ba -NO2
1052
es

es
5 5
Minut

Minut
1052
2+
Ba -NO2
0 0

0 500 1000 1500 0 500 1000 1500

-1 -1
Raman shift (cm ) Raman shift (cm )

€ Pre-oxidation of BaO enables direct nitrate formation at 400°C

In situ Raman spectra during NO2 /O2 exposure
Temperature dependence
1% NO2 / 20% O2 1048 1% NO2 / 20% O2 1049
400 C 300 C

Ba(NO 3 ) 2 Ba(NO 3 ) 2

134
730
136

10
2 732 Ba(NO 2 )
+

824 1337
30
20
es
10
Minut
5

utes
5

M in
0 0

€ Presence of oxygen surpresses formation of nitro species

increases the rate of nitrate formation
Summary - Mechanism for NO2 storage

NO 2
+ NO2 /He + NO2 /He
BaO Ba 2+ [Ba(NO 2 )]+ + [Ba(NO 3 )] +
O + NO2 /He
+ O2 /He He NO

+ NO2 /He
BaO 2 Ba(NO 3 ) 2

C. Hess and J.H. Lunsford, JPCB 106 (2002) 6358

C. Hess and J.H. Lunsford, JPCB 107 (2003) 1982
Summary - NO2 storage capacity

400 C
500 C
400 C/O2
300 C/O2

C. Hess, 2006
Summary: Study reveals Raman key features

• Raman spectra without interference of gas phase

• simple glass/quartz cell
• in situ spectra can be recorded at high temperatures (500°C)
• time-dependent in situ experiments
• Raman spectra down to ~100 cm-1
• detection of IR inactive peroxide vibrations
• detection of adsorbed species and catalyst bulk phase
• quantification using internal reference
• self scattering of MgO support low
p Raman spectra of supported phase
p other supports? C. Hess, 2006
IR vs Raman of typical oxide supports

IR Raman

I.E. Wachs, Catal. Today 27 (1996) 437

n-pentane isomerization over 17 wt% WO3/ZrO2

1% n-pentane in He, 10 ml/min C=C (coke) W=O

250ºC

S(2-methylbutane)
~30%

S. Kuba and H. Knözinger J. Raman Spectrosc. 33 (2002) 325

Relation of Raman intensity to sample reflectance
Raman intensity based on
Kubelka-Munk formalism:
ρI o R∞ (1 + R∞ ) ρI 0
ψ∞ = = G ( R∞ )
s (1 − R∞ ) s

ρ: Raman coefficient (~ν4)

s: scattering coefficient

cv 4 I o R∞ (v)[1 + R∞ (v)]
ψ ∞ (v ) =
s [1 − R∞ (v)]
( [{ }] ) = G[R∞ (v)]ν 4
cI 0
s
R∞ (v) : can be measured by
diffuse reflectance UV-Vis
Raman intensity correction

original data corrected data

plasma line
Structure of vanadia in VxOy/Al2O3

UV laser Visible laser

dehydrated vanadia: LMCT:
isolated vs polymeric OpV

O O O
V V V
OH O O
O O O O O 4.4 V/nm2

alumina 1.2 V/nm2

Preferential excitation
of structurally different 0.03 V/nm2
VxOy species possible?

Z. Wu, H.-S. Kim, P.C. Stair,

S. Rugmini, S.D. Jackson, JPCB (2005)
UV Raman – selective resonance enhancement
V=O in: V2O5 VxOy V=O in: V2O5 VxOy

Vis UV

1030 1018

O O O
V V V
O O OH
O O O O O

alumina
MeOH partial oxidation on polycryst. Ag (SERS)
O2 flow after pretreatment 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)
C.-B. Wang, G. Deo, I.E. Wachs, JPCB 103 (1999) 5645
Summary: Raman for catalytic applications

• Raman spectra accessible without interference of gas phase

• simple glass/quartz cell
• in situ spectra can be recorded at high temperatures (500°C)
• time-dependent in situ experiments
• Raman spectra of adsorbates and catalyst down to ~100 cm-1
• quantification using internal reference
p correction for changes in sample reflectance (p DR UV-Vis)
• self scattering of common support materials low
p Raman spectra of supported phase
• Signal enhancement as result of resonance Raman and SERS

C. Hess, 2006
Questions?