Raman spectroscopy:

Basic principles and applications

Christian Hess
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.V. Raman (1928)

 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

p I = (2/3c3) *
= (1642E02/3c3) 04

2
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

= 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)

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

Intensity

60000
40000
20000
0

Anti-Stokes
-800

-400

Stokes
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
resonance
virtual level

resonance
virtual level

Vis

Stokes

g1
g0

Vis

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Stokes

g1
g0

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ev

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resonant Raman

non-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
virtual level

resonance
virtual level

Absorbance

Vis

514nm
Vis

Stokes

v=1
v=0

non-resonant Raman

Stokes
632nm

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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

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

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

(1) E.m. field enhancement

max. ~ 106 (isolated Ag,Au)
max. ~ 108 (coupled)

EM()
A() =
E0()

(2) Chemical enhancement

max. 10-100
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

CH2
twist/
scissor

CH2
wag

(C-C)

CH3
rock

(C-S)t

SERS example: 1-hexadecanthiol/Ag-LB film

Enhancement factor EF:

EF = [ISERS]/[IRaman] [Mb]/[Mads]

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thiol head group (2.3 )2,

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
p 80% T of Raman light,
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

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

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

{
{
{
{
{
{
{
{
{
{
{
{

Gas outlet

Laser excitation at
low laser power to
minimize heating

Quartz window
Sample

{
{
{
{
{
{
{
{
{
{
{
{

Heating wire
Quartz wool
High-temperature
cement

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Raman cell design

mimics plug-flow
reactor: gases flow
through catalyst bed
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
NO2
Pt

NO
BaNO 3

BaO
BaO

O2

NO2
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

{
{
{
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{
{
{
{
{
{
{
{

Gas outlet

{
{
{
{
{
{
{
{
{
{
{
{

Heating wire
Quartz wool
High-temperature
cement

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Gas inlet

Quartz window
Sample

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Laser excitation at 532 nm,

low laser power of ~6 mW
minimizes heating of sample
Raman cell design mimics
typical plug-flow reactor:
Gases flow through catalyst
bed (50 mg) at ~40 ml/min

O-ring

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

1327

Minutes:
20.0

2+

Ba -NO 2

1200
1400
-1
Raman shift (cm )

9.0
7.5

1020 1050 1080

-1
Raman shift (cm )

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

Formation of nitro species precedes that of nitrates

C. Hess, 2006

In situ Raman spectra during NO2 exposure

Temperature dependence
1% NO 2
475 C

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

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

1% NO2
400 C

1% NO2
400 C

25% O2 pre-flow: 1 min

25% O2 pre-flow: 4 min

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

Raman shift (cm )

1500

500

1000

1500

-1

Raman shift (cm )

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

Minut
es

1052

140

Raman intensity (a.u.)

Raman intensity (a.u.)

Dependence on pre-oxidation time

In situ Raman spectra during NO2 /O2 exposure

Temperature dependence
1% NO2 / 20% O2
400 C

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

Presence of oxygen surpresses formation of nitro species

increases the rate of nitrate formation

utes

10

136

M in

134

1049

Summary - Mechanism for NO2 storage

BaO

+ NO2 /He

NO 2
Ba 2+
O

[Ba(NO 2 )]+ + [Ba(NO 3 )] +

He

+ O2 /He

BaO 2

+ NO2 /He

+ NO2 /He

+ NO2 /He
NO

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 )
s

(1 R )

I 0
s

G ( R )

: Raman coefficient (~4)

s: scattering coefficient

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

diffuse reflectance UV-Vis

Raman intensity correction

original data

corrected data
plasma line

Structure of vanadia in VxOy/Al2O3

UV laser
dehydrated vanadia:
isolated vs polymeric
O

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

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:

Vis

V2O5 VxOy

UV

1018

1030

O
O O

O
O

alumina

OH
O O

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?