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 :
=E (1)
: 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 :
=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)
p emission of light at same frequency 0
2
d
2
p I = (2/3c3) * * =
2

= (1642E02/3c3) 04 dt (4)
C. Hess, 2006
Classical description

Internal vibrational motion with Eigenfrequency vM

q = q0 cos 2 Mt (5)

Polarizability p develop in series

= q=0 + (/q)q=0 q + higher order terms (6)

p=E (7)
= (q=0 + (/q)q=0 q0 cos 2 Mt) E0 cos 2 0t
= q=0 E0 cos 2 0t + (/q)q=0 q0 E0 [cos 2 (0 - M)t
+ cos 2 (0 + M)t

Rayleigh 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 vib < 0 = 0 = 0 vib > 0

h0 h0 h0 h(0 + vib)
~~~~ ~~~~ ~~~~ ~~~~
h0 h(0 - vib) h0 h0
~~~~ ~~~~ ~~~~ ~~~~

=1 =1 =1 =1

=0 =0 =0 =0

Stokes Rayleigh Anti-Stokes

C. Hess, 2006
Q.M. description

Raman intensity?
p Is = Ni R(if) IL (8)
Ni: initial state population
R(if): Raman cross section for transition EiEf
IL: Laser intensity

p thermal equilibrium: Boltzmann distribution for state Ni at T

Ni = N0 exp(-ihvib/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 (single e state):

1 g1 ev ev g 0
=
h v wev,g0 w0 + iev

, : Electric dipole moment operator
i.a. with incident/scattered light
C. Hess, 2006
Example: -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: -Carotin

-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 R,free

I(L)
I(S)

INRS(S) = N I(L) R,free

C. Hess, 2006
SERS mechanism - enhancement factors
Surface-enhanced Raman scattering Molecule
0
r
N with R,ads, N N d

Rough surface
metal
I(L) A(L )2 e.g. metal nanostructure
I(S) A(S)2

EM()
ISERS(S) = N I(L) A(L)2 A(S)2 R,ads A() =
E0()

(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

(C-S)t

(C-C)

scissor
twist/
rock

CH2
CH3

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

thiol head group (2.3 )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 Gads = 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 m) 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 ~4
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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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 900C
* 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 100C, heating at 120C for 2h
Heating to 900C 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

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

475C: 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 400C

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 (500C)
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

250C

S(2-methylbutane)
~30%

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

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

: Raman coefficient (~4)

s: scattering coefficient

cv 4 I o R (v)[1 + R (v)]
(v ) =
s [1 R (v)]
( [{ }] ) = G[R (v)] 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 (500C)
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?